ALTERNATIVE SOLID FUELS FOR THE PRODUCTION OF PORTLAND CEMENT Except where reference is made to the work of others, the work described in this thesis is. my own, or was done in collaboration with my advisory committee. This thesis does not include proprietary or classified information. _______________________________________ Srikanth Akkapeddi Certificate of Approval: _____________________________ Robert W. Barnes James J. Mallet Associate Professor Civil Engineering _____________________________ Mary L. Hughes Instructor Civil Engineering _____________________________ Anton K. Schindler, Chair Gottlieb Associate Professor Civil Engineering _____________________________ George T. Flowers Dean Graduate School ALTERNATIVE SOLID FUELS FOR THE PRODUCTION OF PORTLAND CEMENT Srikanth Akkapeddi A Thesis Submitted to the Graduate Faculty of Auburn University in Partial Fulfillment of the Requirements for the Degree of Master of Science Auburn, Alabama December 19, 2008 iii ALTERNATIVE SOLID FUELS FOR THE PRODUCTION OF PORTLAND CEMENT Srikanth Akkapeddi Permission is granted to Auburn University to make copies of this thesis at its discretion, upon request of individuals or institutions and at their expense. The author reserves all publication rights. _________________________________ Signature of Author _________________________________ Date of Graduation iv VITA Srikanth Akkapeddi , son of Sri. Lakshimpathy Akkapeddi and Smt. Venkata Lakshmi Akkapeddi n?e Thangirala, was born on August 1, 1983 in Hyderabad, India. He has one elder brother, Vijaykanth Akkapeddi. Srikanth graduated with a Bachelors of Technology (Honors) degree in Civil Engineering from Indian Institute of Technology, Kharagpur, India in June 2006. He immediately began his graduate studies at Auburn University. v THESIS ABSTRACT ALTERNATIVE SOLID FUELS FOR THE PRODUCTION OF PORTLAND CEMENT Srikanth Akkapeddi Master of Science, December 19, 2008 (B.Tech. (Hons.), IIT Kharagpur, India, 2006) 497 Typed Pages Directed by Anton K. Schindler Portland cement manufacturing involves the combustion of fuels with various raw materials at approximately 2,700 ?F (1,500 ?C) to produce clinker. Fuel costs and environmental concerns have encouraged the cement industry to explore alternatives to the use of exclusive conventional fossil fuels. The key objective of using alternative fuels is to continue to produce high-quality cement while decreasing the use of conventional fuels and minimizing the impact on the environment. In this study, portland cement was produced at a full-scale cement plant during 3- day trial burns of various alternative fuels along with coal. The fuel combinations investigated were: 1) coal only, 2) coal and scrap tires, 3) coal, scrap tires, and waste plastics, 4) coal, scrap tires, and broiler litter, 5) coal, scrap tires, and woodchips, and 6) coal, scrap tires, and switchgrass. vi During these trial burns, the cement plant was able to maintain its target production rates while utilizing substantial replacement of conventional fuel with alternative fuels. Samples of raw materials, fuels, cement kiln dust, clinker, cement, and emissions were systematically collected. Chemical compositions, physical characteristics, and mechanical properties were obtained for all the samples collected. Scrap tires and waste plastics were found to have higher heat values than coal. Although broiler litter, woodchips and switchgrass have heat values lower than coal, they burned well with no feed problems, and are available in abundance. Chemical analyses showed that the primary chemical compounds of the clinker, cement kiln dust and cement (i.e. Al 2 O 3 , CaO, Fe 2 O 3 , and SiO 2 ) exhibited no changes of practical significance. Various cement and concrete properties were determined for each trial burn. Tests of drying shrinkage, splitting tensile strength, and permeability of concrete showed no significant changes. The compressive strength of concrete from burns using alternative fuels showed an increase relative to the burn involving coal as the only fuel, though it is not possible to attribute this result exclusively to the use of these fuels. All the emission (NO x , CO, SO 2 and Volatile organic compounds) levels were within the allowable limits set by Alabama Department of Environmental Management. Overall, the cement plant was able to use alternative fuels to produce good quality cement with little impact on emissions levels. Therefore, it is concluded from the study described herein that scrap tires, waste plastics, broiler litter, woodchips and switchgrass are good potential alternative fuels for use during cement production. The final decision on the use of a specific alternative fuel will depend on the availability of the fuel, its cost, and its compatibility with the particular cement plant. vii ACKNOWLEDGMENTS First and foremost, I would like to thank my advisor, Dr. Anton Schindler, for providing me with instruction, guidance, inspiration, and support throughout the project. I also thank Dustin Swart for mentoring me through the initial stages of the project and letting me expand on his work. I am also grateful to Billy Wilson who has helped me overcome many technical problems throughout the project. I would also like to gratefully acknowledge the help of the personnel at Lafarge cement plant, who extended timely cooperation and assistance throughout the project. I also thank all my colleagues and the undergraduate students who helped me mix concrete. My warm thanks also go to all my friends at Auburn, who made my stay a memorable experience. I take this opportunity to express my deepest gratitude to my family back home in India; their unremitting affection and support has helped me in every step of my life. viii Style manual used: Chicago Manual of Style, 14 th Edition Computer software used: Microsoft Word 2007 for Windows; Microsoft Excel 2007 for Windows; Minitab 15.1.0.0 for Windows ix TABLE OF CONTENTS LIST OF TABLES?..???????????????????????? xiv LIST OF FIGURES????????????????????????? xviii CHAPTER 1: INTRODUCTION?????????????? 1 1.1 PROJECT BACKGROUND???????????????????... 1 1.2 STATEMENT OF OBJECTIVES?????????????????... 4 1.3 RESEARCH PLAN???????????????????????. 5 1.4 DOCUMENT ORGANIZATION???????????...??????. 7 CHAPTER 2: LITERATURE REVIEW?????????????...??.... 10 2.1 INTRODUCTION???????????????????????... 10 2.2 PORTLAND CEMENT PRODUCTION??.................................................... 11 2.2.1 RAW MATERIALS?????????????????????? 14 2.2.2 PYRO-PROCESSING?????????????????????. 15 2.2.3 CLINKER COOLING?????????????????????. 16 2.2.4 GRINDING AND FINISHING?????????????????... 17 2.3 ALTERNATIVE FUELS AND PORTLAND CEMENT PRODUCTION?? 19 2.3.1 ALTERNATIVE FUELS IN CEMENT KILNS???????????. 19 2.3.2 ADVANTAGES OF ALTERNATIVE FUELS???????????.. 20 2.3.3 DISADVANTAGES OF ALTERNATIVE FUELS?????????? 22 x 2.3.4 ALTERNATIVE FUEL OPTIONS????????????????. 24 2.3.4.1 SCRAP TIRES AS FUEL??????????????????... 25 2.3.4.2 WASTE PLASTICS AS FUEL????????????????... 30 2.3.4.3 BROILER LITTER AS FUEL????????????????? 32 2.3.4.4 WOODCHIPS AS FUEL??????????????????? 36 2.3.4.5 SWITCHGRASS AS FUEL?????????????????? 40 2.4 EMISSIONS??????????????????????????. 43 2.4.1 CARBON EMISSIONS????????????????????... 44 2.4.2 NITROGEN EMISSIONS???????????????????... 48 2.4.3 SULFUR EMISSIONS????????????????????? 50 2.4.4 OTHER PROBLEMATIC EMISSIONS??????????????. 51 2.4.5 DIOXINS AND FURANS???????????????????... 52 2.4.6 METALS??????????????????????????.. 52 2.4.7 PARTICULATES??????????????????????? 53 2.5 CEMENT KILN DUST?????????????????????... 54 2.5.1 COMPOSITION OF CEMENT KILN DUST????????????. 55 2.5.2 ALTERNATIVE FUELS AND CKD???????????????. 56 2.6 THE EFFECTS OF ELEMENTS ON CLINKER, CEMENT, AND CONCRETE?????????????????????????? 59 2.6.1 ALKALIS (SODIUM AND POTASSIUM)????????????? 61 2.6.2 ANTIMONY (Sb)??????????????????????.... 65 2.6.3 ARSENIC (As)???????????????????????? 65 2.6.4 BARIUM (Ba)????????????????????????. 66 xi 2.6.5 BERYLLIUM (Be)??????????????????????.. 67 2.6.6 BORON (B)?????????????????????????. 67 2.6.7 BROMINE (Br)???????????????????????... 68 2.6.8 CADMIUM (Cd)???????????????????????. 68 2.6.9 CARBON (C)????????????????????????... 69 2.6.10 CHLORINE (Cl)??????????????????????? 70 2.6.11 CHROMIUM (Cr)??????????????????????. 71 2.6.12 COBALT (Co)???????????????????????... 74 2.6.13 COPPER (Cu)???????????????????????? 74 2.6.14 FLUORINE (F)???????????????????????.. 80 2.6.15 LEAD (Pb)?????????????????????????. 81 2.6.16 LITHIUM (Li)???????????????????????... 82 2.6.17 MAGNESIUM (Mg)?????????????????????.. 83 2.6.18 MANGANESE (Mn)?????????????????????. 84 2.6.19 MERCURY (Hg)??????????????????????... 85 2.6.20 MOLYBDENUM (Mo)????????????????????. 85 2.6.21 NICKEL (Ni)????????????????????????. 86 2.6.22 NITROGEN (N)???????????????????????. 87 2.6.23 PHOSPHORUS (P)?????????????????????? 88 2.6.24 RUBIDIUM (Rb)??????????????????????... 89 2.6.25 STRONTIUM (Sr)??????????????????????. 90 2.6.26 SULFUR (S)????????????????????????.. 91 2.6.27 THALLIUM (Tl)??????????????????????... 92 xii 2.6.28 TITANIUM (Ti)???????????????????????. 93 2.6.29 VANADIUM (V)???............................................................................... 94 2.6.30 ZINC (Zn)?????????????????????????.. 94 2.6.31 ZIRCONIUM (Zn)??????????????????????. 96 2.7 CONCLUSION????????????????????????? 97 CHAPTER 3: TEST METHODS???????????????????.. 98 3.1 INTRODUCTION???????????????????????... 98 3.1.1 DEFINITIONS????????????????????????. 100 3.2 GENERAL TEST PLANNING OVERVIEW?????????????. 100 3.2.1 COLLECTION OF MATERIALS????????????????.. 102 3.2.2 TYPES OF TESTS??????????????????????.. 104 3.3 DETAILED TEST PROCEDURE?????????????????... 108 3.3.1 PLANT LAYOUT, SAMPLE LOCATIONS, AND COLLECTION METHODS???????????????????????????... 108 3.3.2 SAMPLE PREPARATION, SHIPPING, AND STORAGE??????... 116 3.3.3 ANALYZING THE CHEMICAL COMPOSITION OF RAW MATERIALS??????????????????????????? 117 3.3.4 ANALYZING THE CHEMICAL COMPOSITION OF FUEL SOURCES... 118 3.3.5 ANALYZING THE CHEMICAL COMPOSITION OF CEMENT KILN DUST?????????????????????????????? 120 3.3.6 ANALYZING THE CHEMICAL COMPOSITION OF CLINKER???... 120 3.3.7 ANALYZING THE CHEMICAL COMPOSITION OF CEMENT???... 121 3.3.8 ANALYZING THE PHYSICAL PROPERTIES OF CEMENT?????. 122 xiii 3.3.9 ANALYZING THE PROPERTIES OF CONCRETE????????? 123 3.3.10 ANALYZING THE EMISSIONS????????????????. 126 3.4 CONCLUSION????????????????????????? 126 CHAPTER 4: PRESENTATION AND ANALYSIS OF DATA???????.. 128 4.1 INTRODUCTION???????????????????????... 128 4.2 USE OF STATISTIC TO ANALYZE DATA???????????.?... 132 4.2.1 ANDERSON-DARLING NORMALITY TEST???.???????? 133 4.2.2 TEST FOR SIGNIFICANT DIFFERENCE??????????...??. 134 4.3 PLANT OPERATIONS????????.?????????????. 135 4.4 DATA PRESENTATION AND ANALYSIS?????????????. 137 4.4.1 CHEMICAL COMPOSITION OF RAW MATERIALS???????? 140 4.4.2 CHEMICAL COMPOSITION OF KILN FEED???????????. 154 4.4.3 FUELS??????????????????.????????? 162 4.4.3.1 COAL???????????????????????. 164 4.4.3.2 SCRAP TIRES???????????????????.. 165 4.4.3.3 WASTE PLASTICS?????????????????.. 172 4.4.3.4 BROILER LITTER?????????????????.... 177 4.4.3.5 WOODCHIPS????????????????..???.. 182 4.4.3.6 SWITCHGRASS??????????????..???? 187 4.4.4 CHEMICAL COMPOSITION OF CEMENT KILN DUST??????... 192 4.4.5 CHEMICAL COMPOSITION OF CLINKER???????????? 195 4.4.6 PORTLAND CEMENT?????????????????.???. 206 4.4.6.1 CHEMICAL COMPOSITION OF CEMENT??????.?.. 206 xiv 4.4.6.2 PHYSICAL PROPERTIES OF CEMENT?????.???... 212 4.4.7 PROPERTIES OF CONCRETE?????????????????.. 224 4.4.7.1 CONCRETE WITH MODERATE WATER-CEMENT RATIO (MIX A)?????????????????????????.. 224 4.4.7.2 CONCRETE WITH LOW WATER-CEMENT RATIO (MIX B) 236 4.4.8 EMISSIONS????????????????????????? 244 4.5 CONCLUSION????????????????????????? 250 CHAPTER 5: SUMMARY, CONCLUSIONS, AND RECOMMENDATIONS?. 257 5.1 SUMMARY??????????????????????????. 257 5.2 CONCLUSIONS????????????????????????.. 260 5.3 RECOMMENDATIONS?????????????????????. 265 REFERENCES??????????????????????????? 268 APPENDIX A: TEST PROCEDURE?????????????????? 278 APPENDIX B.1: RAW DATA ? C BURN??????????....................... 291 APPENDIX B.2: RAW DATA ? CT1 BURN???????.............................. 313 APPENDIX B.3: RAW DATA ? CTP BURN??................................................. 334 APPENDIX B.4: RAW DATA ? CT2 BURN??................................................. 357 APPENDIX B.5: RAW DATA ? CTB BURN??................................................. 376 APPENDIX B.6: RAW DATA ? CT3 BURN??................................................. 402 APPENDIX B.7: RAW DATA ? CTW BURN??................................................. 421 APPENDIX B.8: RAW DATA ? CTS BURN??................................................. 447 xv LIST OF TABLES Table 2.1: Typical Sources of Raw Materials (Kosmatka et al. 2002)?????. 15 Table 2.2: Classifications of Many Alternative Fuels (Greco et al. 2004)???? 26 Table 2.3: Various Properties of Tire Derived Fuel Relative to Two Coal Sources (Barlaz et al. 1993)????????????????????? 28 Table 2.4: Emissions of Coal Relative to Coal and Tires (Corti and Lombardi 2004)??????????????????????????. 29 Table 2.5: Effect on Input and Output Quantities for Tires Used as Fuel (Corti and Lombardi 2004)??????????????????????. 29 Table 2.6: Concentrations of Elements in Coal and Plastic Fuels (Miller et al. 2002)??????????????????????????. 31 Table 2.7: Concentrations in Ash From Coal and Plastic Fuels (Miller et al. 2002). 32 Table 2.8: Proximate and Ultimate Analysis of Chicken Litter and Peat (Abelha et at. 2003)????????????????????????? 33 Table 2.9: Ash Analysis of Chicken Litter (Abelha et al 2003)????????. 34 Table 2.10: CO and VOC Concentrations for Various Chicken Litter/Peat Mixtures and Burning Conditions (Abelha et al. 2003)??????? 35 Table 2.11: Elemental Analysis of Poultry Litter at Wet and Dry Moisture Conditions (D?valos et al. 2002)??????????????? 35 xvi Table 2.12: Comparative fuel cost for woodchips (Maker 2004)???????.. 37 Table 2.13: Dry sample heating values for woodchips (Maker 2004)?????.. 38 Table 2.14: As-fired heating values for woodchips corresponding to the moisture content (Maker 2004)??????????????????.. 39 Table 2.15: Chemical analysis of woodchips (Wilen et al. 1996)??????? 40 Table 2.16: Physical and Chemical properties of Switchgrass compared to other bio-fuels (McLaughlin et al. 1999)?????????????? 42 Table 2.17: Chemical analysis of Switchgrass compared to other fuels (Sami et al. 2001)?????????????????????????... 43 Table 2.18: Chemical Composition of CKD Produced in Various Kiln Types (Bhatty et al. 1996)????????????????????. 56 Table 2.19: Cement Plant Information (Eckert and Guo 1998)????????. 58 Table 2.20: CKD Composition (Eckert and Guo 1998)??????????? 58 Table 2.21: Elemental Composition of Clinker Produced with and without Two Alternative Fuels (Mokrzycki et al. 2003)???????????. 60 Table 2.22: Effects of Elements on Concrete Properties??????????... 62 Table 2.23: Setting Time of Cement Specimens with Various Alkali Contents (Lawrence 1998)?????..???????????????.. 64 Table 2.24: Compressive Strength of Cement Specimens with Various Alkali Contents (Lawrence 1998)????????????...????.. 64 Table 2.25: Chemical Analysis of Cement Before Addition of Dosed Elements (Stephan et al 2000)????????????...??????? 73 Table 3.1: Standard Chemical Parameters???????????????... 106 xvii Table 3.2: Approximate Detection Limits for XRF used at the External Laboratory??????????????????????...... 107 Table 3.3: Proximate and Ultimate Analysis Details???????????... 119 Table 3.4: Cement Physical Property Tests by Auburn University??????. 122 Table 3.5: Cement Physical Property Tests by Cement Plant????????.. 123 Table 3.6: Cement Physical Property Tests by Cement Plant Specialty Laboratory??................................................................................... 123 Table 3.7: Mix A Proportions (w/c= 0.44)???????????????.. 124 Table 3.8: Mix B Proportions (w/c=0.37)????????????????.. 125 Table 3.9. Concrete Tests??????????????????????.. 126 Table 4.1: Summary of plant conditions during each trial burn????????. 139 Table 4.2: CPR- Baseline Burns, Percentage change in Raw Materials One, Two and Three relative to CT1 Burn???????????????? 141 Table 4.3: CPR- Baseline Burns, Percentage change in Raw Materials Four, Five and Six relative to CT1 burn????????????????? 141 Table 4.4: ELR- Baseline Burns, Percentage change in Raw Materials One, Two and Three relative to CT1 burn?............................................................ 142 Table 4.5: ELR- Baseline Burns, Percentage change in Raw Materials Four, Five and Six relative to CT1 burn................................................................... 143 Table 4.6: CPR- Fuel Burns, Percentage change in Raw Material One composition from each burn relative to its baseline burn???????????.. 144 Table 4.7: CPR- Fuel Burns, Percentage change in Raw Material Two composition from each burn relative to its baseline burn???????????. 145 xviii Table 4.8: CPR- Fuel Burns, Percentage change in Raw Material Three composition from each burn relative to its baseline burn??????. 145 Table 4.9: CPR- Fuel Burns, Percentage change in Raw Material Four composition from each burn relative to its baseline burn????.??????? 146 Table 4.10: CPR- Fuel Burns, Percentage change in Raw Material Five composition from each burn relative to its baseline burn???.??... 146 Table 4.11: CPR- Fuel Burns, Percentage change in Raw Material Six composition from each burn relative to its baseline burn ???????????. 147 Table 4.12: ELR- Fuel Burns, Percentage change in Raw Material One composition from each burn relative to its baseline burn ???.??... 148 Table 4.13: ELR- Fuel Burns, Percentage change in Raw Material Two composition from each burn relative to its baseline burn ??................ 149 Table 4.14: ELR- Fuel Burns, Percentage change in Raw Material Three composition from each burn relative to its baseline burn ??................ 150 Table 4.15: ELR- Fuel Burns, Percentage change in Raw Material Four composition from each burn relative to its baseline burn ?????? 151 Table 4.16: ELR- Fuel Burns, Percentage change in Raw Material Five composition for each burn relative to its baseline burn ??................... 152 Table 4.17: ELR- Fuel Burns, Percentage change in Raw Material Six composition from each burn relative to its baseline burn ???????????. 153 Table 4.18: CPR- All burns, kiln feed composition????????????? 156 Table 4.19: CPR- Baseline Burns, Percentage difference in kiln feed composition relative to CT1 burn????????????????.??..?.. 157 xix Table 4.20: ELR- Baseline Burns, Percentage difference in kiln feed composition relative to CT1 burn????????????????????.. 158 Table 4.21: CPR- Fuel Burns, Percentage difference in kiln feed composition relative to baseline burns??????????????????. 159 Table 4.22: ELR- Fuel Burns, Percentage difference in kiln feed composition relative to baseline burns??????????????????.. 161 Table 4.23: CPR ?All Burns, Chemical analysis of coal and percent difference relative to CT1 burn????????????.???????? 166 Table 4.24: ELR ?All Burns, Proximate and Ultimate analyses of coal and percent difference relative to CT1 burn?????????.??????... 167 Table 4.25: ELR ?All burns, Chemical analysis of coal and percent difference relative to CT1 burn??????????????.?????? 168 Table 4.26: ELR ?All Burns, Proximate, Ultimate, and Combustion Analyses for tires, and percent difference relative to CT1 burn????????? 170 Table 4.27: ELR ?All Burns, Chemical analysis for tires and percent difference relative CT1 burn?????????????.????????. 171 Table 4.28: ELR ? Proximate, Ultimate, and Combustions Analysis of Plastics from CTP burn??????????????????????.. 173 Table 4.29: ELR - Standard Parameters of Plastics from CTP burn??..???? 174 Table 4.30: ELR ? Proximate and Ultimate analyses of all fuels from CTP burn?. 175 Table 4.31: ELR ? Chemical composition of all fuels from CTP burn?????. 176 Table 4.32: ELR ? Proximate, Ultimate and Combustion analyses of Broiler litter from CTB burn??????????????????????.. 177 xx Table 4.33: ELR - Standard Parameters of Broiler Litter from CTB burn??..?.. 178 Table 4.34: ELR ? Proximate and Ultimate analyses of all fuels from CTB burn? 180 Table 4.35: ELR ? Standard parameters of all fuels from CTB burn?????? 181 Table 4.36: ELR ? Proximate, Ultimate and Combustion analyses of woodchips from CTW burn??????????????????????. 183 Table 4.37: ELR - Standard Parameters of woodchips from CTW burn?..???. 185 Table 4.38: ELR ? Proximate and Ultimate analyses of all fuels from CTW burn... 185 Table 4.39: ELR ? Standard parameters of all fuels from CTW burn?????... 186 Table 4.40: ELR ? Proximate, Ultimate and Combustion analyses of switchgrass from CTS burn??????????????????????.. 188 Table 4.41: ELR - Standard parameters of switchgrass from CTS burn???..?. 189 Table 4.42: ELR ? Proximate and Ultimate analyses of all fuels from CTS burn?. 191 Table 4.43: ELR ? Standard parameters of all fuels from CTS burn??????. 191 Table 4.44: CPR ?Baseline burns, Chemical analysis and percent difference for cement kiln dust???????????????????..??.. 192 Table 4.45: ELR ?Baseline burns, Chemical composition of cement kiln dust??. 193 Table 4.46: CPR ?Fuel Burns, Chemical composition of cement kiln dust relative to baseline burns??????????????????..???. 195 Table 4.47: ELR ?Fuel Burns, Chemical composition of cement kiln dust relative to baseline burns??????????????.?.?.?????. 197 Table 4.48 CPR - Summary statistics of chemical composition of clinker for C, CT1, CTP and CT2 burns???????????.????..??.. 198 xxi Table 4.49 CPR - Summary statistics of chemical composition of clinker for CTB, CT3, CTW and CTS burns????.???????????..??. 199 Table 4.50 CPR ?Baseline Burns, Percent difference and statistical significance for clinker relative to CT1 burn?????????..???????? 200 Table 4.51 CPR ? Percent differences and statistical significance for clinker??.. 202 Table 4.52: ELR ?Fuel Burns, Percent differences for clinker relative to baseline burn????????.??..????????????.. 205 Table 4.53: SLR ?Baseline Burns, Rietveld analysis of clinker relative to CT1 burn???????????..????????? 206 Table 4.54: SLR ?Fuel Burns, Rietveld analysis of clinker relative to the baseline burns??????????????????????????. 206 Table 4.55: CPR ?All Burns, Summary statistics of cement composition????. 208 Table 4.56: CPR ?All Burns, Percentage difference in cement composition relative to CT1 burn???????????????????????.. 209 Table 4.57: ELR ?All Burns, Percentage difference in major parameters of cement relative to CT1 burn??????????????.??????. 213 Table 4.58: ELR ?All Burns, Percentage difference in minor parameters of cement relative to CT1 burn????????????????????.. 215 Table 4.59: SLR ?All Burns, Rietveld analysis of cement???????...??.. 215 Table 4.60: CPR ?All Burns, Physical properties and percentage change for cement?????????????????????????... 217 Table 4.61: AUR ?All Burns ? Physical properties and percentage change for cement?????????????????????????... 218 xxii Table 4.62: AUR ?All Burns, Physical properties and percentage change for concrete Mix A???????????????????.???. 227 Table 4.63: CPR ?All Burns, Physical properties and percentage change for concrete Mix A??????????????????.????. 229 Table 4.64: AUR ?All Burns, Drying shrinkage development for Mix A????. 233 Table 4.65: AUR ?All Burns, Physical properties and percentage change for concrete Mix B?????????????????????.? 237 Table 4.66: AUR ?All Burns, Drying Shrinkage development for Mix B????. 242 Table 4.67: CPR - Summary statistics for emissions????????????.. 247 Table 4.68: CPR ? Emissions, Significant difference between baseline burns??.. 248 Table 4.69: CPR ? Emissions, Significant difference between fuel burns relative to their respective baseline burns????????????????. 249 xxiii LIST OF FIGURES Figure 2.1: Layout of a Typical Dry-Process Portland Cement Production Facility (Kosmatka et al. 2002)?????????????????..?? 13 Figure 2.2: Gas and Material Temperature inside a typical cement kiln (Mokrzycki and Uliasz-Boche?czyk 2003)????????????????.. 18 Figure 2.3: Various fuels and their origin (Adapted from Greco et al. 2004)??.? 21 Figure 2.4: Trend of Tire Use to Fuel in Cement Plants in the U.S. (PCA 2005)?.. 30 Figure 2.5: Energy Content Relative to Water Content of Poultry Litter (D?valos et al. 2002)????????????..???????????...... 36 Figure 2.6: Emissions Data from a Plant Burning Alternative Fuels (modified from Mokrzycki et al 2003)??????????..????????.? 46 Figure 2.7: Change in Emission Levels due to Changes in Fuel Types (Prisciandaro et al. 2003)?????????????..????? 47 Figure 2.8: Particle Size Distribution of CKD Produced in a S (alkali by-pass kiln), G (long wet kiln), and H (long dry kiln) (Todres et al. 1992)????.. 57 Figure 2.9: Heat of Hydration for Cement with Various Concentrations of Cr, Ni, and Zn (Stephan et al. 2000)????????????????.... 75 Figure 2.10: Penetration of Cements Dosed with 25,000 ppm of Cr, Ni, and Zn (Stephan et al. 2000)????????..????.??????... 76 xxiv Figure 2.11: Penetration of Cements Dosed with 5,000 ppm of Cr, Ni, and Zn (Stephan et al 2000)???????????.?..??????? 77 Figure 2.12: Compressive Strength of Cements Dosed with 25,000 ppm of Cr, Ni, and Zn (Stephan et al. 2000)?????? ??????..???... 78 Figure 2.13: Compressive Strength of Cements Dosed with 5,000 ppm of Cr, Ni, and Zn (Stephan et al. 2000)???????.????..????... 79 Figure 2.14: Effect of Various Doses of Li 2 CO 3 on ASR Expansion (Kawamura and Fuwa 2001)?????????..???????????.... 83 Figure 2.15: Compressive Strength for Different P 2 O 5 Concentrations (Miller 1976)????????..????????????????? 89 Figure 3.1: Overall Sampling and Testing Plan?????????????..... 101 Figure 3.2: Sampling Timeline????????????????????.. 103 Figure 3.3: Diagram of the Cement Plant (Adapted from Swart 2007)????..... 109 Figure 3.4: Raw Material Sample Point????????????????..... 110 Figure 3.5: Kiln Feed Sampling???????????????????..... 111 Figure 3.6: Sampling of Clinker???????????????????? 111 Figure 3.7: Automated Plunger Removing Coal Samples?????????..... 112 Figure 3.8: Tires Transported to Kiln?????????????????? 113 Figure 3.9: Tires Entering Kiln????????????????????.. 114 Figure 3.10: Alternative Fuel Kiln Injection System????????????.. 114 Figure 3.11: Automated Plunger Collecting Cement Samples?????.???.. 115 Figure 4.1: Analysis method for the burn data???????????..???.. 131 xxv Figure 4.2: CPR-Fuel Burns, Percentage difference in kiln feed composition relative to baseline burns...????????..?????..???. 160 Figure 4.3: ELR: Dry Heat Values of the fuels???..???????.?.??.. 163 Figure 4.4: CPR-Fuel Burns, Percentage difference in CKD composition relative to baseline burns?????????????????..?.??.. 196 Figure 4.5: CPR- Fuel Burns, Percentage difference in clinker composition relative to baseline burns?????????????????? 203 Figure 4.6: CPR- Fuel Burns, Percentage difference in cement composition relative to CT1 burn?????????????????...?? 210 Figure 4.7: CPR- Fuel Burn, Percentage difference in Bogue compounds in cement relative to CT1 burn?????????.???????.. 211 Figure 4.8: AUR- Fuel Burns, Percentage difference in physical properties of cement relative to CT1 burn??????????.??????.. 219 Figure 4.9: AUR- All Burns, Compressive strength of mortar cubes?????? 221 Figure 4.10: AUR- All Burns- Drying shrinkage of mortar prisms??????? 222 Figure 4.11: SLR- All Burns- Particle size distribution of Cement?????..?.. 223 Figure 4.12: AUR- All Burns, Percentage difference in Mix A concrete results relative to CT1 burn????...??????????????? 228 Figure 4.13: AUR- All Burns, Compressive strength of concrete Mix A???.?. 231 Figure 4.14: AUR- All Burns, Splitting tensile strength of concrete Mix A??.?. 232 Figure 4.15: AUR- All Burns, Drying shrinkage development of concrete Mix A? 234 Figure 4.16: AUR ?All Burns, Semi-adiabatic degree of hydration development for Mix A???????..?????????????..??. 235 xxvi Figure 4.17: AUR ?All-Burns, Percent difference in concrete properties for Mix B 238 Figure 4.18: AUR ?All Burns, Compressive strength for concrete Mix B??.?? 240 Figure 4.19: AUR ? All- Burns, Splitting tensile strength for concrete Mix B?.?. 241 Figure 4.20: AUR- All Burns, Drying shrinkage development of concrete Mix B? 243 Figure 4.21: AUR ?All Burns, Semi-adiabatic degree of hydration development for Mix B?????????..??.?????..?????.?.. 245 Figure 4.22: CPR ? Emissions, Percent difference between fuel burns relative to respective baseline burn????????.??..???????.. 252 1 CHAPTER 1 INTRODUCTION 1.1 Project Background The modern production of portland cement utilizes various materials, complex facilities, and involves closely monitored processes. All of these components are engineered to develop a product that satisfies the construction demands of the entire world. Portland cement is the key component of concrete, which is used to build roads, bridges, buildings, dams and just about any other type of structure used by mankind. However, the production of portland cement requires high temperatures sustained over long periods of time, which are supplied by the combustion of large quantities of fuels. The majority of these fuels have historically come from nonrenewable sources. Portland cement is manufactured by blending raw materials, which are mined from the earth, and by chemically fusing them together in the presence of extremely high temperatures. The new product, known as clinker, is ground with sulfates to a specific particle size distribution, and this final product is known as portland cement. The temperatures necessary to turn the raw materials into clinker are on the order of 1500 ?C. These temperatures are maintained by burning large quantities of combustible fuels inside a rotary kiln, where the fusing of the materials takes place. In order to meet the demands of the construction industry, it is common for a portland 2 cement production facility to operate 24 hours a day and seven days a week. With the quantities of fuels necessary to maintain that level of production, it is easy to see why the fuels used play a vital role in the production process. It has been reported that the costs associated with fuels in a cement plant can be as high as 30 to 40 percent of the total production costs (Mokrzycki et al. 2003). These numbers are associated with traditional fuels such as coal, natural gas, and oil. Alternative fuels are typically a waste product from other industries. Since that is the case, it is often significantly cheaper for a cement plant to acquire waste that would otherwise be landfilled or incinerated. In fact, the cement plant may actually be paid to dispose of certain wastes. If a portland cement production facility is capable of acquiring an alternative fuel at significantly less, or even negative cost, it is worth exploring the fuel?s entire potential. Another reason why the utilization of alternative fuels in the cement production process is beneficial is the decrease in consumption of nonrenewable resources. In an efficient kiln system, where the production rates are high, it is possible for a single facility to consume as much as 1200 tons of coal a day (Manias 2004). All cement production facilities may not consume this quantity of material, but the quantities of fuels consumed in thousands of facilities worldwide are huge. If only a small portion of the nonrenewable resources used in this process are replaced in many of these facilities, a significant decrease in use of nonrenewable resources would result. The emissions released by a cement production facility are an aspect of the production process that is closely monitored and controlled. The use of alternative fuels could influence the emissions. The combustion of the primary fuel currently used at any 3 given cement plant may produce more emissions than the combustion of an alternative fuel that could possibly be utilized. Moreover, the incineration of wastes in a cement plant serves a dual purpose, in that the heat produced during the incineration process is used to manufacture a product. When wastes are incinerated otherwise, the heat developed is not used at all. The utilization, at a cement production facility, of alternative fuels that are derived from waste that would normally be incinerated, combines two emissions-producing processes into a single process (Greco et al. 2004). This consolidation directly reduces the amount of emissions released into the atmosphere. Regardless of the fuel that is used to produce portland cement, the majority of the incombustible material is actually incorporated into the clinker that is being formed. Thus use of alternative fuels could alter the final chemical composition of the portland cement. In turn, this alteration of chemical composition may lead to changes in the properties of the ultimate product, concrete. For this reason, this study focused on measuring the chemical composition of all of the materials involved in the production process and the outputs from the production, with the goal of determining the effect on chemical composition, of the use of alternative fuels. In this study, the physical properties of the cement and concrete were tested to determine if there were any effects that can be directly associated with the implementation of the alternative fuels. In spite of all the positive aspects associated with the utilization of alternative fuels, if the final concrete product suffers from deficiencies in the properties that make concrete the versatile building material that it is, then the fuel in question may not be a viable alternative. 4 1.2 Statement of Objectives The objectives of this project are numerous. However, due to the complex nature of the production process, and the research associated with it, some of the objectives have been given more attention than others. The primary objectives of this project are to determine the impact of using alternative fuels on the following: 1. the ability of the cement plant to maintain productive operations, 2. the chemical composition of clinker and portland cement produced, 3. the physical properties of the portland cement produced, 4. the properties of concrete made from this portland cement, and 5. the emissions released by the cement plant. Researchers at Auburn University and a cement production facility, referred to as the cement plant, partnered to realize these objectives. The first objective was primarily studied by personnel at the cement plant itself. This objective was very important to the study. Obviously, if the utilization of a certain alternative fuel does not allow the plant to maintain production, that fuel cannot be used. The second through fourth objectives listed above are closely related, and are the main focus of this study. Chemical compositions of all materials involved in the production process were determined, and an attempt was made to associate the utilization of alternative fuels with any chemical composition changes in the final product. Many physical properties of cement and concrete were measured, and the differences between the cement from each of the fuels were noted. Finally, an attempt was made to associate the differences in properties of cement and concrete to the chemical changes brought on by the utilization of alternative fuels. 5 The final objective is another one that the cement plant is very concerned with. Because the emissions released by a cement plant are closely monitored and controlled, any effects that the combustion of alternative fuels may have will be assessed. 1.3 Research Plan Based on the objectives listed above, a complex yet thorough sampling and testing plan was developed. The research was conducted using a full-scale production plant that was operated under normal procedures typically used at this cement plant. The only change to the production process was to use the alternative fuels that are part of this study. The research plan consisted of eight trial burns in which unique combinations of fuels were used. The first trial burn utilized pulverized coal as the only fuel. Coal is a common fuel source used by portland cement production facilities, and is the primary fuel used at the cement plant where this research was conducted. The second burn maintained coal as the primary fuel, but supplemented a portion of it with whole scrapped tires. Since this trial burn was completed, this has become the fuel combination that the cement plant currently uses in its everyday operations. Therefore, this fuel combination was considered the baseline to which each of the other fuel options was compared. The third trial burn used a combination of pulverized coal, whole tires, and waste plastics. The waste plastics were considered to be the first alternative fuel used. Since significant time elapsed between the second burn and the third burn, and the sources of raw materials and coal were changed, it was decided to conduct another burn with the standard fuel combination of coal plus tires for comparison for the third burn. Hence the 6 fourth trial burn used a combination of coal and scrap tires. The fifth trial burn used coal, scrap tires, and broiler litter. Broiler litter, which is a byproduct of the broiler farming industry, was considered to be the second alternative fuel. Since it was reported that the coal sources were again changed between the fourth and fifth trial burns, it became necessary to conduct another baseline burn with the standard fuel combination for comparison of results. Hence the sixth trial burn used coal and scrap tires. The seventh trial burn used coal, scrap tires, and woodchips as fuels, while the eight trial burn used coal, scrap tires, and switchgrass as fuels. Woodchips and switchgrass were the considered to be the third and fourth alternative fuels. In order for the cement plant to burn the fuels implemented in this project, many modifications had to be made to the facilities at the cement plant. New equipment had to be installed that was capable of handling, transporting, measuring, and introducing the fuels into the production systems. This was the main reason for the delay between the trial burns. Within each of these trial burns, a thorough sampling and testing procedure was used. Each of the materials used to produce the portland cement was sampled and tested for its chemical composition. Additionally, each of the outputs from the production process was collected and tested for its chemical composition. Each of the inputs and outputs was sampled and tested at different frequencies relative to its importance to the production process. The chemical analyses were conducted at the cement plant on each of these materials. Samples from each of these materials were also sent to an external laboratory for additional testing. This additional testing served to verify the results 7 provided by the cement plant. Some specialty chemical analyses were conducted by a specialty laboratory that is a subsidiary of the company that owns the cement plant. In addition to the chemical analyses, select physical properties of the cement, as well as many properties of concrete made from the cement, were evaluated. Many physical properties of the cement were evaluated at the cement plant. Most of the same properties were also determined by staff from Auburn University. Moreover, some of the concrete tests were conducted at both Auburn University and at the concrete laboratory of the cement plant. However, the testing conducted by Auburn was more extensive than that conducted at the cement plant. At Auburn University, there were two different concrete mixtures that were produced from the cement of each trial burn. Different mixtures were used to examine the interaction of the cement with various chemical admixtures. The final aspect of the research plan was to collect and monitor the emissions during each of the trial burns. The emissions were monitored by the cement plant using a continuous emissions monitoring system. These results were then reported to Auburn University staff and an evaluation of these results is presented in this document. 1.4 Document Organization This document is organized into five chapters, followed by a set of appendices. The current chapter introduces the reader to the possibilities and problems associated with alternative fuels and portland cement production. It is also where the objectives for this project are stated. Finally, Chapter One provides a brief description of the procedures that were implemented in satisfying the objectives. 8 The second chapter of this document is where background research on this study is presented. Literature from other studies pertaining to this research is examined and pertinent information is presented. Another important goal of Chapter Two is to provide a thorough explanation of the production process associated with portland cement. This discussion is based on the process in general, and is not specific to the cement plant used in this study. After that, an introduction to each of the materials involved in the production process, and how each may be affected by the use of alternative fuels is given. Chapter Two concludes with a thorough explanation of how many elemental compounds, that may be introduced into the portland cement by the alternative fuels, can potentially affect the properties of cement and concrete. All of the information in Chapter Two originates from a review of outside literature, and is not the original work of the author. A thorough explanation of the methods used to research the problem at hand is presented in Chapter Three. Each of the input and output materials relating to the production of portland cement was sampled and tested in various manners. Chapter Three expands on this sampling and testing procedure. The results of this study are presented, analyzed, and discussed in Chapter Four. Due to the large quantity of data associated with some of the results, the primary method of data presentation used in this chapter is the utilization of summary statistics. Once the statistics have been presented, they are analyzed and discussed. Where the results allow for conclusions to be drawn, they are discussed, and in some cases, compared to the relevant historical data obtained from prior studies that were presented in Chapter Two. The final chapter of this document contains summaries, conclusions, and recommendations related to this study. A summary of the reasons why this study is 9 important is provided, along with the way this study was conducted. The objectives stated in Chapter One are restated, and conclusions pertaining to each one are provided. In some cases definitive conclusions could not be reached, but in such cases, reasons for this are given. Chapter Five concludes with recommendations on a number of aspects of this study. Suggestions for future work, possible ways to improve the research and aspects that may have been overlooked in the current study are provided. Following Chapter Five, there is a set of appendices. Appendix A presents the sampling and testing plan in tabular form. Chapter Three discusses the plan in more detail, and the same are shown in Appendix A in a simplified table. The final section of this document is Appendix B. This appendix has eight parts. Each part serves to present in a tabular form all of the raw data associated with each trial burn. For instance, Appendix B.1 presents all of the data for the coal only burn. 10 CHAPTER 2 LITERATURE REVIEW 2.1 Introduction Concrete is a material used in building construction, consisting of hard, chemically inert particulate substances, known as aggregates (usually made from different types of sand and gravel), that are bonded together by cement and water. Various types of cementing material are available today; however, the most common one used is portland cement. The invention of portland cement is generally credited to Joseph Aspdin, an English mason (Kosmatka et al. 2002). Aspdin experimented with calcareous cement formulations, and in 1824 he took out a patent. His patented cement was lightly calcined lime with little, if any, lime-silica reaction. It was his son, William Aspdin, who made the first in-depth CaO-SiO 2 reaction by accident when the so-called over-burnt clinker, which had been previously rejected, was incorporated into his product (Blezard 1998). Cement production has advanced dramatically from the days of the Aspdins. High temperatures on the order of 1500 ?C were introduced, enabling the raw materials to blend well enough to form a relatively uniform product. These high temperatures render the process extremely fuel-intensive (Jackson 1998). The typical costs associated with fuels may be as much as 30 to 40% of the total production costs (Mokrzycki et al. 2003). 11 In order to reduce this cost, many cement producers are looking into the utilization of alternative fuels (Mound and Colbert 2004). Alternative fuels (also known as waste-derived fuels) are materials that are rich in energy, such as used tires, waste wood, used oil, and spent solvent, which can be used to replace coal or gas as source of thermal energy in the cement manufacturing process (PCA 2004). The utilization of alternative fuels can be not only economically profitable but also ecologically beneficial. The most significant benefits are preservation of fossil fuel resources, reduction in the volume of wastes that must be disposed of by other means, and a decrease in the global greenhouse effect (Greco et al. 2004). However, it is important that an alternative fuel does not produce adverse side effects, such as changes to product chemistry and performance, or increased emissions (Mokrzycki and Uliasz- Boche?czyk 2003). Therefore, it is imperative that a thorough study establishes the possible effects of the utilization of alternative fuels in cement production before its implementation. This chapter provides a review of literature regarding the parameters that have significant bearing on the feasibility of introducing alternative fuels to the portland cement industry. 2.2 Portland Cement Production In cement manufacturing, appropriate proportions of raw materials containing calcium, silica, alumina, and iron are fused together at approximately 1500 ?C to form a product known as clinker. Such clinker is cooled and ground with an appropriate quantity of sulfate to a predetermined fineness to form portland cement (Taylor 1997). Due to the 12 high level of complexity of the production process, and in order to be as economical as possible, the exact process varies from one facility to another (Jackson 1998). Some facilities adopt a wet process where the raw materials are suspended in water during the processing. However, most modern facilities adopt the more energy-efficient dry process, in which grinding and blending are completed on dry raw material (Kosmatka et al. 2002). Figure 2.1 shows a schematic diagram of the typical dry process. Appropriate proportions of raw materials are ground to powder in a grinding mill, mixed thoroughly in the blending mill, and sent to the storage silo. Throughout the process, dust is removed and collected at various locations. The raw material blend is then fed to the preheater, where it is calcinated before entering the kiln. Once in the kiln, the raw material feed is fused together into clinker which is then cooled and stored in silos. The stored clinker is then mixed with gypsum and ground into cement in the grinding mills. The final product, cement, is then stored, packaged, or shipped to the consumer. 2.2.1 Raw Materials The selection and processing of raw materials are important components of the portland cement manufacturing process. The raw materials used in the manufacture of portland cement generally constitute calcareous (high CaCO 3 content) and argillaceous (high silica and alumina content) material (Kosmatka et al. 2002). Some of the most common sources of raw materials are listed in Table 2.1. 13 Figure 2.1: Layout of a Typical Dry-Process Portland Cement Production Facility (Kosmatka et al. 2002) The raw materials must be crushed and proportioned so that the appropriate chemical composition of the raw material feed is reached (Kosmatka et al. 2002). The goal of the crushing process is to achieve the desired particle size distribution, average particle size, and specific surface area with the least amount of energy consumption and other operating costs (Chatterjee 2004). Just like the chemical composition, the size distribution of the raw materials is crucial to both the quality of the product and the operation of the process. Appropriate fineness of the feed enables the kiln to run at lower temperatures and hence, with lower fuel consumption, than that involving a coarser material (Jackson 1998). Once the appropriate fineness has been reached, the raw materials are mixed together to form a homogenous mixture with the predetermined chemical composition (Chatterjee 2004). Table 2.1: Typical Sources of Raw Materials (from Kosmatka et al. 2002) Calcium Iron Silica Alumina Sulfate Alkali waste Blast-furnace flue dust Calcium silicate Aluminum-ore refuse* Anhydrite Aragonite* Clay* Cement rock Bauxite Calcium sulfate Calcite* Iron ore* Clay* Cement rock Gypsum* Cement-kiln dust Mill scale* Fly ash Clay* Cement rock Ore washings Fuller's earth Copper slag Chalk Pyrite cinders Limestone Fly ash* Clay Shale Loess Fuller's earth Fuller's earth Marl* Granodiorite Limestone* Ore washings Limestone Marble Quartzite Loess Marl* Rice-hull ash Ore washings Seashells Sand* Shale* Shale Sandstone Slag Slag Shale* Staurolite Slag Traprock Note: * Most common source 14 15 2.2.2 Pyro-processing Pyro-processing is the process in which materials are subjected to high temperatures in order to bring about a chemical or a physical change. Once the raw materials have been proportioned and mixed, they are ready to be fused together on a chemical level. The raw mixture is sent through preheater and precalciner to heat it to approximately 850 ?C before it is fed into the kiln. In the process, some of the carbon is removed as CO 2 , leaving a material with a higher CaO content (Jackson 1998). This makes the process much more fuel and cost efficient. The raw material passes through the kiln at a rate determined by the slope and rotational speed of the kiln (Kosmatka et al. 2002). The kiln systems perform the following on the raw mixture, starting from the feed end (Manias 2004): 1. Evaporating free water, at temperatures up to 100 ?C 2. Removal of adsorbed water in clay materials, 100 ?C ? 300 ?C 3. Removal of chemically bound water, 450 ?C ? 900 ?C 4. Calcination of carbonate materials in the preheater, 700 ?C ? 850 ?C 5. Formation of belites, aluminates and ferrites, 800 ?C ? 1250 ?C 6. Formation of liquid phase melt, >1250 ?C 7. Formation of C 3 S, 1330 ?C? 1450 ?C 8. Cooling of clinker to solidify liquid phase, 1300 ?C ? 1240 ?C 9. Final clinker microstructure frozen in clinker, <1200 ?C 10. Clinker cooled in cooler, 1250 ?C ? 100 ?C In this process, the C 3 S (alite), C 2 S (belite), C 3 A (aluminate), and C 4 AF (ferrite), known as Bogue Compounds, are the major clinker phases. When portland cement is 16 mixed with water, these four compounds react with the water to form the majority of the hydrated cement products that give cement its cementitious properties (Taylor 1997). Figure 2.2 shows the gas temperature (solid line), and the material temperature (broken line) as they progress through the various parts of the kiln system. Additionally, the retention times in each area of the system are shown at the bottom. 2.2.3 Clinker Cooling Clinker cooling is essential since it locks in desirable product qualities by freezing mineralogy and makes it possible to use conventional conveying equipment (EPA 1995). Cement exhibits its best strength-giving properties when the clinker is cooled rapidly from the temperature at the burning zone to about 1200?C, which inhibits the further reaction of clinker phases (Jackson 1998). The cooling of clinker takes place in two locations: 1) in the kiln after the burning zone region, and 2) in a specially designed clinker cooler (Manias 2004). The most common types of clinker coolers are 1) reciprocating grate, 2) planetary and, 3) rotary. In these coolers, clinker is cooled from about 1100 ?C to 93 ?C by ambient air that passes through the clinker and into the kiln for use as combustion air. This way about 30 percent of the heat input to the kiln may be recovered (EPA 1995). 2.2.4 Grinding and Finishing The final step in portland cement manufacturing is grinding the blend of clinker and gypsum. Up to 5 percent (by weight) of gypsum, or other sulfate source, is added to the clinker after it is cooled (EPA 1995). The amount of gypsum is adjusted to regulate 17 cement properties such as setting time and shrinkage and strength development (Kosmatka et al. 2002). Typically, the grinding process is accomplished using a ball mill, roller mill, roll press, or a combination of these (Strohman 2004). However, in most modern facilities, finish milling is done almost exclusively by ball mills (EPA 1995). A ball mill consists of a horizontal tube rotating about its axis, filled with steel balls ranging in size from 13 mm to 100 mm. As the mill rotates, the balls frequently collide with the clinker, causing it to fracture into progressively smaller pieces (Jackson 1998). In general, the finished product will be ground so that almost every particle will pass through a 45 micrometer sieve (Kosmatka et al. 2002). Once grinding is completed, the finished product is the portland cement, which is packaged, stored in silos or shipped to consumers. 18 Figure 2.2: Gas and Material Temperature inside a typical cement kiln (Mokrzycki and Uliasz-Boche?czyk 2003) 19 2.3 Alternative Fuels and Portland Cement Production According to Greco et al. (2004), fuels are ?substances that in the presence of an oxidant (usually, but not exclusively, atmospheric air) and provided there is an ?initial energetic impulse,? give rise to a chemical reaction of oxidation that is exothermic, self- sustainable, and very rapid.? The production of portland cement requires a high degree of thermal energy. Based on the endothermal reactions of decarbonation of limestone and dehydration of the kaolinite (Al 2 Si 2 O 5 (OH) 4 ) and exothermal reaction of phase forming, 1 kg of clinker requires about 175 MJ of thermal energy in basic calculation (Wurst and Prey 2002). Figure 2.3 shows both traditional and alternative fuels. In many cases, the terms alternative fuels and waste (or waste-derived) fuels are used interchangeably. For the purpose of this document, the term ?alternative fuels? will refer to anything used as a substitute for traditional fuels. 2.3.1 Alternative Fuels in Cement Kilns Cement kilns have technical conditions very favorable for use of alternative fuels. Some of these important dry process kiln characteristics favorable to alternative fuel use are as follows (Greco et al. 2004): ? The temperatures in the kiln, upwards of 1500?C, are considerably higher than the threshold ignition temperature, as established by environmental regulations, ? Long retention time of products under high temperature combustion, ? The high alkalinity atmosphere readily absorbs most acidic gases released by the oxidation of sulphur and chlorides, 20 ? Most of the non-fuel compounds, such as metallic oxides, do not harm the production of clinker, and ? Most of the noncombustible products, particularly metals, are either incorporated into the clinker itself, or are trapped by and recycled with the cement kiln dust. Since most of the noncombustible products are incorporated into the final product, it is necessary to establish that the performance of the cement is not adversely affected by the altered chemical composition. A thorough discussion of the elements and their possible effects on the product can be found in Section 2.6. Similarly, a discussion of the cement kiln dust and the impact of altered compositions can be found in Section 2.5. 2.3.2 Advantages of Alternative Fuels One major environmental advantage of substituting alternative fuels in the cement industry is the reduction of waste disposal sites. As the consumption of goods increases to satisfy our consumer-driven life-styles, the manufacturing wastes also build up considerably (Barger 1994). As industries produce wastes such as oils, plastics, tires, etc., the environmental impact of landfilling or incinerating these wastes becomes a serious problem (PCA 2004). Landfills require large areas of land that may become unsightly and ecologically detrimental. The waste incinerators too are hazardous to the environment. Incinerators burn garbage, but do not use the heat generated; however a cement plant does the same thing while using the heat generated to manufacture portland cement. Therefore a cement facility serves in both ways (Mokrzycki and Uliasz- Boche?czyk 2003). Natual Natural Originated through synthesis Originated through decomposition Coal originated fuel Petroleum originated fuel Paper cardboard Hydrogen Biodiesel Petcoke Typical Examples Plastic waste Natural gas Bituminous coal Anthracite Lignite Peat Shale Synthetic natural gas LPG Naphta Gasoline Kerosene Diesel oil Fuel oil Coal coke Coke gas Coal gas Synthetic gas Tar Logs Sugar-cane bagass Sawdust Wood chips Cotton seeds Rice hull Charcoal Landfill gas Wood tar Resid ual Co nventio nal Non-con vention a l Methanol Ethanol Lean gas Synthetic Renewable Fuel Origin of Fuel Non-renewable fuel Fossil derived synthetic fuel Fossil Biomass derived Non- biomass derived Biomass 21 Figure 2.3: Various fuels and their origin (Adapted from Greco et al. 2004) 22 Another significant environmental advantage of alternative fuel substitution is the preservation of nonrenewable energy sources (Trezza and Scian 2000). For instance, the process of mining coal takes its toll on the environment (Mokrzycki et al. 2003). Although coal is used for many applications other than firing cement kilns, even a small reduction in coal consumption will make a beneficial difference. In general, a decreased use of nonrenewable resources in cement plants can make a significant difference in the total volume of consumption around the world (Wurst and Prey 2002). It was reported that the utilization of alternative fuels in the Australian cement industry accounted for a reduction of 57,000 tons of coal consumption in 1999 (PCA 2004). Alternative fuels can also supplement the raw material requirement in cement production. For instance, due to the high silica content (78 to 90 percent) in the ash of rice husks, the amount of silica required in the raw feed may be significantly reduced (Jackson 1998). Additionally, the steel belts in tires may be used to replace a portion of the iron required in the raw materials (K??ntee et al. 2002). 2.3.3 Disadvantages of Alternative Fuels In order to make educated decisions concerning the use of alternative fuels in cement production, the disadvantages must be addressed and, if possible, overcome. Fundamentally, the co-firing of alternative fuels must be carried out under conditions guaranteeing total efficiency of combustion. Otherwise, problems associated with the quality of the product and/or environmental protection may occur (Greco 2004). Additionally, in order for alternative fuels to be implemented, many logistical problems 23 such as fuel preparation and conditioning, storing, dosing, feeding, and burning must be overcome (Wurst and Prey 2002). Many studies have previously been conducted to investigate the effect of burning various alternative fuels on the environment. Specifically, a number of these studies have been concerned with changes in emission characteristics. One such study was conducted in California where a cement plant had petitioned to use tires as a fuel supplement. In this study, it was found by the air quality management district of Cupertino, California, that tire burning substantially increases emissions of potentially toxic chemicals such as benzene, nitrogen oxides, furans and lead, as well as others (Martinez 1996). A detailed discussion of emissions can be found in Section 2.4. If results such as these were found to be true of any alternative fuel, it would be very difficult to make use of this type of fuel substitution. One potential constraint on the implementation of alternative fuels is the final clinker composition (Mound and Colbert 2004). Because the combustion byproducts are incorporated into clinker, any undesirable compounds/elements present in the fuels may be deposited into the cement itself. If even one of these compounds/elements affects the quality of the cement, the very benefits derived may be negated. The replacement of traditional fuels by alternative fuels inherently requires investment costs associated with adjustment or replacement of a burner, implementation of alternative fuel delivery systems, new fuel storage facilities, and fuel distribution systems (Greco et al. 2004). 24 The production of clinker requires an even combustion of fuels in order to consistently heat the raw materials (Peray 1986). Considering this, the fuels must be processed and conditioned to have the following characteristics (Wurst and Prey 2002): ? even particle size distribution ? as high and uniform calorific value as possible ? free of detrimental contents like some metals, glass, and minerals, and ? low moisture content. In most situations, modifications to facilities will have to be made in order to process and condition alternative fuels to meet these criteria. Each of the other logistical hurdles listed above must be overcome within economical constraints. 2.3.4 Alternative Fuel Options In addition to the ability of a substance to release large amounts of energy when consumed, there are a number of other characteristics that a substance must possess in order to be considered for implementation. For instance, composition and heat value are of significant importance to the operation of a kiln (Peray 1986). It would make little sense to replace coal with a fuel that has a heating value too small to allow for its utilization with reasonable quantities. The specific criteria that a material must meet in order to be considered as a fuel are typically specific to either the facility or the corporation that owns the facility. In general, each company that may be considering alternative fuel substitution usually develops its own set of standards. As an example of some of these standards, the 25 following criteria must be met in order for the Lafarge Cement Polska group to use a substance as an alternative fuel (Mokrzycki et al. 2003): ? Energy value ? over 14 MJ/kg (6019 BTUs/lb) ? Chlorine content ? less than 0.2 percent ? Sulphur content ? less than 2.5 percent ? Polychlorinated Biphenyls (PCBs) content ? less than 50 parts per million (ppm), and ? Heavy metals content ? less than 2500 ppm. It can be seen that a wide range of materials can be considered as viable alternative fuels. Alternative fuels are categorized by the phase in which they exist, those phases being solid, liquid, and gas (Peray 1986). A variety of fuels fall into each of the classifications, all of which present their own unique advantages as well as problems. Table 2.2 shows a number of alternative fuels from each classification that have been successfully burned in cement kilns. In this study, only the solid fuels have been considered, and hence, liquid or gas fuels will not be discussed here onwards. Solid fuels are the most commonly used, and particularly, pulverized coal is the predominant fuel used for cement production worldwide (Greco et al. 2004). Therefore, coal is quite obviously not an alternative fuel, and due to widespread literature on its use, it will not be addressed any further. The alternative fuels investigated in this study are: scrap tires, waste plastics, broiler litter, woodchips, and switchgrass. 2.3.4.1 Scrap Tires as Fuel Scrap tires were recognized as a serious waste threat in the mid 1980s, when an estimated 2 to 3 billion scrap tires had accumulated in both legal and illegal dump sites in the United States (Schmidthals 2003). As reported in 1993, 234 million scrap tires were produced annually in the U.S., 82 percent of which were landfilled, stockpiled or illegally dumped. A mere nine percent were consumed by energy recovery projects (Barlaz et al. 1993). This trend is not unique to the U.S.; it is present around the world. Corti and Lombardi (2004) reported that during the year of 1999, Italy produced 330,000 tons of waste tires. These staggering quantities of scrap tires represent considerable environmental and public health hazards to which the cement kiln could be a tremendous solution (Greco et al. 2004). For instance, if all Italian cement plants were able to use tires as fuel at a replacement rate of fifteen percent, 646,000 tons of tires could be disposed of per year, almost 100 percent more than is actually produced in that country (Corti and Lombardi 2004). Table 2.2: Classifications of Many Alternative Fuels (Greco et al. 2004) 26 27 Fifteen percent replacement is not unreasonable, but it is approximately the upper limit for whole tire substitution through conventional means. Whole tire replacement rates are typically limited to 10 to 15 percent, because the excess energy supply may result in localized overheating and reducing conditions. This promotes the volatilization of sulphur, which leads to material melting and build-ups in the kiln and preheater (Schmidthals 2003). There is no known upper limit for shredded tires due to the fact that they are typically fed through the primary burner. Some typical characteristics of tires used as fuel in the kiln system are: ash content of 12.5 to 18.6 percent (by weight), 1.3 to 2.2 percent sulphur, one to two percent zinc, and an energy value of 26,987 to 33,472 kJ/kg (11,602 to 14,390 BTUs/lb) (Jackson 1998). Wurst and Prey (2002) report average energy values of tires to be 25,104 to 29,288 kJ/kg (10,793 to 12,592 BTUs/lb), with zinc and sulphur as the primary elements of concern. Table 2.3 shows the energy value of tire-derived fuel (TDF) relative to two sources of coal. Sulphur, nitrogen, and chlorine are also shown in terms of content in the tires, as well as production. Finally, this report also gives zinc concentrations of 1.4 percent and 1.53 percent in chipped tires with and without the steel belts present, respectively. Waste tires not only act as fuel, they supplement some of the raw materials needed for cement production (K??ntee et al. 2002). When the iron belts in tires are not removed before introduction to the kiln, a portion of the raw feed iron is replaced, thus decreasing the quantities of iron that must be otherwise acquired (Corti and Lombardi 2004). Table 2.3: Various Properties of Tire-Derived Fuel Relative to Two Coal Sources (Barlaz et al. 1993) TDF Coal (Eastern U.S.) Coal (Western U.S.) Energy Value (kJ/kg ) 34,000 27,000 27,000 Sulfur (%) 1.2 2.0 0.8 Sulfur Production (kg x 10 6 /kJ ) 0.35 0.74 0.30 Nitrogen (%) 0.24 1.76 1.76 Nitrogen Production (kg x 10 6 /kJ ) 0.07 0.65 0.65 Chlorine (%) 0.15 0.08 0.08 Chlorine Production (kg x 10 6 /kJ ) 0.04 0.03 0.03 Energy Source One cement plant in Redding, California, which replaces 25 percent of its energy requirements with shredded tires, has reported a decrease in iron ore costs of 50 percent (Kearny 1990). Obviously, tire substitution can make a significant contribution to decreased raw materials cost. Corti and Lombardi (2004) reported on a study in which tires were substituted for coal at a replacement rate of 15 percent. Table 2.4 shows the change in emission characteristics between a kiln fired with coal alone, and the same kiln fired with coal and tires. The two abbreviated compounds presented are non-metallic volatile organic compounds (NMVOC) and particulate matter (PM). Table 2.5 shows the change in input characteristics required for the substitution of the tires. The latter shows a decrease in the amount of coal and iron required, while at the same time, an increase in the amount of electricity required to run the tire-specific feed system. Additionally, the diesel fuel 28 required for transportation of the tires a distance of 35 km is shown. The final result of this study, by life-cycle assessment, was that the substitution of tires for coal in the cement production process was a better source of waste tire disposal than as mechanically or cryogenically pulverized filler, or conventional waste-to-energy processes. Table 2.4: Emissions of Coal Relative to Coal and Tires (Corti and Lombardi 2004) Table 2.5: Effect on Input and Output Quantities for Tires Used as Fuel (Corti and Lombardi 2004) The results of the studies shown above reveal the tremendous possibilities for tire- derived fuel usage in cement plants. Figure 2.4 shows the rate of increase in facilities 29 using tires in the United States (PCA 2005). This trend is certainly a step in the right direction as far as scrap tire disposal and cement production is concerned. Figure 2.4: Trend of Tire Use as Fuel in Cement Plants in the U.S. (PCA 2005) 2.3.4.2 Waste plastics as Fuel Currently, very little literature exists on the use of plastic wastes as an alternative fuel in the cement industry. However, it is certainly a viable option that is continuously gaining consideration for such applications. Wurst and Prey (2002) have reported a limited amount of data on plastic waste fuels. Based on their research, plastics typically have an energy value on the order of 28,870 kJ/kg (12,412 BTUs/lb). Additionally, the elements that are deemed the most 30 worthy of concern in cement production applications are cadmium, lead, and zinc. The final result which is reported is that the optimum particle size for implementation is 10 mm (0.4 inch). This is to avoid conglomeration of particles upon introduction to the kiln, which may result in noncombusted plastic fractions. The results of a study done by Miller et al. (2002) are presented in Tables 2.6 and 2.7. Table 2.6 shows typical concentration ranges of various elements present in plastic used as fuel, relative to the same elements and their concentrations in coal. Table 2.7 shows relative percentages of the same elements that were retained in the ash after each of the fuels was combusted at a temperature of 800 to 900 ?C in a suspension firing reactor. Therefore, the elements with the lowest retention quantities are the elements that were the most volatilized, and would have the greatest tendency to end up in stack emissions. Also, the elements with the highest retention quantities would be most likely to be incorporated into the clinker if these fuels were burned in a cement kiln. The results of this study, as they relate to plastics, are that Cd, Cu, Hg, Pb, and Tl have the greatest potential to end up in emissions, while Be, Co, Mo, and Ni are the most likely to be incorporated into the clinker. A discussion of these elements and their effects on cement properties is presented in Section 2.6. Table 2.6: Concentrations of Elements in Coal and Plastic Fuels (Miller et al. 2002) Fuel less than 1 ppm 1 to 10 ppm 10-100 ppm greater than 100 ppm Colombian coal Be, Cd, Hg, Sb, Tl As, Co, Cu, Ni, Mo, Pb, Se Ba, Cr, Mn, Sr, V, Zn Polish coal Cd, Hg, Mo, Tl As, Be, Co, Sb, Se Cr, Cu, Ni, Pb, Sr, V, Zn Ba, Mn plastic waste As, Be, Hg, Se, Tl Cd, Co, Ni, Mo, Sb, V Cr, Cu, Mn, Pb, Sr Ba, Zn 31 Table 2.7: Concentrations in Ash From Coal and Plastic Fuels (Miller et al. 2002) Fuel 0-20% 21-40% 41-60% 61-80% 81-100% Colombian coal Hg, Se As, Cd Cr, Mn, Mo, Sb, Sr, Tl Ba, Be, Pb, Co, Cu, Ni, V, Zn Polish coal Hg, Se Tl As, Cd, Pb, Sb Ba, Cr, Cu, Mo, Sr Be, Co, Mn, Ni, V, Zn plastic waste Hg Cd, Cu, Pb, Tl, V Cr, Ba, Mn, Sr Be, Co, Mo, Ni percentage of trace elements retained in ash 2.3.4.3 Broiler Litter as Fuel Broiler litter is the material removed from the floors of poultry houses. The two main components are chicken litter and some sort of bedding material, such as sawdust. Other components that are generally present are feathers, dirt, etc. The UK produces 1.5 million tons of poultry litter per year, which is typically land-applied as fertilizer. However, some environmental problems have manifested themselves, such as phosphorus-rich water runoff (D?valos et al. 2002). Broiler litter is oftentimes also referred to as poultry litter, and for the purpose of this document, these terms will be used interchangeably. Due to the lack of research conducted utilizing broiler litter in cement kilns, a basic discussion of its composition and combustion characteristics will be presented. In a study reported by Abelha et al. (2003), poultry litter alone, and mixed with 50 percent (by weight) peat, was burned in a fluidized bed combustor, under various combustion conditions. The results of a proximate and an ultimate analysis on the litter and peat are shown in Table 2.8, along with an ash analysis of the litter in Table 2.9. 32 Table 2.8: Proximate and Ultimate Analysis of Chicken Litter and Peat (Abelha et at. 2003) HHV- Higher heating value Table 2.10 shows the ranges in CO and Volatile Organic Content (VOC) emissions concentration. In the case of CO with no secondary air, the concentrations are excessively high, which indicates incomplete mixing of air with the fuel, and possibly incomplete combustion of the fuel. In all other cases, CO levels were at or below the regulated levels. VOC concentrations followed the same trends as CO. Although these tests were not conducted in a cement kiln, this study provides results that may be typical of broiler litter combustion. 33 Table 2.9: Ash Analysis of Chicken Litter (Abelha et al 2003) The primary problem Abelha et al. (2003) encountered was the feeding of the litter. The screw-type feeder that was used could not handle the litter when it had a moisture content greater than 25 percent. This could certainly cause problems in cement plant applications as well. In fact, the moisture content of litter is also a problem for other reasons. The most prominent of these is combustibility. D?valos et al. (2002) reported on a study in which combustion characteristics of poultry litter were evaluated for various moisture contents. Table 2.11 shows the elemental analysis of a wet sample (approximately 68 percent water content) and a dry sample. Figure 2.5 illustrates the energy content versus water content. A linear approximation is fitted to the experimental data. Based on this approximation, a completely dry sample will have a calorific value of 14,447 kJ/kg (6,211 BTUs/lb), and a sample has a calorific value of 4,000 kJ/kg (1,720 BTUs/lb) when its water content reaches 78 percent. These data clearly illustrate the detrimental effect that increasing moisture content has on the heating value of broiler litter. 34 Table 2.10: CO and VOC Concentrations for Various Chicken Litter/Peat Mixtures and Burning Conditions (Abelha et al. 2003) Table 2.11: Elemental Analysis of Poultry Litter at Wet and Dry Moisture Conditions (D?valos et al. 2002) 35 Ene r gy Con t en t (kJ/kg ) Ene r gy Con t en t (kJ/kg ) Figure 2.5: Energy Content Relative to Water Content of Poultry Litter (D?valos et al. 2002) 2.3.4.4 Woodchips as fuel Woodchips have been burnt to make heat for decades, but the use of this energy source has significantly increased over the past 20 years. At the heart of this new application of wood energy is the attraction of using a renewable, locally-produced energy source that is generally the least expensive fuel available (Maker 2004). Woodchips are solid fuels made from woody biomass in the process of woodchipping. They can be made from waste wood, brush, saplings, limbs, tree slash, logging operations, and from forestry and roadside maintenance operations (Redmond 2006). In Table 2.12, woodchip fuel costs are compared to coal, as reported by Maker (2004). 36 Table 2.12: Comparative fuel cost for woodchips (Maker 2004) Woodchip prices are relatively stable. They can be transported and unloaded by dump trucks. Because they are available locally, long distance haulage, packaging, and energy consumption can be reduced. Fuel growing methods such as brush and coppice farming can produce ideal wood for chipping on a sustainable basis and hence may reduce dependence on fossil fuels (Redmond 2006). Woodchips have primarily been used in commercial heating systems, manufacturing plants and power plants (Maker 2004). Since there is not much literature available for use of woodchips as fuel in cement production, only the characteristics and chemical composition of woodchips will be discussed in this section. The heat content of woodchips mainly depends on their moisture content. As reported by Maker (2004), the average energy content of the bone-dry woodchips sample is typically about 19,771 KJ/Kg (8,500 BTUs/lb). But the actual energy content of any sample will depend on the mixture of species included in the sample and can only be determined in the laboratory (Maker 2004). Table 2.13 shows some typical dry-sample heating values for certain wood species. 37 Table 2.13: Dry sample heating values for woodchips (Maker 2004) However, woodchips fuel, as it is delivered, is never completely dry. The as- delivered or as-fired woodchips fuel can be characterized by its moisture content and the resulting heat content of the wood. Table 2.14 lists the average as-fired heating values of woodchips corresponding to the moisture content. The heating value of 11,863 KJ/Kg (5,100 BTUs/lb) corresponding to moisture content of 40 % is a good all-round figure to use for typical woodchips fuel (Maker 2004). 38 Table 2.14: As-fired heating values for woodchips corresponding to the moisture content (Maker 2004) Teislev (2002) reported that, typically, woodchips fuel contains 42% of moisture and has the following (dry) chemical analysis: Carbon 50.00%, Hydrogen 6.17%, Oxygen 42.64%, Nitrogen 0.17% and ash 1.00%. The high amounts of volatiles and low ash content of woodchips is suitable particularly for the cement kiln as the lower the ash incorporated into the clinker, the less effect it has on the clinker. Table 2.15 shows the typical chemical analysis of woodchips fuel reported by Wilen (1996) Woodchips have practically no sulphur and so, unlike fossil fuels, produce no SO x gases. Woodchips combustion does create NO x , CO and VOC emissions, but at levels comparable to fossil fuels (Maker 2004). 39 Table 2.15: Chemical analysis of woodchips (Wilen et al. 1996) 2.3.4.5 Switchgrass as fuel Switchgrass is a warm-season grass and is one of the dominant species of the central North American tall prairie grass. In the United States, switchgrass is considered the most valuable native grass for biomass production on a wide range of sites. It can be found in remnant prairies, along roadsides, pastures and as an ornamental plant in gardens. It is noted for its heavy growth in late spring and early summer (Sami et al. 2001). Switchgrass requires little fertilization and herbicide, and can be harvested twice a year with existing farm equipment. The grass is tough and has high productivity. Grown by farmers on marginal land, switchgrass could offer a cash crop and a boost to the farm economy (Boylan et al. 2000). It is also valuable for soil stabilization, erosion control, and for use as a windbreak (Sami et al. 2001). 40 41 Though switchgrass has not been used in cement kilns before, it has been co-fired successfully with coal in power generating plants. However, in power plants, some elements in switchgrass such as potassium, sodium, chlorine, silica, etc. cause problems when burned due to erosion, slagging and fouling, hence decreasing efficiency while increasing maintenance costs (Sami et al. 2001). In a cement kiln, such problems can be avoided since the ash is incorporated into the clinker. So, if it does not change the properties of the clinker drastically, use of a cement kiln can be a viable option for co- firing of switchgrass with coal. One of the major variables affecting economics of co-firing coal and switchgrass is the degree of preparation (shredding) necessary for the switchgrass material (usually transported as bales) before it is fed into the kiln. Some size reduction of the 8 to 10 foot stalks of grass will be required, and ways to minimize either the amount or the difficulty of pre-processing the grass are being investigated (Boylan et al. 2000). McLaughlin et al. (1999) reported that the energy content of switchgrass is about 18,400 KJ/Kg (7,910 BTUs/lb), which is comparable to that of other bio-fuels such as wood. The ignition process of switchgrass and coal is similar to that for coal only except that there is more volatile matter available for reaction in such fuel. Therefore, it is more likely that homogeneous ignition will occur for such fuels (Sami et al. 2001). Table 2.16 shows a list of physical and chemical properties of switchgrass compared to other common bio-fuels. As is typical with many other biomass fuels, handling issues appear to be the toughest problems. The bulk density of switchgrass is very low, and is considerably less dense than coal. As a result, a mixture of 10% switchgrass with 90% coal (by mass) is a roughly 50% mixture of the two constituents by volume (Boylan et al. 2000). Table 2.16: Physical and Chemical properties of Switchgrass compared to other bio-fuels (McLaughlin et al. 1999) 1.8 Table 2.17 shows the proximate and ultimate analyses of switchgrass fuel in comparison to other fuels as reported by Sami et al (2001). The ash content of switchgrass is notably higher than coal while moisture content is lower. 42 Table 2.17: Chemical analysis of Switchgrass compared to other fuels (Sami et al. 2001) HHV- Higher heating value A: F ? Air to Fuel ratio (dry ash free basis) AFT ? Adiabatic flame temperature (ultimate analysis) Boylan et al. (2000) conducted combustion tests with 10% switchgrass ? 90 % coal mixtures and compared the results to bituminous coal combustion tests. It was observed that there was no degradation of unburned carbon. There was a reduction in sulfur emissions which could be attributed to the low sulfur content of switchgrass. Also, there was a decrease in the NO x emissions as well. 2.4 Emissions A portland cement manufacturing facility that produces one million tons of cement annually will also produce roughly 1.5 billion cubic meters of gases in the process (Jackson 1998). The primary components of these gaseous emissions are CO 2 , 43 44 NO x , and SO x . Lesser pollutants emitted into the atmosphere are carbon monoxide, dioxins, furans, particulate matter, and metals (Schuhmacher et al. 2003). Due to the highly variable nature of portland cement manufacturing, the specific composition of plant emissions will be unique to each facility. Although many factors affect the specific makeup of a plant?s emissions, there are three fundamental aspects of the process, which the manufacturer can control, that ultimately determine their emissions state. These three parameters are the chemical composition of the raw materials, the chemical and physical properties of the fuel, and the kiln conditions (Marengo et al. 2006). Based on the focus of this project, a discussion of each of the primary emission components and their relationship with alternative fuels will be discussed in the following sections. Brief mention of the lesser emission compounds will also be made. 2.4.1 Carbon Emissions Carbon dioxide (CO 2 ) and carbon monoxide (CO) are major emission components with which portland cement production facilities must be concerned. CO 2 is the primary agent responsible for the ?greenhouse effect,? and is therefore closely monitored by environmental agencies around the world. Portland cement production facilities are a significant contributor to atmospheric carbon dioxide worldwide. In 2000, global CO 2 emissions from portland cement production were estimated at 829 million metric tons, which accounts for 3.4 percent of all CO 2 emissions for that year (Hanle et al. 2004). On a more regional scale, in 1999 the portland cement industry in the United States was responsible for 22.3 million metric tons of carbon dioxide emissions, which accounted for 4 percent of the total CO 2 emissions in the United States in that year (Bhatty 2004). 45 Carbon dioxide emissions come from combustion of fossil fuels and the calcination of limestone, each of which contribute approximately half of the CO 2 during production (Worrell et al. 2001). Calcining is the process of heating limestone and converting CaCO 3 into CO 2 and CaO. This process is typically carried out in a preheater, which may also be known as a precalciner. The CO 2 is released into the atmosphere, and the CaO enters the kiln where it becomes a primary component in the formation of the clinker. Carbon monoxide is primarily produced when fuels are not completely consumed due to insufficient mixture of oxygen and fuel at the location of combustion and/or a rapid decrease in local temperature to levels below those required for ignition (Bhatty 2004). The amount of CO 2 produced during combustion is a partially a function of the type of fuel being consumed (Worrell et al. 2001). The same can be said of carbon monoxide. In an experiment conducted at the Malogoszcz cement plant in Poland, up to 40 percent of the heat required for clinkerization was provided by two different alternative fuels called PASr and PASi. PASr fuel was a composite mixture of grain- sized particles made from paper, cardboard, foil, cloth, textile, plastic containers, tapes, cables and cleaning agent. The PASi fuel was composed of sawdust or tobacco dust mixed with wastes derived from paint, varnish, heavy post-distillation fractions, diatomaceous earth contaminated with petroleum-based waste, etc. The emissions data for the three major compounds are shown in Figure 2.6. 46 0 100 200 300 400 500 600 700 800 CO NO2 SO2 Emission Type Emissio n s to A i r (% ) Allowable Without PASr Fuel With PASr Fuel CO SO 2 NO 2 Figure 2.6: Emissions Data from a Plant Burning Alternative Fuels (modified from Mokrzycki et al 2003) Prisciandaro et al. (2003) have also reported emissions results of tests run when comparing traditional fuels with alternative fuels. Two Italian cement plants were used for the study. Both plants used petcoke as their traditional fuel. Plant 1 replaced up to 20 percent of its energy with that from tires. Plant 2 replaced the same percentage of its energy with that from recycled oils. Figure 2.7 shows the change in emissions concentrations due to the changes in fuel types. CO levels remained approximately unchanged in Plant 1 and Plant 2. 47 Figure 2.7: Change in Emission Levels due to Changes in Fuel Types (Prisciandaro et al. 2003) 48 2.4.2 Nitrogen Emissions Nitrogen Oxides (NO x ) are a family of nitrogen-based compounds that are found in the stack emissions of a portland cement production facility. The two most common forms are NO and NO 2 . Typically, more than 95 percent of exhaust gases produced by a cement kiln are NO, with the remainder of the gases mostly comprising NO 2 (Gardeik et al. 1984; Greer 1989). Just like carbon-based emissions, NO x concentrations are also susceptible to the temperamental nature of cement kilns. The independent variables which have the greatest influence on NO x levels are fuel type, feed rate, amount of air flow, and the temperatures in the burning zone of the kiln (Walters et al. 1999). There are three mechanisms by which NO x is formed in the kiln. In order of decreasing contribution to overall concentration, they are thermal NO x , fuel NO x , and feed NO x (Young 2002). Thermal NO x (primarily NO) is the most abundant source of NO x in the kiln system. It is formed when atmospheric nitrogen present in the combustion air is oxidized in the presence of high temperatures. The threshold at which thermal NO x begins to form is commonly thought to be around 1400?C, above which NO levels increase dramatically. The majority of the thermal NO x are formed in the burning zone where flame temperatures easily reach 1600?C (Bhatty 2004; Greer 1989; Marengo et al. 2006; Young 2002). Fuel NO x is formed when chemically bonded nitrogen in the fuel is released and oxidized due to combustion. Therefore, as long as the temperatures are above the ignition temperature of the fuel, fuel NO x is being formed (Gardeik et al. 1984). The quantity of nitrogen present in fuel is significantly less than that present in the 49 combustion air, which means that the contribution of fuel NO x in the burning zone is relatively small. However, in a system where a preheater is utilized, the temperature at the secondary combustion zone is much less than the threshold for thermal NO x formation. This allows fuel NO x to be the primary contributor at this location (Young 2002). Greer (1986) stated that if all the other factors controlling NO x formation are held constant, the total amount of NO x can be altered by controlling the content of nitrogen in the fuel (Greer 1986). The final source of NO x , is the raw material feeds. Feed NO x is similar to fuel NO x in that it is formed when the nitrogen that is chemically bonded within the feeds is released and oxidized. This process takes place at temperatures in the range of 300 ?C - 800 ?C (Marengo et al. 2006). An upper limit of 50 percent has been reported for the amount of feed nitrogen that may be converted to NO x . Ratios this high will only occur when the raw materials are heated slowly (Gartner 1983). Considering this theoretical maximum along with the natural limit of the amount of nitrogen present in feeds, it is evident that the contribution of feed NO x to the overall NO x production in the kiln is minimal (Young 2002). There are two major implications of large volumes of NO x emitted into the atmosphere. The first is that NO 2 combines with moisture in the atmosphere to form either nitrous acid or nitric acid. These two compounds are the primary components of acid rain (Bhatty 2004). Although the majority of the NO x produced in the kiln system is NO, it is largely converted into NO 2 in the atmosphere (Greer 1989). The second product that forms when NO x is released into the atmosphere is smog. Smog is formed when NO x combines with hydrocarbons in the presence of solar radiation (Bhatty 2004; Greer 50 1989). Therefore, it is important that all NO x levels are monitored and limited throughout the portland cement industry. Because the majority of the NO x produced in cement kilns comes from thermal NO x , alternative fuels cannot change its concentration substantially in either direction. However, the nitrogen concentration of fuels does have some effect on the amount of NO x produced. The results of the study conducted by Mokrzycki et al. (2003) show that NO 2 emissions were decreased by 81 percent between traditional fuels and the PASr fuel, as shown in Figure 2.6. The study conducted by Prisciandaro et al. (2003) shows an increase in NO x emissions in Plant 1, and a decrease in NO x emission at Plant 2, as shown in Figure 2.7. 2.4.3 Sulphur Emissions Sulphur Oxides (SO x ) are a family of sulphur-based compounds that are commonly released as emissions from industrial applications. In the portland cement industry, SO 2 and SO 3 are the most prevalent members of this family. Although both of these compounds are typically present in a cement kiln, it has been reported that as much as 99 percent of the SO x emissions are in the form of SO 2 (Marengo et al. 2006). The SO 2 that is released from the kiln system is produced by the oxidation of sulphur compounds that enter the kiln in either the fuel or the raw materials. The quantity of SO 2 released is highly variable based on factors such as the form in which it enters the kiln, the presence of certain other elements, such as alkalies and chlorine, in the kiln, and the kiln operation and design (Miller and Hawkins 2000). Although significant quantities of sulphur are released via emissions, the majority of sulphur that enters the kiln is either 51 incorporated into the clinker, usually as alkali-sulfates, or deposited in the kiln/preheater system in the form of deposits or kiln rings. Greer (1989) reported 50 to 90 percent of the sulphur that enters the kiln either remains in the kiln or is incorporated into the clinker. When SO x are emitted into the atmosphere, they typically take one of two forms. SO 2 readily combines with the moisture in the atmosphere to form H 2 SO 4 , also known as sulphuric acid, which is a major contributor to acid rain (Bhatty 2004). SO x may also remain solid and become what is known as dry deposition, which is a solid reaction product (Greer 1989). The consequences of either of these phenomenons are certainly detrimental. The former speaks for itself in terms of potentially harmful effects. The latter exists as particles small enough to be inhaled by both animals and humans, where it is harmful to the respiratory system and potentially fatal (Schuhmacher et al. 2003). Just as with NO x and carbon-based emissions, the type of fuels used have a direct effect on the amount of SO x in the emissions. This can be illustrated by examining the study by Mokrzycki et al. (2003), which was shown previously. It was reported that there was a decrease in SO 2 emissions by 7 percent between traditional fuel and PASr fuel as shown Figure 2.6. 2.4.4 Other Problematic Emissions In addition to the three major types of emissions that have been previously discussed, many other compounds may be created in the kiln system and emitted into the atmosphere. Just as with NO x , SO x , and carbon-based emissions, the concentrations of each are affected, to some extent, by the type and quantities of fuels being used. Due to 52 the lack of literature directly relating alternative fuels and the emission of these compounds, a brief discussion of their formation and potential dangers will be presented, and the ability of alternative fuels to affect their presence will be briefly discussed. 2.4.5 Dioxins and Furans ?Polychlorinated dibenzodioxins (PCDD) and polychlorinated dibenzofurans (PCDF) are halogenated aromatic hydrocarbons that are byproducts of combustion below 400?C and chemical processes in the presence of chlorine? (Kirk 2000). Although the formation of these compounds is not completely understood, many of the precursors can be readily identified. Many chlorine compounds, including polyvinyl chloride (PVC) and sodium chloride, are the primary harbingers of dioxins and furans (Bhatty 2004). The major concern with dioxins and furans is that they are extremely harmful to animals and humans when they are ingested. Human ingestion typically arises from the consumption of animals, such as fish, that have been contaminated. Some of the effects in humans are eye irritation, dermatitis, gastrointestinal disturbances, liver and kidney damage, and possibly cancer (Kirk 2000). Therefore, increases in dioxin and furan emissions due to implementation of alternative fuels would be a serious setback for the viability of those fuels. 2.4.6 Metals Metals in the emissions from cement plants are also a concern. Many metals present in the kiln system are incorporated into the clinker and are not emitted in measurable quantities. However, some metals are extremely volatile in the kiln, and are 53 present in the stack gases. Some of the metals of greatest concern are mercury, lead, cadmium, and chromium. Detailed discussion of each metal is presented in Section 2.6. The concentration of metals in the emissions is directly related to the concentration of that metal in both the fuel and raw materials. Therefore, if the concentration of a metal typically found in emissions is changed by utilizing an alternative fuel, the concentration of that metal in the stack gases may change by a similar amount. One example of this phenomenon is reported by Bhatty (2004), who reported that ZnO mass flow rates in stack emissions decreased from 2.97 mg/sec to 1.53 mg/sec in U.S. cement plants using traditional fuels and waste fuels, respectively. 2.4.7 Particulates One final emissions component that must be considered is particulate matter. These solids are fine enough to remain suspended in the gases flowing through the kiln and into the stack. Although particulates are common in stack gases, they typically do not actually exit the stack in appreciable quantities. It is common practice for portland cement plants to have electrostatic precipitators installed in the stack, which filter out and collect this dust. A precipitator works by imparting an electrical charge to the dust particles as they pass, then these charged particles are attracted to oppositely charged plates to which they stick. When a plate becomes completely coated, the dust is removed and collected. The amount of particulates collected is dependent upon local regulations and how much the facility is willing to spend on removal devices. The price of a precipitator increases exponentially with a decrease in the size of the particles it is capable of removing. The implementation of electrostatic precipitators has significantly 54 reduced the concern over particulate emissions from a portland cement facility (Jackson 1998). 2.5 Cement Kiln Dust It has been mentioned previously that all products that enter the kiln are either incorporated into the clinker, or they are volatilized and become suspended in the gas flow. When these gases reach the cooler parts of the kiln, many of the suspended particles precipitate out and are absorbed into the incoming raw material stream. This is particularly true in kilns with a suspension preheater system. In this way, a cycle is established in which particularly volatile elements, such as K, Na, S, Cl, and some metals, are continuously redeposited into the raw material feed (Taylor 1997). The particles that remain aloft in the gases are collected by what are known as particulate matter control devices (PMCD) (Hawkins et al. 2004), thus removing them from the remainder of the emissions. These particulates are collectively referred to as cement kiln dust (CKD). The amount of cement kiln dust produced by a portland cement facility varies based on the chemical composition, type, and quantity of raw materials and fuels present, as well as the type of kiln being used. Bhatty and Miller (2004) reported CKD production of a typical facility to be five percent of the total cement produced. Shoaib et al. (1999) report the production rate may be as high as 12 percent. The United States is responsible for producing over 4 million tons of CKD that must be disposed of yearly (Todres et al. 1992). On a global scale, there are about 30 million tons produced in the average year (Konsta-Gdoutos and Shah 2003). With quantities such as these produced annually, it is easy to see why CKD poses tremendous disposal problems for the industry. 55 Many portland cement facilities are able to reuse all, or at least a major portion of, the CKD they generate as a replacement for some of the raw material feed or the fuels (Taylor 1997). However, due to chemical composition limits related to concrete durability issues, particularly those associated with alkalies, sulfates, and chlorides, most facilities are forced to find other applications for this industrial waste (Bhattacharja 1999). Some common alternative applications, in lieu of landfilling, are use as a supplementary cementing material (Mishulovich 1999; Shoaib et al. 2000), for stabilization of soils (Bhatty et al. 1996), and as a waste stabilization/solidification agent (Hawkins et al. 2004). 2.5.1 Composition of Cement Kiln Dust Cement kiln dust varies from plant to plant in chemical, mineralogical, and physical composition, based upon factors such as the feed raw materials, type of kiln operation, dust collection facilities, and the type of fuel(s) used (Klemm 1980). In Table 2.18, the chemical composition, as a percentage of total weight, of the CKD produced in three different types of kilns is shown (Bhatty et al. 1996). In Figure 2.8, the particle size distribution of the same three CKDs, where, ?Dust G? is from the long-wet kiln, ?Dust H? is from the long-dry kiln, and ?Dust S? is from the alkali by-pass kiln is shown (Todres et al. 1992). Table 2.18: Chemical Composition of CKD Produced in Various Kiln Types (Bhatty et al. 1996) 2.5.2 Alternative Fuels and CKD The type and quantity of fuel used to fire a cement kiln has a direct effect on the chemical composition of the kiln dust (Bhatty 2004). Eckert and Guo (1998) reported on a study conducted at numerous cement plants across the United States whose purpose was to determine the chemical composition of cement and CKD when waste-derived fuels (WDF) were used as a replacement for a portion of the traditional fuels. These chemical compositions were determined by means of X-ray fluorescence (XRF). Table 2.19 provides information about each of the plants, which includes whether it used waste- derived fuels as its primary (P) or alternate (A) fuel source. 56 Figure 2.8: Particle Size Distribution of CKD Produced in a S (alkali by-pass kiln), G (long wet kiln), and H (long dry kiln) (Todres et al. 1992) The results for seven of the seventeen kilns studied are shown in Table 2.20. Although these results provide only a snapshot of the effects that fuel has on CKD, they do provide some understanding of the link between these two components of portland cement manufacturing. 57 Table 2.19: Cement Plant Information (Eckert and Guo 1998) Company Name Plant Location WDF use Sample Designation Giant Harleyville, SC P Giant(SC)-1 Holnam Holly Hill, SC P Holnam(SC)-1 Giant Harleyville, SC P Giant(SC)-2 Holnam Holly Hill, SC P Holnam(SC)-2 Texas Industries Midlothian, TX P TXI(TX)-1 Texas Industries Midlothian, TX P TXI(TX)-2 North Texas Midlothian, TX A NTXC(TX)-1 WDF usage: P=Primary, A=Alternate Table 2.20: CKD Composition (Eckert and Guo 1998) 58 59 2.6 The Effects of Elements on Clinker, Cement, and Concrete There are many elements that may be incorporated into portland cement throughout the manufacturing process that could alter the performance of the final product. The assimilation of these elements into the cement is highly complex, and depends on the kiln process conditions. The first aspect of their inclusion is the source of the element. It has previously been discussed that many materials must be fed into the kiln in order to produce cement. Raw materials, fuels, and air could potentially be sources of altered composition of the clinker (Bhatty 2004). Another factor that determines whether an element will be detrimental is the concentration at which it is present. The concentration at which an element becomes harmful is unique to that element. In the case of many of the elements, it may not be known if there is any effect on the product or the process at any concentration. A project conducted by Mokrzycki et al. (2003) was described in Section 2.1 of this document. In this research, a portland cement facility produced clinker using traditional fuels alone, as well as two different alternative fuels. In Table 2.21, the change in chemical composition of the clinker based on changes only in fuel types is shown. It is evident from these data that the chemical composition of the fuels has an effect on some of the chemicals in the clinker. In order for an alternative fuel to be implemented, it must be established that changes such as these will not adversely affect the properties of the final product (Gartner 1980). One criterion that must be considered when evaluating data relating changes in chemical composition to cement or concrete properties, is the method by which the variation in chemical composition is brought about. Many tests are conducted in which specific elements are isolated and cement or clinker samples are artificially dosed with predetermined concentrations of the corresponding compound after the cement has been formed (Trezza and Scian 2000). In such cases, the results may be substantially different from those in which the concentration changes came about through the clinkering process. These results can serve illustrative purposes nonetheless. Table 2.21: Elemental Composition of Clinker Produced with and without Two Alternative Fuels (Mokrzycki et al. 2003) Table 2.22 is a summary, based on previous research, of the effects that selected elements have on concrete properties. The effects shown resulted from an increase in the respective element concentration in the cement from which the concrete was made. 60 61 Many elements have been found to affect compressive strength, the predominant property of concrete, differently at different ages. Therefore, compressive strength is divided into three age groups: early strength (less than 28 days), strength at 28 days, and long-term strength (later than 28 days). In many cases, the literature was contradictory. In such cases, multiple effects are shown for the same element-property interaction. Discussions of the source, resulting destination, and effect on the properties of the product for many selected elements are included in the following sections. 2.6.1 Alkalis (Sodium and Potassium) These two elements are typically addressed together because their effects are so closely related in the cement/concrete industry. Sodium and potassium are both metals and are numbers 11 and 19 on the periodic table, respectively. Alkalis are present in both raw materials and fuels, particularly coal (Gartner 1980). Bhatty (2004) reported alkali concentrations of 0.13 percent for sodium and 0.47 percent for potassium in raw feeds. When alkalis are present in the kiln process, they will primarily be incorporated into the clinker. They will most likely take the form of sulfates, if adequate sulphur is present, and will combine with the major clinker phases (Taylor 1997). The amount of alkalis in the major phases is dependent on the degree to which they can react with sulphur. This reaction will continue until all sulfates are consumed (Gartner 1980). Alkalis are potentially detrimental to the kiln process. It is likely that some will volatilize in the hottest portions of the kiln and will condense in the cooler parts (Jackson 1998). This produces clogs in the preheater (when present) and rings in the kiln (Gartner 1980). Table 2.22: Effects of Elements on Concrete Properties (Swart 2007) Early Comp. Str. (< 28 days) Comp. Str. (@ 28 Days) Long Term Comp. Str. ( > 28 Days) Setting Time (? = accelerated) Heat of Hydration Shrinkage Water Demand Leaching Concerns? Other Alkalis ?? ?? ?,? ? Antimony Arsenic Y Barium ?? ?? Beryllium Possibly effects color of clinker/cement Boron Bromine Cadmium ?? ? ? Y Carbon Chlorine Promotes corrosion of reinforcing steel Chromium ?, ? ?? ?? ?, ? ? Cobalt ?? ? ? Copper ?? ?? Produces darker colored clinker/cement Fluorine ?, ? ?? Lead ? ?? Y Discourages Alkali-Silica Reaction Lithium Magnesium ? ?? Manganese ?, ? ?, ? ? Effects color of clinker/cement Mercury Y Molybdenum ?,? ? Nickel ??,? ?? ?? ? Produces brown color in clinker/cement Nitrogen Phosphorus ?? ?? ?? ?? ? ? ? Rubidium ? ? Strontium ?? Sulfur ?? ?, ? Thallium Y Titanium ?, ? ? ? ? Produces yellow color in clinker/cement Vanadium ?? ? ? Zinc ?,? ?,? ?,? ?? ??? Produces color changes in clinker/cement Zirconium ?? ? ? ? Major Increase Minor Increase Major Decrease Minor Decrease Multiple Sources ?? ? ?? ? Single Source ?? ? ?? ? Key Property Element 62 63 One method for avoiding this phenomenon is to by-pass the alkalies into the CKD. Many facilities do this, and CKD is usually high in alkali concentration because of this process (Bhatty 2004). Alkalis incorporated into the cement typically produce high early strengths and lower long-term strengths (Gartner 1980; Taylor 1997). At alkali levels greater than 0.8 percent, Jackson (1998) reported increases in early strength of approximately 10 percent, with a corresponding decrease in 28-day strength of 10 to 15 percent. If alkalis are present at levels too large to completely combine with sulphur, they are detrimental to setting and hardening properties (Gartner 1980). The presence of alkalis, together with reactive silica in the aggregates, also promotes a reaction known as the alkali-silica reaction, which causes significant cracks in concrete (Bhatty 2004; Gartner 1980; Taylor 1997). Taylor (1997) also reported that if the concentration of alkalis is increased, the optimum amount of gypsum is also increased. Jackson (1998) reported high alkali cements exhibit higher drying shrinkage characteristics, accelerated rates of hydration, and decreased setting times. The effects of alkalis on setting time and compressive strength are shown in Tables 2.23 and 2.24, as reported by Lawrence (1998). In Table 2.23, the initial and final setting times, in minutes, for concrete with various concentrations of alkalis are shown. In this study, it was found that as the concentration of Na 2 O increased, so did both initial and final setting times. This contradicts what Jackson (1998) reported. As the concentration of K 2 O increased, both initial and final setting times decreased. In Table 2.24, the variation in compressive strength, at four ages, for the same concrete specimens as in Table 2.23, is shown. As the concentration of Na 2 O increased, the compressive strength decreased at all ages. The compressive strength for the various concentrations of K 2 O was more variable. For the concrete with 0.88 percent K 2 O, the compressive strength, relative to the control sample, was increased at 1 and 3 days, but decreased at 7 and 28 days. The concrete strength with 1.48 percent K 2 O was decreased at 1 and 3 days, and increased at 7 and 28 days relative to the strength of the concrete with 0.88 percent K 2 O. This is consistent with what Gartner (1980) and Taylor (1997) reported. Table 2.23: Setting Time of Cement Specimens with Various Alkali Contents (Lawrence 1998) H 2 O (%) Initial Final Control 25 180 215 0.72% Na 2 O in clinker 25 185 290 1.26% Na 2 O in clinker 25 295 360 0.88% K 2 O in clinker 25 150 205 1.48% K 2 O in clinker 25 50 135 Setting Time (min) Cement + sodium or potassium oxide in clinker Table 2.24: Compressive Strength of Cement Specimens with Various Alkali Contents (Lawrence 1998) 1 day 3 days 7 days 28 days Control 20.0 41.5 61.8 74.2 0.72% Na 2 O in clinker 19.5 39.8 59.6 68.7 1.26% Na 2 O in clinker 18.4 39.2 57.5 68.2 0.88% K 2 O in clinker 21.9 44.8 60.7 72.1 1.48% K 2 O in clinker 20.0 43.1 61.0 73.2 Cement + sodium or potassium oxide in clinker Compressive strength (MPa) 64 65 2.6.2 Antimony (Sb) Antimony is element number 51 on the periodic table, and is classified as a semi- metal. Typically, antimony is not found in large quantities in any of the components used to produce portland cement. However, it is not uncommon to find trace amounts, on the order of 0.08 ppm, in the raw materials (Bhatty 2004). Antimony could possibly be introduced by fuels, but more than likely it would be at levels even lower than those found in the raw materials (Bhatty 2004). When antimony is introduced into the kiln, it is uncertain where it will establish itself. Bhatty (2004) stated that, ?a considerable portion of antimony gets incorporated in clinker.? It is also known that antimony has a tendency to be combined with the CKD (Gartner 1980). Although it is possible to find antimony in portland cement, it is not known how its presence affects the properties of the final product. This is likely due to its very low concentration levels in cement. 2.6.3 Arsenic (As) Arsenic is number 33 on the periodic table, and is classified as a nonmetal. It can generally be found in both raw materials and in fuels. Bhatty (2004) claimed that As can be present in levels up to 12 ppm in limestone, 23 ppm in clay, 50 ppm in coal, and 0.6 ppm in petroleum coke. Therefore, it is evident that some arsenic will be present in cement manufacture. Although it is well known that As will almost certainly be present in at least one of the products introduced to the kiln, it is far less certain where that arsenic ends up. 66 Typically, arsenic takes the form of a volatile compound and would seemingly be incorporated into the CKD (Gartner 1980). It has been argued, however, that As enters into the clinker due to excess CaO, oxidizing conditions, and high temperatures within the kiln (Weisweiler and Kr?mar 1989). No significant results are known to have been collected on the effects of As on the properties of cement or concrete. There is another concern with arsenic. Because it is a toxic and volatile element, its presence in emissions must be closely monitored in order to ensure the health of people, animals, and the environment (Moir and Glasser 1992). 2.6.4 Barium (Ba) Barium, classified as a metal, is number 56 on the periodic table. Ba is typically found in the raw materials, particularly limestone or clay. In some instances, barium can also be found in fuels, such as coal, at levels up to 24.5 ppm (Bhatty 2004). Because barium is not a volatile metal, it is generally incorporated into the clinker when introduced into the kiln. Unlike many of the elements present in this study, links have been made between varying concentrations of Ba and the properties of the cement produced. It has repeatedly been reported that additions of barium have produced an increase in compressive strength of the concrete (Miller 1976; Gartner 1980). Specifically, Jackson (1998) reported that at small amounts, barium may increase 28-day strengths. Particularly, a 0.3 percent increase in BaO may increase 28-day strengths by up to 20 percent, and a 0.5 percent increase in BaO may increase 28-day strength by 10 percent. 67 It is also thought that cement paste shrinkage is affected by changes in barium concentrations. Both Miller (1976) and Gartner (1980) report that increases in Ba levels produced increases in paste shrinkage. Finally, it is also possible that additions of Ba produce a decrease in water demand (Miller 1976). 2.6.5 Beryllium (Be) Beryllium is element number four and is classified as a metal. Although it is rarely present in any appreciable amounts, trace amounts can be found in the raw materials or in fly ash if it is being used as a raw material substitute (Bhatty 2004). Bhatty (2004) reported that Be can be found in levels up to 0.5 ppm in limestone, 3 ppm in clay, and 2.27 ppm in coal. When beryllium is present in products introduced into the kiln, it is usually incorporated into the clinker. This is due to the fact that Be is a stable, nonvolatile element (Bhatty 2004; Gartner 1980). Because beryllium is typically present in such low concentrations, its effect on cement and concrete is debatable. It is thought that additions of beryllium may cause the clinker to be blacker than without it. Also, Be could possibly have significant effects on the setting and strength properties of cement, but no data are reported (Bhatty 2004). 2.6.6 Boron (B) Boron is element number five, and is a nonmetal. It is usually only found in small quantities in the raw materials, specifically the ones used as an iron source. In general, the upper limit on the concentration of boron is about 3 ppm. B is usually absorbed by the clinker when it is introduced into the kiln (Miller 1976). 68 The effects of boron addition are most notable in the chemical reaction of the raw materials. Gartner (1980) reported that quantities as low as 0.04 percent can be deleterious to cement properties, but its effects are highly unpredictable. Besides this, not much is known about the effect of boron on the properties of portland cement. 2.6.7 Bromine (Br) Bromine is a nonmetal that is number 35 on the periodic table. Br is typically only found in appreciable amounts in the raw materials. Bhatty (2004) gives the following values as reasonable upper limits on the concentration of bromine: limestone (6 ppm), clay (58 ppm), and coal (11 ppm). Due to the volatility of bromine, if it were introduced into the kiln, it is most likely to end up in either the emissions or the CKD. Negligible amounts of Br would be found in the clinker (Bhatty 2004). Because bromine is volatilized in the kiln, it does not end up in the clinker. Therefore, the effects of Br on portland cement are unknown. 2.6.8 Cadmium (Cd) Cadmium is element number 48, and is classified as a metal. Cd can be found in small amounts in the raw materials as well as the fuels. Bhatty (2004) gives possible concentration values for cadmium: limestone (0.035 to 0.1 ppm), clay/shale (0.016 to 0.3 ppm), coal (0.1 to 10 ppm), and used oil (4 ppm). It is most likely that the majority of Cd introduced into the kiln will end up in the preheater cyclones, in facilities that have them, or in the CKD (Bhatty 2004; Taylor 1997). Bhatty (2004) claimed that, ?in a cyclone preheater kiln, 74 to 88 percent of the 69 total Cd entering the kiln is incorporated in clinker as opposed to 25 to 64 percent for that produced in the grate preheater kilns.? The most significant findings regarding the effect of Cd on the properties of portland cement were presented by Murat and Sorrentino (1996). They claim that cadmium in the clinker slows the setting time, and decreases the compressive strengths. Additionally, Gartner (1980) reported that the addition of Cd(OH) 2 to mortars produced a slight reduction in strength. In addition to the effect that Cd may have on the final product, its introduction into the environment must be closely monitored due to its toxic nature. Therefore, emission levels must be observed in order to prevent Cd from being released. Additionally, the leachability of Cd from cement/concrete must be monitored. Murat and Sorrentino (1996) noted that no cadmium was detected in the leached material from concrete after one month. Although leaching of Cd is not typically a problem, its consequences are something that anyone placing concrete high in cadmium levels should be aware of. 2.6.9 Carbon (C) Carbon is element number six on the periodic table, and is classified as a nonmetal. It is present in very large quantities in both the raw materials and in the fuels. Limestone is the major contributor of carbon to the raw materials. Any fuel that is used will contain carbon in high concentrations. Almost without exception, any carbon that is introduced into the kiln will be released through the stack emissions as CO 2 . This is one of the most significant problems 70 that portland cement manufacturers have to deal with. A detailed discussion of carbon- based emissions can be found in Section 4.1. Due to the fact that all of the carbon is released in the emissions, there is no C that is incorporated into the clinker. Therefore, its effect on cement and concrete is negligible. 2.6.10 Chlorine (Cl) Chlorine is the 17 th element, and a nonmetal. Chlorine is commonly found in both the raw materials and fuels. Bhatty (2004) has reported the following typical concentrations: less than 0.02 percent by weight in raw materials and 10 to 2800 ppm in traditional fuels. Limestone is quite often closely associated with Cl, as well as other CaCO 3 sources, particularly those derived from marine origins (Gartner 1980), which may contain chloride levels up to 240 ppm (Bhatty 2004). The tendency toward refuse- derived fuels, including scrap tires, is prone to contributing meaningful increases in chloride levels (Miller 1976). Alkali chlorides that volatilize and condense in the kiln may lead to the formation of kiln rings. If the volatilized alkali chlorides escape into the preheater stack, they have a tendency to cause buildups which lead to poor performance of the facility (Bhatty 2004; Jackson 1998; Taylor 1997). It has been reported that as much as 99 percent of all chlorides in the preheater are recaptured by the incoming raw feeds (Ritzmann 1971). If no preheater stacks are present, these compounds are generally incorporated into the CKD, if they do not form kiln rings (Bhatty 2004). Jackson (1998) also claimed that chlorides will end up in emissions. 71 Due to the volatile nature of chlorine and its tendency to be deposited elsewhere, typical concentrations of Cl in clinker are not very high (Gartner 1980). These levels are generally less than 0.03 percent (Bhatty 2004). One effect of chlorides on concrete that is a cause of major concern in the concrete industry is the acceleration of corrosion of the reinforcing steel (Taylor 1997). If the reinforcing steel found in most structures is exposed to chlorides and oxygen, corrosion may occur over time. Overall, the greatest concern with increased levels of chlorine is the deleterious effect it has on the production process. 2.6.11 Chromium (Cr) Chromium is element number 24 on the periodic table, and it falls into the metal classification. Cr is a common element that can be found in any of the materials introduced into the kiln. Reports have shown chromium levels from 1.2 to 16 ppm in limestone, as well as 90 to 109 ppm in clay and shale. Additionally, the levels of chromium in fuels are on the order of 80 ppm in coal and 50 ppm in used oils (Bhatty 2004). Bhatty also reported that it is not unusual to introduce meaningful levels of Cr into the cement during the grinding of the clinker. The grinding balls as well as the added gypsum may contain significant amounts of chromium. The volatility of Cr is generally very low, thus it is primarily deposited in the clinker. However, if conditions in the kiln are right, Cr may volatilize and be concentrated in either the CKD or emissions at levels as high as 100 to 1000 ppm (Gartner 1980). One statistic that is particularly relevant to this study is that Bhatty (2004) reported Cr concentrations in the range of 0.01 to 299 ppm in CKD from facilities 72 that use waste-derived fuels, which is as much as an 11 percent increase relative to facilities using traditional fuels. The common presence of chromium has led to many studies on its effect on the properties of cement. Many researchers have found that chromium is directly related to concrete compressive strength. It has been reported that increased concentrations of Cr in the raw materials have shown improved early strength, but have resulted in a decrease in 28-day strength (Bhatty 2004; Gartner 1980; Miller 1976; Murat and Sorrentino 1996). Other effects attributed to increased Cr concentrations, as reported by Miller (1976), were higher heat of hydration, lower autoclave expansion, and increased 24-hour paste shrinkage. Gartner (1980) confirms that higher levels of Cr reduced autoclave expansion. Kakali, Tsivilis, and Tsialtas (1998) studied the effect of Cr on rate of hydration and found that it is slowed during the first two days, but the effect is negligible at 28 days. Stephan et al. (1999) reported decreases in setting time, as well as a lowered heat of hydration, for increased Cr concentrations, which contradicts Miller (1976). In a study conducted by Stephan et al. (2000), clinker samples were prepared using a raw mix dosed with various concentrations of Cr 2 O 3 , NiO, and ZnO, ranging from 5000 to 25,000 ppm. It should be noted that these are very high dosages of these compounds. The chemical composition of the raw meal before dosing is shown in Table 2.25. Once the cement was produced, a number of physical tests were conducted. Figure 2.9 shows the heat of hydration for the samples dosed with 25,000 ppm of each of the oxides. The sample dosed with chromium exhibited an accelerated rate of heat liberation, and a decrease in total amount of heat released. Figures 2.10 and 2.11 show the penetration, which is related to initial setting time, for the samples dosed with 25,000 and 5,000 ppm, respectively. The samples dosed with chromium showed accelerated setting times in both cases. This phenomenon was significantly more pronounced in the sample containing 25,000 ppm, however. The final tests conducted were compressive strengths on mortar cubes. Figures 2.12 and 2.13 show these results for the samples dosed with 25,000 ppm and 5,000 ppm respectively. In both cases, the compressive strength of the samples dosed with Cr 2 O 3 decreased at both dosage levels. The difference between the strength effects of the two concentrations was minimal. The results of the samples dosed with the other elements will be discussed in the following appropriate sections. Table 2.25: Chemical Analysis of Cement before Addition of Dosed Elements (Stephan et al. 2000) Oxide Portland Cement SiO 2 (wt.%) 14.1 Al 2 O 3 (wt.%) 3.5 Fe 2 O 3 (wt.%) 2.2 CaO (wt.%) 41.3 MgO (wt.%) 1.7 K 2 O (wt.%) 1.1 SO 3 (wt.%) 0.6 Cr (ppm) 51 Ni (ppm) 15 Zn (ppm) 88 Specific surface (m 2 /cm 3 )1.71 One additional concern with chromium is that it is a toxic element. Many authors, including Murat and Sorrentino (1996), agree that Cr may be easily leached from concrete. Therefore, special considerations must be made in order to prevent harmful 73 74 effects from concrete manufactured with portland cement with high concentrations of chromium. 2.6.12 Cobalt (Co) Cobalt is the 27 th element on the periodic table and a metal. Co is generally found in the raw materials as a trace element, with concentrations no more than 23 ppm (Bhatty 2004; Kolovos et al. 2002). It may also be found at levels significantly higher if fly ash is used a supplementary raw material (Bhatty 2004). When cobalt is present in the kiln, it is typically incorporated into the clinker, where it may be found at concentrations up to 130 ppm (Bhatty 2004). At concentrations this high, it has been reported that the clinker may exhibit changes in its properties such as altered color and increased hardness (Gartner 1980). Cobalt is typically found in cement at low levels, and the effects on the physical properties are therefore not well known. However, Miller (1976) reported that additions of Co might slightly reduce long-term strengths, as well as slightly increase water demand. Additionally, cobalt has been shown to retard hydration during the first two days (Kakali et al. 1998). 2.6.13 Copper (Cu) Copper is a metal and is the 29 th element on the periodic table. Cu is introduced into the kiln system predominantly by the raw materials. Approximate concentrations are on the order of 10 ppm in such components (Bhatty 2004). 75 Figure 2.9: Heat of Hydration for Cement with Various Concentrations of Cr, Ni, and Zn (Stephan et al. 2000) 76 Figure 2.10: Penetration of Cements Dosed with 25,000 ppm of Cr, Ni, and Zn (Stephan et al. 2000) 77 Figure 2.11: Penetration of Cements Dosed with 5,000 ppm of Cr, Ni, and Zn (Stephan et al. 2000) 78 Figure 2.12: Compressive Strength of Cements Dosed with 25,000 ppm of Cr, Ni, and Zn (Stephan et al. 2000) Figure 2.13: Compressive Strength of Cements Dosed with 5,000 ppm of Cr, Ni, and Zn (Stephan et al. 2000) 79 80 Copper is a volatile element, and the majority therefore attaches itself to the CKD. In fact, Cu has been known to show up in the CKD at levels up to 500 ppm (Bhatty 2004). A much smaller amount of the element is incorporated into the clinker. Bhatty (2004) claimed concentrations of Cu in clinker may reach values as high as 90 ppm. When copper is fused into the clinker, it has been known to influence a number of properties of the final product. First of all, copper in clinker has a tendency to produce a darker colored, sometimes tan, product (Bhatty 2004; Kolovos et al. 2002). Copper also affects the hydration properties of portland cement. Specifically, the addition of CuO to the raw mix has shown significant retardation of the hydration process, as well as a retardation of the amount of heat released during this hydration (Gartner 1980; Kakali et al. 1998; Miller 1976). In fact, Kakali et al. (1998) claim that CuO causes the greatest delay of hydration, even at 28 days, of all the transition elements. 2.6.14 Fluorine (F) Fluorine is the 9 th element and is a nonmetal. It is found in nearly all raw materials and fuels alike. Bhatty (2004) reported levels between 50 and 370 ppm in coal, and as much as 0.06 percent by mass in commercial raw materials. Fluorine is a prominent element in the manufacture of portland cement. 88 to 98 percent of all F introduced into the kiln may be incorporated into the clinker (Bhatty 2004). However, fluorine may take a number of different forms during clinkering, each of which has a different melting point. Therefore, it is not uncommon to find fluorine in both CKD and emissions, almost without exception at levels lower than in the clinker (Bhatty 2004). Gartner (1980), Miller (1976), and Taylor (1997) all claim that if F is 81 volatilized, it has a tendency to cycle in the CKD where it may lead to kiln rings or clogging of the precalciner. One of the properties that may be affected by concentrations of fluorine over 0.2 percent, by mass, is setting time. When the ambient temperature is below 5 degrees Celsius, setting time may be significantly slowed (Jackson 1998). However, setting time is slowed by a decrease in temperature in all cement. Miller (1976) reported that high levels of fluorine increase 28 day compressive strength. Jackson (1998) reported, however, that concentrations over 0.5 percent decrease compressive strength. 2.6.15 Lead (Pb) Lead is element number 82 and is a semi-metal. It may be present in both raw materials and fuels, the latter of which has a tendency to exhibit higher concentrations. Lead is of particular concern with nontraditional fuels, such as used oils and tires, where its concentrations may be higher (Bhatty 2004). Lead is a volatile element, which results in higher concentrations in the emissions and CKD (Bhatty 2004; Gartner 1980; Taylor 1997). Despite this fact, substantial concentrations of lead have been detected in the clinker (Bhatty 2004; Gartner 1980). When lead is present in clinker, it has been shown to have a number of different effects. Many researchers have found that lead in portland cement has a direct retarding effect on setting time (Gartner 1980; Murat and Sorrentino 1996; Taylor 1997). This is especially true at levels above 0.2 percent by weight (Miller 1976). Although retarded 82 setting times would generally be detrimental, Miller (1976) claimed that when setting time is not an issue, lead may actually increase the 28-day compressive strength. In addition to the effects that lead may have on the properties of cement, its effects on the environment must also be considered. Lead is a toxic chemical, whose introduction into the environment must be closely monitored in order to ensure a healthy environment is sustained. Additionally, the leachability of the element must also be studied in order to prevent its introduction through the placement of concrete. Gartner (1980) and Murat and Sorrentino (1996) agree that at lead dosages as high as five percent it does not generally leach from concrete. 2.6.16 Lithium (Li) Lithium is element number three, and is classified as a metal. Its presence in the kiln is usually attributed to raw materials, but in almost undetectable quantities. If wastes are being used as a fuel source, concentrations may be considerably higher (Bhatty 2004). If Li is present in the kiln, it will be incorporated into the clinker since it is not a volatile element. However, this is generally at very low concentrations. If levels of Li are elevated, the most reported effect is that it may slow the rate of reaction between the alkalis and the aggregate in concrete (Gartner 1980). In fact, lithium has been proven very effective at reducing concrete?s susceptibility to alkali-silica reaction. Figure 2.14 shows the results of a test conducted by Kawamura and Fuwa (2001) in which expansion due to alkali-silica reaction was monitored. The expansion of the concrete was reduced when 1 % and 1.5 % dosages of LiCO 3 compared to when no dosage was used. Figure 2.14: Effect of Various Doses of Li 2 CO 3 on ASR Expansion (Kawamura and Fuwa 2001) 2.6.17 Magnesium (Mg) Magnesium is element number 12 and classified as a metal. It is very common in most of the raw materials, where it may be present at concentrations as high as 0.63 percent (Bhatty 2004). The Mg that is introduced into the kiln is almost exclusively incorporated into the clinker. Trace amounts may be found in the CKD or emissions. Bhatty (2004) reported that Mg may be found in the clinker at concentrations as high as 8900 ppm. Magnesium concentrations of 0.5 percent, by mass, or greater can potentially decrease early strengths (Taylor 1997). Gartner (1980) claimed no dramatic changes in setting or hardening properties are brought about by high concentrations of Mg. 83 84 Generally speaking, Mg is regarded as a good thing in cement due to its benefits on the production process with minimal effects on the properties. ASTM C150 specifies an upper limit of six percent MgO in cement. 2.6.18 Manganese (Mn) Manganese is element number 25 and is classified as a metal. Mn is a common element, and has a marked presence in the production of portland cement. Manganese can be found in both raw materials and fuels. It is not uncommon to find levels of Mn 2 O 3 in limestone up to 1.91 percent, as well as up to 58.9 percent in shale and 36.7 percent in bauxite (Bhatty 2004). Nontraditional raw materials such as slag may contain higher levels of Mn than their traditional counterparts (Miller 1976). It is highly unlikely that Mn will vaporize in the kiln process, and will therefore be incorporated into the clinker in most cases (Gartner 1980). The boiling point of Mn is 1960?C. It will therefore not typically volatilize and attach to CKD particles (Bhatty 2004.) An increase in manganese has been reported to produce decreased compressive strengths (Bhatty 2004; Miller 1976). However, at levels of 0.7 percent or more, it has been shown to impart high early strength (Gartner 1980). Mn has also been found to cause various changes in color to clinker (Gartner 1980; Taylor 1997). In particular, ?reddish-brown to blue casts have been observed in manganese-containing clinkers (Bhatty 2004; Miller 1976).? 85 2.6.19 Mercury (Hg) Mercury is the 80 th element and is classified as a metal. Hg may be found in very small quantities in both raw materials and fuels. Some typical concentrations, provided by Bhatty (2004), are limestone 0.03 ppm, clay/shale 0.45 ppm, and coal 0.27 ppm. Mercury is a volatile element, and will therefore be found in the CKD and emissions. The concentrations in either place are primarily very low due to the low levels of the element entering the kiln. However, it has been found that plants that use waste fuels in place of traditional fuels have shown an increase in mercury emission mass flow rates from 0.984 mg/sec to 2.14 mg/sec (Mantus et al. 1992). Due to the scarcity of substantial levels of mercury in the clinker, very little is known about its effect on the product. It is nevertheless necessary to monitor mercury levels due to its toxic nature. Gartner (1980) reported that if mercury forms the HgO compound and is incorporated into the clinker, it has a tendency to leach from concrete. This is certainly a concern, and must be closely observed. 2.6.20 Molybdenum (Mo) Molybdenum is number 42 and is a metal. Mo can be present in both raw materials and fuels in significant quantities. One supplementary raw material of particular interest is coal fly ash, which has been shown to contain molybdenum at levels up to 1.5 percent by weight (Bhatty 2004). Molybdenum is not a volatile element and, in conjunction with its abundant presence in the kiln components, can potentially be found at high concentrations in the 86 clinker. Blaine, Bean, and Hubbard (1965) have reported that these concentrations could be as high as 0.05 percent. Due to the potentially high levels of Mo in clinker, the effects that it may have on cement and concrete properties have been well documented. Taylor (1997) reported that concentrations up to 0.5 percent increase 28-day strength, but at concentrations above three percent that same strength may be significantly reduced. Another effect that has been attributed to high concentrations of Mo is the rate of setting. The effects of hydration are slightly retarded during the first two days (Kakali et al. 1997). 2.6.21 Nickel (Ni) Nickel is element 28 and a metal. Oil and coal have been observed to have high levels of nickel (Miller 1976). These may be on the order of 3 to 30 ppm and 20 to 80 ppm, respectively (Bhatty 2004). Additionally, Bhatty (2004) reported levels of 1.5 to 7.5 ppm in limestone, 61 to 71 ppm in clay/shale, and 208 ppm in petroleum coke. Miller (1976) also reported higher levels of nickel in black shale as well as in refuse-derived fuels. It has been shown that Ni may exhibit volatile characteristics when subjected to coal combustion, resulting in its incorporation into the CKD (Gartner 1980). However, nickel amounts of up to 0.02 percent in clinkers have also been reported (Blaine et al. 1965). Bhatty (2004) confirms that the location of Ni is dependent on the compound it forms, and may be incorporated in clinker or CKD. Compressive strengths have reportedly been improved by higher concentrations of Ni. Levels of 0.5 to one percent have been responsible for increases in 1-day and 5- 87 year strengths (Gartner 1980). Another property that may be affected by nickel is hydration. Miller (1976) stated that water-soluble nickel is an accelerator for cement hydration, while nickel in clinker at levels up to 0.02 percent has very little effect on hydration. High levels of Ni may also produce a dark brown color in clinker (Bhatty 2004). The results concerning nickel additions in the study conducted by Stephan et al. (2000) (as described in section 6.11) can be seen in Figures 2.9 through 2.13. From Figure 2.9, the rate of hydration and the total hydration energy were approximately unchanged due to nickel addition. Figures 2.10 and 2.11 show the rate of setting was also approximately unchanged for both levels of nickel addition. Finally, Figures 2.12 and 2.13 show that the compressive strength decreased at early ages and increased at later ages for both nickel addition levels. 2.6.22 Nitrogen (N) Element number seven is nitrogen. In its natural state, nitrogen is a gas. N, in solid form as an oxide, can be found in both raw materials and fuels, and may be present at high levels. Specifically, nitrogen may be found at 0.01 percent in raw materials, and as high as two percent in fuels (Bhatty 2004). Nitrogen is always present in kiln systems in the form of combustion air. However, it generally remains in the gaseous form and is released with the stack emissions. A detailed discussion of nitrogen emissions can be found in Section 2.4.2. 88 2.6.23 Phosphorus (P) Phosphorus is element number 15 and is classified as a nonmetal. The most common form of phosphorus in the cement process is P 2 O 5 . Phosphorus is generally introduced into the kiln through limestone (Jackson 1998), but is present at some levels in most raw materials. It may exist at concentrations above one percent in many raw materials (Gartner 1980). Research conducted by the Portland Cement Association (PCA) has found that waste lubricating oil, as well as other refuse-derived fuels may exhibit substantial levels of phosphorus (Miller 1976). P 2 O 5 is not a volatile compound in the kiln process, and will usually be incorporated into the clinker. A typical concentration for P 2 O 5 in cement clinker is 0.2 percent (Taylor 1997). Jackson (1998) agrees, reporting typical values of 0.03 to 0.22 percent. Although Miller (1976) claimed that P 2 O 5 at levels below 0.5 percent have no measurable effect, if that threshold is surpassed, phosphorus may produce a slight decrease in water requirements, slightly lower heat of hydration, and shows a tendency toward paste shrinkage. Gartner (1980) also reported serious decreases in strength at P 2 O 5 levels above 2.5 percent. Concrete hardening becomes slower with high levels of P 2 O 5. Figure 2.15 shows the effect of P 2 O 5 content on compressive strength (Miller 1976). From this figure, it can be seen that there is an optimum P 2 O 5 content at approximately 2.5 percent, above which compressive strength decreases. However, based on the P 2 O 5 concentrations reported by Taylor (1997) and Jackson (1998), it may be concluded that most cements will contain less than this optimum P 2 O 5 concentration. Figure 2.15: Compressive Strength for Different P 2 O 5 Concentrations (Miller 1976) 2.6.24 Rubidium (Rb) Rubidium is element number 37 and a metal. It is generally found only in small concentrations in the raw materials (Bhatty 2004). Gartner (1980) claimed that Rb acts similarly to potassium, in that it has a tendency to form rings in the kiln and to promote clogging throughout the system. 89 90 The levels at which rubidium is present in clinker are typically very low. Miller (1976) stated that although the concentrations may be low, Rb may affect cement in a number of ways. First, it may have a negative effect on compressive strength at all ages. Additionally, the paste may shrink more than a paste with lower concentrations of Rb. Rubidium may also be a culprit in the expansion of concrete, as well as in reducing its ability to resist freezing and thawing cycles. More water may also be required to properly hydrate cement with high levels of Rb (Bhatty 2004). More research is required to determine if these changes in properties can be accurately attributed to rubidium. 2.6.25 Strontium (Sr) Strontium is the 38 th element and a metal. The presence of Sr is not uncommon in the raw materials, particularly in CaCO 3 sources, such as limestone (Bhatty 2004). The concentrations are not especially high, however. Because Sr is not volatile, it is generally trapped in the clinker, where it would not be uncommon to find strontium at levels on the order of 0.5 percent by weight (Bhatty 2004; Gartner 1980). Although the concentrations at which strontium has been observed in the clinker are not high, researchers have reported that the effects on the physical properties may be many. Miller (1976), in particular, outlined a number of possible effects Sr may produce. Namely, lower strengths, higher autoclave expansion, lower heat of hydration at 28 days, and increased concrete shrinkage were observed. Gartner (1980) confirmed that strontium ?is marginally deleterious to cement strength and other physical properties.? 91 2.6.26 Sulphur (S) Sulphur is a nonmetal and element number 16. Sulphur may be introduced into the kiln through both raw materials and fuels (Jackson 1998). Fuels such as coal and oil are particularly prone to high levels of sulphur (Gartner 1980). Limestone, clayey sediments, and marl also contain appreciable quantities of sulphur (Bhatty 2004). The primary source of SO 3 in cement is the addition of gypsum during grinding of the clinker. The levels of SO 3 added are closely monitored in order to produce the desired effects in the cement, such as control of setting times. The optimum quantity of SO 3 added is on the order of three to five percent (Taylor 1997). ASTM C150 limits the amount of gypsum that may be added. Some sulphur in the form of SO 2 is released through the stack emissions. A detailed discussion of sulphur emissions can be found in Section 2.4.3. The most common place for sulphur to be found is in the clinker. This is likely to occur because sulphur prefers to combine with alkalis (Gartner 1980), which are readily available in most kiln systems. As was mentioned in Section 2.6.1, alkali sulfates have a tendency to volatilize in high temperature areas, and condense in cooler temperature areas, where they may form kiln rings or clogs in the preheater system (Gartner 1980). This is obviously detrimental to the production process. Many production facilities have chosen to break the cycle of vaporization and condensation by removing alkali sulfates from the system in the CKD (Bhatty 2004; Gartner 1980). ?The effect of the presence of sulfates is intimately connected with those of the alkalis? (Jackson 1998). Gartner (1980) claimed that the presence of sulphur in clinker has no deleterious effects, so long as it is maintained at acceptable concentrations. 92 Otherwise, it may retard setting time and inhibit strength gain. If SO 3 is present at excessive levels, the cement paste will have a tendency to expand at an increased magnitude. The overall early hydration rate of portland cement is retarded as the levels of sulfate are increased (Jackson 1998). Jackson (1998) also reported that sulphur incorporated into the clinker phases has an accelerating effect on setting. There is an optimum gypsum content for all portland cements, which is specific to the chemical composition of that particular clinker. If SO 3 is added in excess of this optimum concentration, strengths, especially at early ages, are known to decrease (Jackson 1998). 2.6.27 Thallium (Tl) Thallium is element number 81, and is classified as a semi-metal. Another trace element, Tl may be found in small quantities in both raw materials and fuels. The largest values reported were on the order of 1 ppm in coal (Bhatty 2004; Gartner 1980). One of the most volatile of all elements introduced into the kiln, thallium almost certainly ends up in the CKD or emissions. Therefore, it has little to no effect on clinker properties. However, in a facility where the CKD is recycled without regular disposal, thallium has been shown to build up to concentrations as high as 10,000 ppm (Bhatty 2004). If this happens, serious problems may form in the kiln system such as clogging of the precalciner. One additional concern with Tl is its high toxicity. Because of this, its levels must be monitored closely in order to ensure health and safety. 93 2.6.28 Titanium (Ti) Titanium is the 22 nd element and is classified as a metal. It may be found in concentrations on the order of 0.1 to one percent in most kiln feeds (Gartner 1980). Ti may also be found in certain auxiliary raw materials such as slag (Miller 1976). Bhatty (2004) reported TiO 2 levels in such materials of 1.7 percent in slag and two to eight percent in bauxite. Miller (1976) also claimed there may be substantial Ti content in some refuse-derived fuels. Titanium is not volatile in the kiln system (Gartner 1980). Therefore, it is typically incorporated into the clinker (Bhatty 2004). Jackson (1998) claimed that the levels of TiO 2 in typical portland cement clinkers are between 0.14 percent and 0.43 percent. Knofel (1976) reported that titanium concentrations in the range of one to two percent as TiO 2 produces improved cement strengths. Jackson (1998) reported TiO 2 levels up to one percent decrease one-to-two day strengths, but may improve strengths at ages greater than three days. Two percent Titanium has also been reported to slightly retard hydration during the first two days (Kakali et al. 1998). Miller (1976) reported that at Ti levels less than one percent there is little evidence to support any substantial deleterious effects. Titanium may lead to increased water demand as well as may give the cement a yellow color (Miller 1976). Taylor (1997) claimed the color change associated with Ti is of a darker nature. 94 2.6.29 Vanadium (V) Vanadium is the 23 rd element and a metal. V can be readily found in both raw materials and fuels. Limestone has been known to contain V at concentrations of 10 to 80 ppm, with even higher levels reported in clay and shale. Coal may have vanadium up to 50 ppm (Bhatty 2004). Gartner (1980) reported that vanadium may be found at ?very high levels? in crude oil, and when introduced into the kiln at such levels, it has a tendency to deteriorate the kiln lining. When vanadium is introduced into the kiln, its tendency is to combine with oxygen to form V 2 O 5 . This compound is mostly stable throughout the clinkering process, and will therefore be incorporated primarily into the clinker (Bhatty 2004). It is not uncommon, however, to be present in detectable quantities in both the CKD and emissions. The effects of vanadium on cement and concrete are numerous. V has a tendency to produce increased expansion characteristics in the presence of sulfate (Gartner 1980; Miller 1976). It has also been suggested that vanadium additions result in a higher water demand (Miller 1976). In the study conducted by Kakali et al. (1998), concerning the effects of certain elements on hydration, it was determined that vanadium slightly retards hydration in the first 2 days. Jackson (1998) stated that 0.2 percent, by mass, may lead to a 10 percent reduction in the 28-day compressive strength. 2.6.30 Zinc (Zn) The metal zinc is element number 30 on the periodic table. Zinc may be present in concentrations from 22 to 115 ppm in limestone and clay/shale, 16 to 220 ppm in coal, 95 and as high as 10000 ppm in alternative fuels such as tires (Bhatty 2004). Certain byproduct raw materials such as fly ashes may have appreciably higher levels of zinc than more traditional materials (Miller 1976). Some refuse-derived fuels have shown high levels of zinc as well (Miller 1976). About 10 to 20 percent of zinc is volatile in the kiln process. This portion has a tendency to be incorporated into the CKD (Miller 1976). Gartner (1980) claimed ?virtually all of the ZnO is retained in the clinker if the kiln dust is recycled.? In this case, zinc may be incorporated into the clinker at levels up to 0.2 percent (Blaine and Bean 1965). Barros et al. (2004) claimed that 90 percent of ZnO may be incorporated into the clinker. Bhatty (2004) reported that between 80 and 90 percent of ZnO in the kiln feed may end up in the clinker. If zinc is captured and recycled in the CKD, it is possible for it to form deposits in the preheater as well as in the kiln in the form of kiln rings (Taylor 1997). When this phenomenon occurs, serious problems may arise throughout the production process. Blaine et al. (1965) have reported increased strength at five and ten years, decreased paste shrinkage at 1 and 28 days, and decreased concrete shrinkage due to increased levels of ZnO. Gartner (1980) claimed that additions of Zn in the raw mix decreased early strength while increasing long-term strength, and soluble Zn 2+ leads to severe retardation of hydration. Miller (1976) also reported retarded setting times, decreased strengths, and changes in color when appreciable levels of zinc are present. Kakali and Parissakis (1995) agreed, reporting a brown color being imparted on the clinker. Zinc at concentrations on the order of 0.01 to 0.2 percent have been shown to lead to retardation of setting time, but when the level is maintained below 0.5 percent, 96 there are no profound effects on other hydraulic properties (Jackson 1998). Murat and Sorrentino (1996) have shown that when extremely large quantities of ZnO (approximately ten percent) are mixed with cement, setting time is retarded and strengths are reduced. The results of the study conducted by Stephan et al. (2000) concerning zinc additions can be seen in Figures 2.9 through 2.13. Figure 2.9 shows that zinc severely retards setting time, and increases the amount of heat released during hydration. Figures 2.10 and 2.11 show that zinc severely decreases setting time at concentrations of 25,000 ppm, but has little effect on setting at the 5,000 ppm level. Finally, Figures 2.12 and 2.13 show the effect of zinc on compressive strength. At both concentrations reported, the effects were negligible. 2.6.31 Zirconium (Zr) Zirconium is the 40 th element on the periodic table. It is classified as a metal. Although the raw materials are the most meaningful source of Zr, the concentrations there are not very high. Miller (1976) reported zirconium levels of 0 to 0.5 percent by weight in the raw materials. A number of possible effects of zirconium on the properties of cement have been reported. Modestly higher compressive strengths at all ages, a reduction in water requirements, and higher heat of hydration were all mentioned by Miller (1976). Additionally, Gartner (1980) reported that zirconium may increase early strengths, but admits the effects of high concentrations are unknown. 97 2.7 Conclusion The production of portland cement is a tremendously fuel-intensive process. Typically, the cost of fuel accounts for 30 to 40 percent of the total production costs (Mokrzycki et al. 2003). Because of this, cement producers are turning to cost-efficient alternative fuels at an increasing rate. Typically these fuels are derived from byproducts from other industries. Using such fuels allows the cement industry to save substantial amounts of money. Additionally, the use of wastes is beneficial to the environment. By reducing the amount of fossil fuels consumed, reducing landfill demand, and typically decreasing harmful greenhouse gases, the implementation of wastes in this way benefits us all. Although the benefits of using waste fuels in the cement industry are significant, there are issues that must be considered in order to fully utilize these fuels. Primarily, the composition and performance of the cement must not be compromised. If it is, the use of these fuels is not a viable option. Additionally, it has been shown that, in some cases, emissions of potentially harmful elements have increased due to the incineration of some material waste. If alternative fuels are to be used, these emissions must be monitored and effectively controlled. Careful consideration of alternative fuel implementation must be made by the cement industry. If the appropriate fuels are selected in the appropriate situations, the producers, the environment, and the world will benefit from this technology. 98 CHAPTER 3 TEST METHODS 3.1 Introduction The production of portland cement is a complex process, involving many materials and complex systems working in tandem. In Section 2.2 the production process is discussed in detail. In order to satisfy the objectives of this project, a thorough sampling and testing program was developed. The program described in the following sections was used to collect and analyze samples of every material used in the production of portland cement at this particular facility. The scope of this project included eight distinct collection and testing periods, which are referred to as burns. They are as follows: 1. C burn utilized only coal as fuel. 2. CT1 burn utilized coal and tires. This is the standard fuel combination used at the cement plant, and was therefore considered the baseline for comparison purposes. This is the first baseline burn. 3. CTP burn used coal, tires, and waste plastics. These plastics were considered alternative fuel one. 99 4. CT2 burn utilized coal and tires. Again, the standard fuel combination was used, and this is the second baseline burn. 5. CTB burn used coal, tires, and broiler litter. Broiler litter was the second alternative fuel tested. 6. CT3 burn utilized coal and tires. Again, the standard fuel combination was used, and this is the third baseline burn. 7. CTW burn used coal, tires, and woodchips. Woodchips was the third alternative fuel tested. 8. CTS burn used coal, tires, and switchgrass. Switchgrass was the fourth alternative fuel tested. All these burns, here onwards in this document, will be referred to by their respective lettered names as indicated above. In each burn, all materials were sampled and tested in accordance with the program described in the following sections. A schematic of the overall sampling and testing plan is shown in Figure 3.1 The first phase in the testing program was to collect samples of all of the materials involved in the process. The cement plant already had a program in place for collecting samples of these materials as a part of their quality control process. Due to their established collection frequencies and for convenience, it was decided to collect samples at the same frequencies as were used by the plant. These frequencies, as well as the particular materials and sample quantities, are discussed in the following sections. 100 The second half of the testing program was the actual testing of the materials that were collected. Many different tests were implemented in this program to be as thorough as possible. This was particularly true for the testing of the portland cement itself. The specific tests that were conducted are discussed in the appropriate sections that follow. 3.1.1 Definitions The process of sampling refers to the method by which a quantity of material is collected at the cement plant. A specimen is the material on which a test is conducted. A discrete sample is a batch of material collected at a specific time and location at the cement plant. A composite specimen is prepared, in accordance with Section 3.3.2, using discrete samples taken over a given period of time. A daily composite is a composite specimen that is prepared from discrete samples that were collected over a 24-hour period. A three-day composite is a composite specimen that is prepared using discrete samples taken over a 72-hour period. 3.2 General Test Planning and Overview The comprehensive testing plan, presented in tabular form, is given in Appendix A. This testing plan presents an overview for the materials that were sampled, sampling frequency, specimen preparation methods, tests conducted, as well as other pertinent information concerning sampling and testing. 101 Figure 3.1: Sampling and Testing Plan 102 Sampling frequency refers to the frequency at which discrete samples were collected at the cement plant. Specimen preparation method describes the manner in which samples were prepared for testing, that is, whether the discrete samples were tested directly , or if composite specimens were prepared from the discrete samples collected. Discussion of specimen preparation methods is given in Section 3.3.2. The actual dates of burns conducted are given in chapter 4. A graphical timeline for the typical sampling period of all the burns can be found in Figure 3.2. 3.2.1 Collection of Materials All of the materials used in the production process were sampled and tested for various properties. All of these materials (except cement kiln dust) can be divided into two categories. These categories are process inputs and process outputs. Process input materials are those that are used to produce portland cement. The inputs at this specific cement plant were six raw materials and the different fuels. The sources of the raw materials were classified as proprietary information by the cement plant and hence cannot be revealed, however, they shall be referred to as Raw Materials One to Six in this document Five of the six raw materials were combined in strictly controlled proportions in order to produce a material known as kiln feed. The kiln feed is the material that is sent into the kiln, where in the presence of high temperatures produced by the combustion of the fuels, it is chemically transformed into clinker. The sixth raw material is combined with the clinker prior to grinding to produce portland cement. Each of these process input materials was sampled and tested for various properties as described in the following sections. 103 Figure 3.2: Sampling Timeline 104 The process output materials are clinker, portland cement, and emissions. Each of these process output materials was sampled and tested for various properties as described in the following sections. However, an emphasis was placed on the primary output of the plant, portland cement. The cement kiln dust (CKD) is primarily composed of fine particulate matter that does not combine with the other materials in the kiln to become clinker. It is discussed in detail in Section 2.3. What distinguishes CKD from the other materials is that it is both an output and an input of the process. It is a byproduct of the clinkering process, but it is recycled back into the kiln feed just before entering the kiln. CKD was sampled and tested for various properties as described in Section 3.3.5. It must be noted that the CTS burn had a pre-burn period of coal and tires as fuel for only one day and the burn itself lasted for only two days due to insufficient supply of switchgrass. 3.2.2 Types of Tests The primary test conducted on all materials was a chemical analysis. The chemical compounds were determined by X-Ray Fluorescence (XRF), and the components were reported either as percent by weight (wt. %), or as parts per million (ppm). The former is the percentage of the total unit weight of the chemical or component in question. Parts per million (ppm) is actually measured as ?g/g. PPM units were used for many of the elements that had a relatively small presence in the material being examined. 105 XRF was used to determine the chemical compositions at the cement plant and the external laboratory, with one exception. Raw Material Three was not tested by XRF at the cement plant. In this case, the chemical composition was determined by a Prompt Gamma Neutron Activation Analyzer (PGNAA). The testing of the emissions did not include a chemical analysis and the details of this testing are discussed in Section 3.3.10. The cement plant and the external laboratory both tested the chemical composition of the materials; however, the standard elements tested for differed somewhat between the two testing entities. In Table 3.1, the standard parameters that were examined by personnel the cement plant and by those at the external laboratory are shown. Each of the parameters shown in Table 3.1 was determined by XRF, except for Na 2 O eq , which was calculated from the concentrations of Na 2 O and K 2 O by the formula presented in ASTM C 150. The approximate detection limits for the XRF used at the external laboratory are shown in Table 3.2. Concrete was made from the portland cement collected during each of the burns. The specific tests associated with concrete are described in Section 3.3.9. Any other tests that were specific to only one material are discussed in the section pertaining to that material. Table 3.1: Standard Chemical Parameters Standard Cement Plant Parameters (wt. %) (wt. %) (ppm) Al 2 O 3 Al 2 O 3 Arsenic (As) CaO CaO Barium (Ba) Fe 2 O 3 Fe 2 O 3 Cadmium (Cd) K 2 OK 2 O Chlorine (Cl) MgO MgO Cobalt (Co) Na 2 ONa 2 O Chromium (Cr) Na 2 O eq P 2 O 5 Copper (Cu) SiO 2 SiO 2 Mercury (Hg) SO 3 SO 3 Manganese (Mn) Moisture TiO 2 Molybdenum (Mo) Loss On Ignition Moisture Nickel (Ni) Loss On Ignition Lead (Pb) Tin (Sb) Selenium (Se) Strontium (Sr) Vanadium (V) Zinc (Zn) Standard External Lab Parameters 106 Table 3.2: Approximate Detection Limits for XRF used at the External Laboratory Parameter Lower Limit of Detection Al 2 O 3 (wt. %) 0.01 CaO (wt. %) 0.01 Fe 2 O 3 (wt. %) 0.01 K 2 O (wt. %) 0.01 MgO (wt. %) 0.01 Na 2 O (wt. %) 0.01 P 2 O 5 (wt. %) 0.01 SiO 2 (wt. %) 0.02 SO 3 (wt. %) 0.01 TiO 2 (wt. %) 0.01 Moisture (wt. %) 0.01 LOI (wt. %) 0.01 As (ppm) 2 Ba (ppm) 40 Cd (ppm) 3 Cl (ppm) 5 Co (ppm) 10 Cr (ppm) 16 Cu (ppm) 13 Hg (ppm) 0.01 Mn (ppm) 12 Mo (ppm) 9 Ni (ppm) 9 Pb (ppm) 4 Sb (ppm) 20 Se (ppm) 1 Sr (ppm) 16 V (ppm) 20 Zn (ppm) 9 107 108 3.3 Detailed Test Procedure 3.3.1 Plant Layout, Sample Collection Locations, and Collection Methods Figure 3.3 shows a schematic layout of the cement plant, including material paths, sample collection points, and important facilities. As mentioned earlier, due to the proprietary nature of the raw materials, they can only be identified as Raw Material One through Six. The main raw material, Raw Material Three, is mined from the quarry and unloaded into the primary crusher where it is reduced to a manageable size. From the primary crusher, Raw Material Three is sent by conveyor through the Prompt Gamma Neutron Activation Analyzer (PGNAA) for determining its chemical composition, which is discussed in Section 3.3.3. Once it is analyzed by the PGNAA, it is either stockpiled for later use, or sent directly to the proportioning equipment. Based on the chemical analysis of Raw Material Three, Raw Materials One, Two, Four, and Five are added to the stream by the proportioning equipment in order to meet the chemical requirements to produce portland cement. Sample Points One through Four in Figure 3.3 apply to Raw Materials One, Two, Four, and Five respectively. These raw material samples were collected by removing approximately one gallon of material directly out of the stream just before they were added to Raw Material Three. The one gallon tin pail in which they were collected is referred to as the typical container from this point forward. Figure 3.4 shows a typical sample point for the raw materials. 109 Figure 3.3: Diagram of the Cement Plant (Adapted from Swart 2007) Figure 3.4: Raw Material Sample Point Once the raw materials have been proportioned, they are sent to the roller mill, which grinds the material to the desired particle size distribution. They are then sent to the homogenizing silo. Just before the raw materials enter the homogenizing silo, recycled cement kiln dust (CKD) is added. Once the materials enter the silo, they are mixed to produce a homogeneous mixture known as the kiln feed. After the kiln feed was blended, a sample was taken at Sample Point Five in Figure 3.3, by inserting a pint- sized tin container directly into the stream, as shown in Figure 3.5. Before the CKD was added to the raw materials, a sample was collected at Sample Point 14 in Figure 3.3, in the same manner as for the kiln feed. From the homogenizing silo, the kiln feed is sent to the preheater/precalciner. Once the kiln feed makes its way completely through the preheater/precalciner, it goes into the rotary kiln where it is chemically fused to produce clinker. The clinker then exits 110 the kiln and is sent directly to the clinker cooler. The clinker was sampled at Sample Point Six immediately after it exited the kiln, as shown in Figure 3.3. A rod with the top half partially removed to form a trough was inserted directly into the clinker stream, where a small volume of clinker was removed and collected into the typical container as shown in Figure 3.6. Figure 3.5 : Kiln Feed Sampling Figure 3.6 : Clinker Sampling 111 The preheater/precalciner-rotary kiln system has two locations at which fuel is introduced. The back end is considered to be the upper end of the kiln. This is where approximately 60 percent of the coal is consumed at this particular plant. Additionally, because of their large size, all of the alternative fuels are introduced at this end of the kiln. The remaining 40 percent of the coal is injected at the front end of the kiln, which is the lower end. The coal was sampled at Sample Point 16 in Figure 3.3 by an automated plunger system that removes material from the stream, and empties it into the typical container, as shown in Figure 3.7. The tires are sent into the kiln through a conveyor system that drops them directly in one at a time. This process is shown in Figure 3.8 and Figure 3.9. 112 Figure 3.7: Automated Plunger Removing Coal Samples The broiler litter, plastics, woodchips and switchgrass are injected just below the tires? injection point using a conveyor and screw system as shown in Figure 3.10. The tires, plastics, broiler litter, woodchips and switchgrass were sampled at Sample Points Nine, Ten, Eleven, Twelve and Thirteen in Figure 3.3, respectively. Tires were sampled by removing a single tire from the conveyor at a time. Preparation of tire samples is discussed in Section 3.3.2. All other alternative fuels were sampled by inserting the typical container directly into the feed stream. Figure 3.8: Tires Transported to Kiln 113 Figure 3.9: Tire Entering Kiln Conveyor Screw Figure 3.10: Alternative Fuel Kiln Injection System 114 115 Once the clinker has cooled, it is sent, along with Raw Material Six, which was sampled at Sample Point Seven in Figure 3.3, to the finish mill. The finish mill grinds these two materials together to form the final product, portland cement. After the materials are ground, the portland cement was sampled at Sample Point Eight in Figure 3.3, by an automated plunger that removes the product from the mill, and empties it into a five-gallon plastic bucket. This process is shown in Figure 3.5. Finally, the finished product is either sent to storage, placed in bags, or loaded directly into trains or trucks for distribution. Figure 3.11: Automated Plunger Collecting Cement Samples 116 3.3.2 Sample Preparation, Shipping, and Storage Once all of the samples were collected for a given sampling period, the samples were prepared for shipping or testing. Containers that were filled with samples were each emptied into a two-gallon, heavy-duty, plastic bag, which was labeled with the material type, date of sampling, and time of sampling. In many cases, single discrete specimens were tested by the external laboratory. In this case, a small portion (approximately two kilograms) was removed from the sample bag, placed into a separate bag, labeled with a sample identification number, and sent directly to the external laboratory. Many of the samples were not tested as discrete specimens, but as composite specimens produced over either an entire day of sampling, or over a three-day period of sampling. In order to produce composite specimens, a small quantity (approximately one half kilogram) was taken from each of the sample bags pertaining to the composite period, and placed into a five-gallon bucket. Once the bucket was filled with all the appropriate samples, it was rolled on its side 60 feet in one direction and back again along same path. This method was used to minimize the human interference in the composite specimen creation process. Once the material had been thoroughly mixed, two kilograms were removed, placed in a plastic bag, and labeled. Once all of the composite specimens were produced, and all necessary specimens (both composite and discrete) had been bagged and labeled, they were placed into boxes and sent to the external lab for testing. For the sake of possible future testing, the samples originally collected at the plant were only partially used for testing. Approximately two kilograms of each sample were stored in a cool, dry place 117 indefinitely. The specimens that were tested by the cement plant were not prepared by Auburn University staff. 3.3.3 Analyzing the Chemical Composition of Raw Materials There were seven raw materials that were tested. The raw materials? sources and names were not used, because that information is proprietary information of the cement plant. The primary raw material sampled and tested was known as the kiln feed( labeled Raw Material Seven), which was produced by combining Raw Materials One through Five in closely controlled proportions. The kiln feed, Raw Material Seven, was sampled at a frequency of two times a day over the standard sampling period. Each of the discrete samples was tested by the cement plant as described later in this section. Additionally, after each of the discrete samples was collected, a single composite specimen was prepared, in accordance with Section 3.3.2, over each three-day period during the standard sampling period. These composite specimens were tested by the external laboratory as described below. In addition to the kiln feed, each of the individual raw materials from which it is composed, Raw Materials One through Five,was sampled and tested. The samples of these individual raw materials were collected less frequently than the kiln feed. A single discrete sample of each was collected during every burn. Both the cement plant and the external laboratory tested these discrete specimens as described below. The final raw material collected and tested was Raw Material Six, which was mixed with the clinker, prior to grinding, to produce portland cement. The frequency of sampling for Raw Material Six was one discrete sample collected during the grinding 118 process for each of the burn phases. A single discrete specimen was tested by both the cement plant and the external laboratory as described below. The test specimens for each of the raw materials were analyzed for the standard parameters shown in Table 3.1 by XRF, with the exception of Raw Material Three. The chemical composition of Raw Material Three was not determined by XRF, but instead by a Prompt Gamma Neutron Activation Analyzer (PGNAA), which was capable of determining these concentrations in real time. This device determined the concentration of all of the standard cement plant parameters shown in Table 3.1, except for moisture and loss on ignition (LOI). 3.3.4 Analyzing the Chemical Composition of Fuel Sources Each of the six fuel sources was sampled at different frequencies. Although the quantity of testing was different for each of the fuels, the actual tests conducted were the same. Coal, the primary fuel source, was sampled twice a day over the standard sampling period. Three-day composites were then prepared from the discrete samples in accordance with Section 3.3.2. These composites were tested by the external laboratory as described below. A single discrete specimen was tested by the cement plant as described below. Tires were sampled by collecting eight different tires during each burn. From these tires, eight discrete radial sections were removed, one section from each tire. These radial sections were then cut down into one inch square pieces, which were made into individual composite specimens to be tested by the external laboratory alone. Tires were sampled once during each burn in which they were used. Sampling of all the alternative fuels was the same. Eight discrete samples were taken for each fuel in a single day. These samples were collected only in the burn phase to which they applied. Each of the discrete specimens was tested by the external laboratory only. In addition, two of the discrete samples from each day were tested in duplicate in order to ensure accuracy. The testing of the fuel sources at the external laboratory was the same for all of the fuels. First, an XRF scan was conducted on the specimen. Then, proximate and ultimate analyses were conducted on each sample. A detailed list of the data collected in each of these analyses is shown in Table 3.3. In addition to the proximate and ultimate analyses, a combustion analysis was conducted to determine the energy content (BTU/lb) of the fuel. Once this test was completed, the ash was analyzed, by XRF, in order to determine the concentration of the standard parameters shown in Table 3.1. The cement plant did not conduct any tests on the tires, plastics, broiler litter, woodchips or switchgrass. For the coal, the cement plant conducted the same tests as the external laboratory. Table 3.3: Proximate and Ultimate Analysis Details Moisture Ultimate Analysis (wt. %) Hydrogen Carbon Nirtogen Sulphur Oxygen Ash Proximate Analysis (wt %) Moisture Ash Volatile Matter Fixed Carbon 119 120 3.3.5 Analyzing the Chemical Composition of Cement Kiln Dust The cement kiln dust (CKD) was sampled twice a day over the standard sampling period. These discrete specimens were tested without making composite samples. The standard parameters shown in Table 3.1 were determined by XRF at the cement plant and at the external laboratory. At the cement plant, moisture and loss on ignition were not determined. The standard external laboratory parameters were all tested for, with no exceptions or additions. 3.3.6 Analyzing the Chemical Composition of Clinker Clinker was sampled at the cement plant twelve times per day in accordance with Section 3.3.1. The standard sampling period was used for collection of clinker samples. The standard cement plant parameters, as shown in Table 3.1, were determined for each of the discrete specimens collected. In addition to the standard cement plant elements, the equivalent alkali content and Bogue compounds content were calculated in accordance with ASTM C 150. The cement plant also determined the free lime (FCaO) content in each of these discrete specimens. In addition to the tests conducted at the cement plant, Rietveld Analysis was also conducted on clinker samples by the cement plant?s specialty lab. Reitveld Analysis is a procedure used to determine the Bogue compounds more accurately than the formulas given by ASTM C 150. This test was conducted on one composite specimen per day, which was created in accordance with Section 3.3.2, using each of the twelve discrete samples collected during that day. 121 Finally, the standard external laboratory parameters, as shown in Table 3.1, were determined by XRF. These determinations were made on single-day composite specimens, prepared in accordance with Section 3.3.2, using all twelve of the discrete samples from that day. Each of the daily composite specimens was tested for the standard external laboratory elements twice. 3.3.7 Analyzing the Chemical Composition of Cement Portland cement was sampled at the cement plant eight times per day, in accordance with Section 3.3.1. The standard sampling period was used for collection of cement samples. The standard cement plant parameters, as shown in Table 3.1, were determined on each of the discrete specimens collected, as well as on daily composites made from each of the discrete samples. In both cases, the equivalent alkali content and Bogue compounds content were calculated in accordance with ASTM C 150. Additionally, the free lime content and Blaine specific surface area were determined. In addition to the tests conducted at the cement plant, Rietveld Analysis was conducted on cement samples by the cement plant?s specialty lab. This test was conducted on one composite specimen per day, which was created by the process described in Section 3.3.2, using each of the eight discrete samples collected during that day. Finally, the standard external laboratory parameters, shown in Table 3.1, were determined by XRF. These determinations were made on single-day composite specimens prepared using all eight of the discrete samples from that day. In addition to the standard external laboratory elements, the total organic carbon (TOC) content was determined on each of the daily composites using a TOC analyzer. 3.3.8 Analyzing the Physical Properties of Cement The cement samples collected were also used to conduct physical property testing. The physical properties of cement were tested by three different entities: the cement plant, Auburn University, and the cement plant?s specialty lab. All of the tests conducted by the cement plant were conducted on one-day composite specimens prepared from the eight daily discrete samples. Auburn University tested a single composite specimen prepared for each of the burns. The physical property tests of cement performed by Auburn University, the cement plant, and the cement plant?s specialty laboratory are shown in Tables 3.4, 3.5, and 3.6 respectively. These tables also show the specifications and units associated with each test. Table 3.4: Cement Physical Property Tests Performed by Auburn University Property Units ASTM Specification Autoclave Expansion % C 151 Cube Flow % C 230 Compressive Strength at MPa C 109 Normal Consistency % C 187 Gillmore Initial Set Min C 266 Gillmore Final Set Min C 266 Vicat Initial Set Min C 191 Vicat Final Set Min C 191 Drying Shrinkage Development % C 596 122 Table 3.5: Cement Physical Property Tests Performed by Cement Plant 123 Vicat Final Set Min C 191 Property Units ASTM Specification Air in Mortar % C 185 Blaine Specific Surface Area m 2 /kg C 204 Autoclave Expansion % C 151 Cube Flow % C 230 Compressive Strength at 1, 3, 7, and 28 days MPa C 109 Normal Consistency % C 187 Gillmore Initial Set Min C 266 Gillmore Final Set Min C 266 Vicat Initial Set Min C 191 Table 3.6: Cement Physical Property Tests Performed by Cement Plant?s Specialty Laboratory Property ASTM Specification Particle Size Distribution Laser Diffraction 3.3.9 Analyzing the Properties of Concrete For each of the burns, cement was used to make concrete in an attempt to establish any links between the fuels and the properties of concrete. The bulk cement from C burn was collected at the end of the grinding period through the typical bagging process used at the cement plant. The cement from each of the subsequent burns was collected by making a composite specimen over the entire burn using the samples taken at each of the discrete sampling times. There were two different mixture designs from which concrete was made using the cement from each burn. The primary mixture design, named Mix A, is shown in Table 3.7. Mix A had a water-to-cement ratio of 0.44, and used #57 crushed limestone and a natural river sand as the aggregate. The secondary mixture design, named Mix B, is shown in Table 3.8. The water-to-cement ratio in Mix B was 0.37, and utilized #78 crushed limestone and a natural river sand as the aggregate. In an attempt to eliminate the variability in aggregates, enough of each was collected from the same source on the same date to make all the concrete for all burns. Table 3.7: Mix A Proportions (w/c = 0.44) Water 273 lbs/yd 3 4.38 ft 3 Cement (Type I) 620 lbs/yd 3 3.15 ft 3 Coarse Aggregate (# 57 Crushed Limestone) 1,900 lbs/yd 3 10.61 ft 3 Fine Aggregate (Natural River Sand) 1,272 lbs/yd 3 7.78 ft 3 Air 4.0 %1.08 ft 3 Air-Entraining Admixture 1.2 oz/yd 3 0.00 ft 3 Materials Item Volumes Mix A was produced by Auburn University and the cement plant?s specialty lab. The aggregate used by the cement plant for Mix A was collected and provided by personnel at Auburn University. All the tests conducted by both entities, as well as those conducted only by Auburn University are listed in Table 3.9. The specification associated with each test is also shown. 124 Table 3.8: Mix B Proportions (w/c = 0.37) The typical concrete mixture at Auburn University was made by preparing enough material, in the proportions shown in Table 3.7 or Table 3.8, to produce 6.5 ft 3 of concrete. Once the concrete had been mixed, a slump test and total air content test were conducted in accordance with ASTM C 143 and ASTM C 231, respectively. Next, a setting time test specimen was prepared in accordance with ASTM C 403. The following step was to prepare three 3 x 3 x 11.25-inch bars to be used in the drying shrinkage development test (ASTM C 157). Finally, one 6-in. x 12-in. cylinder was prepared for the heat of hydration under semi-adiabatic conditions test, along with ten 6-in. x 12-in. cylinders for both compressive strength (ASTM C 39) and splitting tensile strength (ASTM C 496) tests. Two cylinders were tested at each age for each test. Additionally, six 4-in. x 8-in. cylinders were prepared in order to conduct the rapid chloride ion permeability (RCPT) test at 91 and 365 days. The various concrete tests that were conducted are listed in Table 3.9. 125 Table 3.9. Concrete Tests Test Specification Slump ASTM C 143 Setting Time ASTM C 403 Total Air Content ASTM C 231 Compressive Strength at 1, 3, 7, 28, and 91 days ASTM C 39 Drying Shrinkage Development ASTM C 157 Permeability (RCPT) ASTM C 1202 Test Specification Heat of Hydration (Semi-Adiabatic) Rilem 119-TCE Splitting Tensile Strength at 1, 3, 7, 28, and 91 days ASTM C 496 Tests Conducted by Both Entities Tests Only Conducted at Auburn University 3.3.10 Analyzing the Emissions The emissions were collected by the cement plant using a Continuous Emissions Monitoring System (CEMS). Although the emissions were continuously monitored, they were reported as an hourly average. The sampling period for emissions was four days before, during, and two days after each burn as shown in Figure 3.2. The emissions that were monitored from the main stack were carbon monoxide (CO), nitrogen oxides (NO x ), sulfur dioxide (SO 2 ), and volatile organic compounds (VOC). 3.4 Conclusion The test procedure described in the previous sections was developed to provide the most complete data possible regarding the effects of the alternative fuels on the production process, as well as on the products themselves. All materials involved in the 126 127 production process were sampled and tested. These included the raw materials, fuels, and CKD. Also, all of the products of the process were sampled. These included clinker, portland cement, and emissions. A chemical analysis was conducted on each of the materials listed above in order to determine any variations that may be attributed to the utilization of the alternative fuels. Additionally, special testing was conducted to determine any effects that the fuels may have had on concrete produced using the portland cement collected from each burn. 128 CHAPTER 4 PRESENTATION AND ANALYSIS OF DATA 4.1 Introduction This chapter presents the collected data along with an analysis and discussion of the results. The data pertaining to each material tested follow the same order described in Chapter Three. For the discussion of each material, there are three objectives to be met: presentation of data, analysis of data, and discussion of results. For each material, the results presented by the various testing laboratories are discussed separately. Comparisons are made between results from different testing laboratories when it is deemed necessary. Since this effort is a continuation of the research initiated by Swart (2007), the data and results from his thesis are directly used for study and comparison. Swart only investigated the use of scrap tires and waste plastics as fuels in cement manufacturing; in this study, broiler litter, woodchips and switchgrass are also being investigated. In order to gain better insight into the potential of alternative fuel options through comparison, the data from all the alternative fuel burns including scrap tires and waste plastics fuel burns are presented and discussed in this document. 129 Swart (2007) had remarked that due to the delays between the trial burns and the changes introduced into the production process at the cement plant in those delay periods, it had become difficult to conclusively evaluate the possible effect of alternative fuels on the various process outputs (i.e. clinker, cement, CKD and emissions). To address this concern to an extent, two additional baseline burns (coal and tires burns) closer to the alternative fuel trial burns were conducted, whenever it was found to be necessary. All non-baseline burns will be referred to as Fuel Burns from here onwards. As already mentioned in Section 3.1, the following notations shall refer to the different trial burns conducted: 1. C burn utilized only coal as fuel. 2. CT1 burn utilized coal and tires. This is the standard fuel combination used at the cement plant, and was therefore considered the baseline for comparison purposes. This is the first baseline burn. This is the baseline burn exclusively for the C burn. 3. CTP burn used coal, tires, and waste plastics. Waste plastics were the first alternative fuel tested. 4. CT2 burn utilized coal and tires. Again, this is the second baseline burn with standard fuel combination. This is the baseline burn exclusively for the CTP burn. 5. CTB burn used coal, tires, and broiler litter. Broiler litter was the second alternative fuel tested. 6. CT3 burn utilized coal and tires. Again, the standard fuel combination was used and this is the third baseline burn. This is the baseline burn for the CTB, CTW, and CTS burns. 130 7. CTW burn used coal, tires, and woodchips. Woodchips was the third alternative fuel tested. 8. CTS burn used coal, tires, and switchgrass. Switchgrass was the fourth alternative fuel tested. Due to economic constraints and lack of availability of adequate storage for isolation and grinding of the produced clinker, cement was not sampled or tested for CT2 and CT3 burns. However, all the raw materials, fuels, CKD, emissions and the primary product, clinker, were sampled and tested for chemical properties. Over the project period, it was realized that the emissions were actually more sensitive to the raw material and fuel composition changes than the clinker or cement properties. This could be due to the fact that certain volatile compounds or elements present, even if in trace amounts, in the process inputs may directly end up in emissions as a major constituent of emissions, which are in amounts in the order of one millionth ton per hour, whereas the same constituents may not have as significant an effect on clinker or cement, which is produced in amounts in the order of 200 tons per hour. To estimate the effects of alternative fuels on the process outputs at different levels, a new analysis approach was developed, based on the available budget constraints, data limitations, and the individual product sensitivities to the fuels. Figure 4.1 depicts the actual analysis methodology adopted for studying the effects on various process inputs and outputs in the alternative fuel trial burns. In the figure, the baseline burn for the individual fuel or group of fuels is represented by gray shading in its box. The results for all the process inputs and outputs except fuels and cement for all the fuel 131 burns were compared to the respective baseline burns. Fuel data will be presented for all burns in Section 4.3.3. Comparisons were made for all burns, wherever applicable. Cement and concrete properties for all the fuel burns were analyzed using CT1 burn as the baseline burn (Swart 2007). In this chapter, graphical representations are presented showing the difference in means between each of the burns relative to its own baseline burn (coal and tires burn). Since the cement plant, during its normal operations, uses coal and scrap tires as the fuel, it was decided to use this fuel combination as the baseline for comparison. The final objective of this chapter is to discuss the results. In this section, an emphasis is placed on the tests or parameters that showed the greatest change in means. Any conclusions that can be drawn for the cause of these changes are presented. A discussion of whether the findings of this project agree or disagree with the literature presented in Chapter Two is given. The previous chapters in this document address the utilization of four alternative fuels. It was the aim of this study to produce portland cement using all the alternative fuels and to evaluate the properties of concrete made from these cement. However, certain results concerned with long-term durability of concrete like later-age drying shrinkage and permeability for later trial burns could not be obtained within the timeframe necessary to be presented and discussed in this document. Since this study will continue, the complete data associated with those burns will be presented in future documentation related to this project. 132 Figure 4.1: Analysis method for the burn data 133 4.2 Use of Statistics to analyze data In this chapter, the data pertaining to each test or parameter for every material are presented. When there are ten or more data points for a set of results, a complete set of summary statistics is also presented along with the data The summary statistics consist of the average, coefficient of variation (as a percentage), and an indication of how well the data are represented by a normal distribution based on Anderson-darling statistic (Section 4.2.1). The coefficient of variation is calculated by dividing the standard deviation of the data set by the average (arithmetic mean), and is reported as a percentage. If the minimum requirement for summary statistics is not met, only the average value is presented. The complete data sets for which only summary statistics are given are shown in Appendices B.1 through B.8. Further, when ten or more data points for two comparable set of results are available, they are tested for significance of the difference (Two-sample t-test) in the means of each data set. Both the Anderson-Darling test and the Two-sample t-test are based on the Test of hypotheses method in which there are two competing hypotheses under consideration. Initially, one of the hypotheses, the Null Hypothesis (H 0 ), is assumed to be correct. Then evidence from the sample data is obtained and the null hypothesis is rejected in favor of the competing claim, called the Alternative Hypothesis (H a ), only if there is convincing evidence against the null hypothesis (Devore 2005). 134 The evidence obtained is in form a p-value, which represents the probability of failing to reject the null hypothesis. A small p-value is an indication that the null hypothesis is false and hence can be rejected in favor of the alternative hypothesis (Minitab 2006). 4.2.1 Anderson-Darling Normality Test The Anderson-Darling normality test is used to assess whether the data comes from a normal distribution. It uses a sample's p-value to measure whether sample data is normal. P-value is the probability that the sample being tested was drawn from a population with a normal distribution. The hypotheses in Anderson-Darling test (Minitab 2006) are defined as: H 0 : The data follow a normal distribution. H a : The data do not follow a normal distribution where, H 0 ? Null Hypothesis H a ? Alternative Hypothesis The p-values are obtained from running the test in Minitab 15.1.0.0 software. If the p-value is less than 0.10, which corresponds to 90% confidence level, the null hypothesis is likely to be false and differences between the sample data sets (one being the test sample data and the data from a pre-defined normal distribution) are likely to exist, and hence the data cannot be assumed to be normally distributed, which is the alternative hypothesis (Romeu 2003). 135 As the P-value obtained for the normality test decreases, the coefficient of variation becomes less meaningful (Devore 2005). For this reason, when the P-value is below the limiting value of 0.10, the data are considered not normally distributed, and the coefficient of variation is noted with a superscript. 4.2.2 Test for Significant difference To assess the difference in means of various parameters obtained from each burn with respect to its baseline burn, the Two-sample t-test was run on the sample data sets. The test assumes null and alternative hypotheses and produces a p-value corresponding to the sample data, which as discussed earlier, represents the probability of failing to reject the null hypothesis (i.e. in this particular case, the probability of the null hypothesis being true). The hypotheses of the test in the context of the experiment (Minitab 2006) are defined as: H 0 : The means of two sample data sets are equal H a : The means of two sample data sets are not equal where, H 0 ? Null Hypothesis H a ? Alternative Hypothesis In this context, the p-value is a measure of how much evidence we have against the assumption that the two data sets that are being compared are identical. The limiting p-value used for determination of statistical significance was selected to be 0.10, which corresponds to 90 % confidence level. This was done because the sample sizes for all materials except emissions were considered to be small to very small. It means that any 136 p-value above this limiting value will imply that the difference in means for that specific result is not statistically significant or a p-value of less than 0.10 will help reject the null hypothesis and suggests that there is a significant difference in means of the two sample data sets (Devore 2005). While using this test in the context of the experiment, it must be noted that just because some sample data sets for any parameter show a statistically significant difference, it may not mean that the parameter shows a difference of practical significance. Practical significance is determined by the performance of the cement, and whether a statistically significant difference in a parameter significantly alters the behavior of the cement. 4.3 Plant Operations Each of the trial burns lasted a total of three days, with the exception of the CTS burn, which lasted only for two days due to insufficient in-time supply of switchgrass. Considerable time elapsed between each burn, which allowed the cement plant to establish its typical production process without the influence of the additional testing and fuel usage associated with this study. Furthermore, because the cement plant is concerned with its production, many aspects of the production process like kiln feed rate, fuel feed rates, and production rates were changed relative to each burn, in order to assure maximum production. Since these aspects of the production process are proprietary information, the ranges for each of these parameters are given, instead of the averages. A summary of plant conditions during each of the burns is presented in Table 4.1. 137 The cement plant was able to start using alternative fuels with minimal impact on its operations. Equipment had to be installed to help shred, store, meter (by weight), and feed the various alternative fuels into the precalciner. The quantity of tires that could be burned was limited by the development of sulfur build-ups within the system, which limited the airflow, and effectively choked the system. These build-ups were primarily composed of sulfur-derived compounds, and were directly responsible for limiting the air flow through the kiln, which reduced oxygen levels necessary for good combustion in the kiln. The feed rates of tires for the CTS burn reported in Table 4.1 are unusually high, which may be an anomaly arisen from malfunctioning of the weighing scale, as suggested by the cement plant personnel. The introduction of waste plastics into the system was affected by the ability of the fuel feed equipment to convey the low-density material into the precalciner. The average density of waste plastics was measured to be 5.26 lb/ft 3 , which is very low and resulted in low feed rates for the waste plastics. Broiler litter handled easily and did not cause any problems while in use. The major concern with woodchips was the high moisture content. However, woodchips burned well and did not cause any problems in the plant operation. Switchgrass preprocessing was labor-intensive, especially with the shredding of huge bales, before feeding into the system. But it flowed smoothly once shredded and did not cause any problems. The feed rate was limited due to its low density. 138 4.4 Data Presentation and Analysis For all of the tables and figures presented in this chapter, a specific terminology will be implemented in order to designate the origin of the data. ? Cement plant results (CPR) refers to data that were obtained from the cement plants laboratory. ? Auburn University results (AUR) refers to data that were collected at Auburn University. ? External laboratory results (ELR) are those that were collected at the external laboratory. ? Specialty laboratory results (SLR) are those that were collected at the cement plant?s specialty laboratory. The external laboratory provided results concerning all chemical compositions. Although more parameters were reported by the external laboratory than by the cement plant, only the major parameters (those which are measured as percent by weight) are discussed in most cases. The major parameters were determined by both the cement plant and the external laboratory. In all tables that present summary statistics, the abbreviation C.V. stands for coefficient of variation and % Diff. stands for a percent difference. This percent difference is relative to the results of the baseline burn, from the testing agency in question. For instance, in any given table of results as presented by the cement plant (or external laboratory), the percent difference is relative to the baseline, as reported by the cement plant (or external laboratory). 139 As discussed earlier in Section 4.2, the summary statistics do not include the coefficient of variation or the p-value from the normality test for data sets that contain less than ten data points. The same limit is utilized for determining statistically significant differences relative to a baseline burn. Even though statistical significance is not reported for such small data sets, a graphical representation of percent difference between means relative to baseline burn is given. These percent difference plots may show the results from different testing agencies. Once again, these differences are relative to the baseline burn as reported by the testing agency in question. In the plots of percent difference for chemical compositions, the same major parameters are plotted. These major parameters are Al 2 O 3 , CaO, Fe 2 O 3 , K 2 O, MgO, Na 2 O, SiO 2 , and SO 3 . First, for every material composition and property discussed, the results of the baseline burns, CT2 burn and CT3 burn are compared to those from CT1 burn. This helps in determining if the plant conditions have indeed changed between the burn conditions that used the same fuel, i.e. coal and scrap tires (baseline burns). Then, the fuel burns are compared to the respective baseline burns to determine if any observable changes occurred in the properties. Table 4.1: Summary of plant conditions during each trial burn 140 141 4.3.1 Chemical Composition of Raw Materials The chemical compositions of the raw materials were tested using XRF by both the cement plant and the external laboratory. The kiln feed is obtained by blending various raw materials, and it becomes the primary material entering the kiln; therefore, only a single specimen of each of the individual raw materials was tested during each burn. In Tables 4.2 to 4.5, the percentage difference in chemical composition of Raw Materials One, Two, Three, Four, Five and Six from CT2 and CT3 burns relative to CT1 burn are shown. These raw materials are not identified because the cement plant considered this to be confidential information. In the tables, the percentage difference value is reported as NA (not applicable) wherever the data is not available or was not detected. The raw material data for CTS burn from the cement plant is not reported since it was not collected by the cement plant. The cement plant also did not test for the compositions of Raw Material Three for some of the burns. However, all the raw material data is tested for and reported by the external laboratory. From the data it can be deduced that the raw material composition used in the baseline burns are varied greatly. This justifies the use of different baselines for comparison of data collected from different trial burns. Although the percent change of each parameter is presented for the raw materials, no conclusions can be drawn based on these data alone. Table 4.2: CPR- Baseline Burns, Percentage change in Raw Materials One, Two and Three relative to CT1 burn CT2 burn CT3 burn CT2 burn CT3 burn CT2 burn CT3 burn Al 2 O 3 4.8 -3.9 130.0 183.7 NA NA CaO -31.1 65.1 -2.0 -2.8 NA NA Fe 2 O 3 -76.9 -59.1 -100.0 -100.0 NA NA K 2 O 12.5 -10.1 700.0 860.0 NA NA MgO -11.0 33.9 26.3 89.5 NA NA Na 2 O -25.0 -26.0 NA NA NA NA SiO 2 28.5 16.3 115.3 149.4 NA NA SO 3 -23.1 -46.4 -84.8 -89.8 NA NA Moisture 51.9 -33.4 72.2 100.0 NA NA LOI -40.7 -26.1 1.2 -0.2 NA NA Notes: NA - Not Applicable Parameter Percent Difference Relative to CT1 burn Raw Material One Raw Material Two Raw Material Three Table 4.3: CPR- Baseline Burns, Percentage change in Raw Materials Four, Five and Six relative to CT1 burn CT2 burn CT3 burn CT2 burn CT3 burn CT2 burn CT3 burn Al 2 O 3 68.8 68.8 102.6 23.2 -60.4 -58.4 CaO -9.7 -3.4 132.4 -36.6 48.5 40.9 Fe 2 O 3 -32.8 -43.2 NA NA 63.3 NA K 2 O 400.0 160.0 18.8 13.1 -52.6 -38.4 MgO 23.1 17.3 384.2 -57.4 -63.6 -58.7 Na 2 O NA NA NA NA NA NA SiO 2 44.2 41.2 -4.9 2.8 -58.1 -60.6 SO 3 52.6 55.7 252.7 86.6 14.2 12.6 Moisture NA 61.4 14.0 55.8 187.4 190.8 LOI NA 19.6 -72.4 -74.4 -77.9 -58.6 Notes: NA - Not Applicable Raw Material Four Raw Material Five Raw Material Six Parameter Percent Difference Relative to CT1 burn 142 143 Zn 4.3 -2.90 -68.8 -61.76 -91.6 -25.40 Notes: NA - Not Applicable Table 4.4: ELR- Baseline Burns, Percentage change in Raw Materials One, Two and Three relative to CT1 burn CT2 burn CT3 burn CT2 burn CT3 burn CT2 burn CT3 burn Al 2 O 3 11.5 11.50 2611 822.1 -40.1 -11.39 CaO 3.1 9.60 64.0 71.82 99.1 80.36 Fe 2 O 3 12.6 10.51 560.7 71.85 -18.2 -3.87 K 2 O 24.8 12.85 399.7 86.96 25.5 14.54 MgO 36.8 35.64 115 145.4 105.3 48.79 Na 2 O -12.3 -11.91 133.2 375.9 -51.9 70.74 P 2 O 5 1.3 7.98 NA NA -79.4 -21.60 SiO 2 17.4 18.16 826.6 363.4 -12.4 11.37 SO 3 14.8 75.98 33.7 -2.02 -43.3 -2.00 TiO 2 25.8 18.69 NA NA -77.0 -72.33 Moisture -8.9 -33.12 14807 15529 128.3 490.5 LOI -45.3 -29.99 -6.1 0.23 11.6 14.88 As 18.9 20.16 NA NA -72.5 -11.14 Ba 52.3 39.03 465.8 126.3 -13.6 2.45 Cd NA NA NA NA NA NA Cl -39.2 -27.20 -85.3 -86.79 -81.0 -76.58 Co 47.8 41.62 NA NA NA NA Cr 17.3 25.39 NA NA -27.8 4.99 Cu -8.1 -27.28 NA NA NA NA Hg NA 34100 NA 6300 NA 4267 Mn 65.7 132.0 1010 455.0 162.4 211.1 Mo NA NA NA NA NA NA Ni 6.1 0.13 NA NA NA -40.55 Pb 18.8 -13.33 NA NA NA -79.67 Sb NA NA NA NA NA NA Se NA -23.12 NA NA NA NA Sr 45.6 38.33 166.9 122.4 54.7 93.33 V 20.4 16.17 NA NA -65.5 -47.46 Property Percent Difference Relative to CT1 burn Raw Material One Raw Material Two Raw Material Three Table 4.5: ELR- Baseline Burns, Percentage change in Raw Materials Four, Five and Six relative to CT1 burn 144 CT2 burn CT3 burn CT2 burn CT3 burn CT2 burn CT3 burn Al 2 O 3 15.5 73.60 -28.6 -73.91 -27.3 11.70 CaO 10.1 -1.02 1005.7 -4.23 39.5 30.77 Fe 2 O 3 -23.8 -27.76 195.1 -63.93 40.0 49.81 K 2 O -5.4 86.08 -53.8 -61.20 -7.8 -5.38 MgO 7.3 15.26 723.1 -17.23 -14.9 -12.17 Na 2 O 57.6 -68.99 -71.2 -73.40 -1.2 -5.38 P 2 O 5 -21.5 -18.00 34.4 -100 -100 26.16 SiO 2 -6.5 9.57 -6.7 3.63 -4.1 -2.34 SO 3 54.3 188.9 303.1 -100 21.1 26.42 TiO 2 -5.4 15.37 -36.5 -34.48 31.7 26.16 Moisture 667.3 1282 -18.7 3.16 2327 1029 LOI NA NA -55.2 -76.93 -64.6 -33.69 As NA NA -28.0 NA NA NA Ba ND NA NA NA NA NA Cd NA NA NA NA NA NA Cl -87.4 -44.12 -28.8 -79.66 -84.8 -81.90 Co NA NA NA NA NA NA Cr -22.2 -18.11 NA NA NA NA Cu -46.0 -24.68 NA 162.7 NA NA Hg NA 1820 NA 6700 NA 477.8 Mn 124.7 103.9 8742 284.4 143.7 21.84 Mo 58.0 -37.53 NA NA NA NA Ni 209.5 365.2 NA -60.09 NA NA Pb NA NA -37.0 62.95 -65.8 NA Sb NA NA NA NA NA NA Se NA 94.87 279.3 NA NA NA Sr 77.2 77.15 -18.3 -18.25 41.4 94.40 V -0.9 -1.26 NA NA NA NA Zn -39.4 22.16 -100.0 0.87 NA NA Notes: Property Percent Difference Relative to CT1 burn Raw Material Four Raw Material Five Raw Material Six NA - Not Applicable Tables 4.6 to 4.11 present the percentage change in each parameter of raw materials one to six, for each burn relative to its own baseline burn. Table 4.6: CPR- Fuel Burns, Percentage change in Raw Material One composition from each burn relative to its baseline burn C burn 1 CTP burn 2 CTB burn 3 CTW burn 3 CTS burn 3 Al 2 O 3 13.2 -2.8 16.4 16.4 NA CaO -9.8 41.4 -58.6 -62.1 NA Fe 2 O 3 10.0 573.4 -86.8 88.7 NA K 2 O 23.6 -8.1 40.6 20.9 NA MgO 11.0 127.8 -30.1 -29.5 NA Na 2 O -5.0 40.0 26.7 28.4 NA SiO 2 -2.7 -25.4 8.8 -4.0 NA SO 3 -45.5 -86.0 12.3 -58.3 NA Moisture -54.2 15.0 140.2 140.2 NA LOI -22.0 2.9 -14.0 2.3 NA Notes: NA - Not Applicable 1 Parameter Percent Change Relative to Baselines Raw Material One Relative to CT1 burn 2 3 Relative to CT2 burn Relative to CT3 burn 145 Table 4.7: CPR- Fuel Burns, Percentage change in Raw Material Two composition from each burn relative to its baseline burn C burn 1 CTP burn 2 CTB burn 3 CTW burn 3 CTS burn 3 Al 2 O 3 10.0 -43.5 8.1 -53.0 NA CaO -0.2 -0.3 -2.3 -1.4 NA Fe 2 O 3 -17.6NANANANA K 2 O 600.0 -12.5 -19.8 -27.1 NA MgO 21.1 -19.2 -5.6 -46.1 NA Na 2 O NA NA NA NA NA SiO 2 12.9 11.5 6.1 -5.7 NA SO 3 -82.9 -37.5 -41.1 21.5 NA Moisture 222.2 -3.2 -16.7 -2.8 NA LOI 1.7 0.5 2.6 -0.5 NA Notes: 2 Relative to CT2 burn 3 Relative to CT3 burn NA - Not Applicable 1 Relative to CT1 burn Parameter Percent Change Relative to Baselines Raw Material Two Table 4.8: CPR- Fuel Burns, Percentage change in Raw Material Three composition from each burn relative to its baseline burn C burn 1 CTP burn 2 CTB burn 3 CTW burn 3 CTS burn 3 Al 2 O 3 -15.2NANANANA CaO Fe 2 O 3 14.0 NA NA NA NA K 2 O 5.9NANANANA MgO 06 Na 2 O -85.7NANANANA SiO 2 -2.4 NA NA NA NA SO 3 -14.3NANANANA Moisture NA NA NA NA NA LOI NA NA NA NA NA Notes: 2 Relative to CT2 burn 3 Relative to CT3 burn NA - Not Applicable 1 Relative to CT1 burn Parameter Percent Change Relative to Baselines Raw Material Three 146 Table 4.9: CPR- Fuel Burns, Percentage change in Raw Material Four composition from each burn relative to its baseline burn C burn 1 CTP burn 2 CTB burn 3 CTW burn 3 CTS burn 3 Al 2 O 3 -32.8 -28.3 -11.0 -41.9 NA CaO -17.7 20.2 13.6 -2.2 NA Fe 2 O 3 38.8 -13.7 -3.5 93.6 NA K 2 O 850.0 -50.0 130.8 -61.5 NA MgO -15.4 0.8 -1.6 -5.5 NA Na 2 O NA NA NA NA NA SiO 2 -6.7 3.4 2.6 -44.5 NA SO 3 110.6 -55.4 -15.9 -28.6 NA Moisture 79.4 NA -36.1 NA NA LOI 62.5 NA -86.4 96.8 NA Raw Material Four Parameter Percent Chan Notes: 2 Relative to CT2 burn 3 Relative to CT3 burn NA - Not Applicable 1 Relative to CT1 burn ge Relative to Baselines Table 4.10: CPR- Fuel Burns, Percentage change in Raw Material Five composition from each burn relative to its baseline burn C burn 1 CTP burn 2 CTB burn 3 CTW burn 3 CTS burn 3 Al 2 O 3 135.5 -26.0 13.2 22.9 NA CaO -59.7 -66.9 -34.1 16.8 NA Fe 2 O 3 18.6 NA NA NA NA K 2 O 100.0 47.4 -17.1 10.5 NA MgO -57.9 -79.3 4.9 146.9 NA Na 2 O NA NA NA NA NA SiO 2 1.6 9.4 1.1 1.1 NA SO 3 -66.1 -94.7 -33.0 -90.4 NA Moisture 79.1 -30.6 -38.8 -47.8 NA LOI -69.2 -7.0 25.0 0.0 NA Notes: 2 Relative to CT2 burn 3 Relative to CT3 burn NA - Not Applicable 1 Relative to CT1 burn Percent Change Relative to Baselines Raw Material Five Parameter 147 Table 4.11: CPR- Fuel Burns, Percentage change in Raw Material Six composition from each burn relative to its baseline burn C burn 1 CTP burn 2 CTB burn 3 CTW burn 3 CTS burn 3 Al 2 O 3 -53.5 254.2 -3.9 221.3 NA CaO 26.5 -24.6 5.9 -23.2 NA Fe 2 O 3 50.0 -49.0 NA NA NA K 2 O -42.1 177.8 -19.7 113.7 NA MgO -25.0 517.6 6.4 462.3 NA Na 2 O NA NA NA NA NA SiO 2 -51.1 297.7 -9.0 323.7 NA SO 3 6.6 -26.6 0.6 -29.7 NA Moisture 41.4 -58.4 4.3 -60.0 NA LOI -30.6 192.3 -31.5 57.8 NA Parameter Percent Chan Notes: NA - Not Applicable 1 Relative to CT1 burn 2 Relative to CT2 burn 3 Relative to CT3 burn ge Relative to Baselines Raw Material Six The proportion of each material that was combined to produce the kiln feed was not provided by the cement plant, because it is proprietary information. This is the reason for emphasizing the chemical composition of the kiln feed above that of the individual raw materials. This is also the reason that no graphical representation of the percent changes is presented in this report. Tables 4.12 to 4.17 present the percentage change in Raw Materials One to Six compositions for each burn relative to the appropriate baseline burn as reported by the external laboratory. The actual raw data for all the burns can be found in Appendix B. 148 Table 4.12: ELR- Fuel Burns, Percentage change in Raw Material One composition from each burn relative to its baseline burn C burn 1 CTP burn 2 CTB burn 3 CTW burn 3 CTS burn 3 Al 2 O 3 2.9 0.10 1.9 -12.5 -3.7 CaO 7.8 13.32 0.7 -1.8 -16.4 Fe 2 O 3 -9.2 -0.03 -4.6 -21.7 -14.3 K 2 O -0.3 -4.38 8.7 -8.0 -5.7 MgO 18.4 4.14 -3.3 -23.3 -15.0 Na 2 O -4.2 23.33 4.2 -12.0 59.5 P 2 O 5 11.3 10.31 -2.0 -14.6 -11.3 SiO 2 0.8 -0.79 -1.0 -15.9 -6.3 SO 3 106.8 -46.82 54.7 -34.5 -46.0 TiO 2 4.4 -1.12 11.2 -8.2 -7.4 Moisture -25. 32632.53345.9 LOI -5.0 63.17 -12.7 60.2 -26.9 As 26.5 83.57 3.4 -16.8 9.9 Ba 23.6 -13.04 14.3 -4.8 -4.8 Cd NA NA NA NA NA Cl -81.6 -67.11 -80.2 -60.4 -15.4 Co -5.3 -3.95 5.3 0.2 15.9 Cr 3.0 27.96 -2.2 29.7 -7.4 Cu 34.4 19.00 28.0 -0.5 -4.6 Hg 600.0 NA NA -97.1 -98.7 Mn -7.3 100.00 -42.9 -42.9 -14.3 Mo NA 122.47 8.7 76.9 -64.6 Ni -1.1 1.19 8.7 -0.6 13.4 Pb -6.1 145.83 21.8 26.2 83.2 Sb NA NA NA NA NA Se 34.0 NA 100.0 50.0 NA Sr 4.3 -10.00 10.5 -26.3 -31.6 V 12.1 -0.23 4.5 -1.7 5.6 Zn -44.2 131.90 -3.2 -2.5 4.3 Notes: Property NA - Not Applicable 1 Relative to CT1 burn Raw Material One Percent Difference Relative to Baseline burns 2 Relative to CT2 burn 3 Relative to CT3 burn 149 Table 4.13: ELR- Fuel Burns, Percentage change in Raw Material Two composition from each burn relative to its baseline burn C burn 1 CTP burn 2 CTB burn 3 CTW burn 3 CTS burn 3 Al 2 O 3 179.7 -53.24 -6.8 -52.6 -58.9 CaO -8.1 2.01 0.0 -43.2 -43.1 Fe 2 O 3 -13.7 -53.93 46.2 -39.7 -62.3 K 2 O -2.3 -53.35 10.6 -46.6 -55.5 MgO -6.8 71.71 9.8 -50.5 -31.7 Na 2 O -100.0 683.1 -74.7 -83.7 -10.2 P 2 O 5 NA -77.78 NA NA NA SiO 2 4.7 -36.88 -8.2 -47.0 -70.4 SO 3 -15.9 2.54 -34.8 -37.0 -23.0 TiO 2 NA -100.0 NA NA NA Moisture 16650 29.61 -88.6 20.3 -31.2 LOI 10.2 5.52 -4.5 0.3 0.4 As NA9. NANANA Ba -23.4 -40.00 0.0 -50.0 -50.0 Cd NA NA NA NA NA Cl -90.9 -25.64 31.4 14.3 34.3 Co NA -20.02 204.1 -51.0 -2.0 Cr NA -11.13 -17.6 210.2 79.6 Cu NA 299.9 -32.4 NA NA Hg -66.7 NA NA -94.8 -95.6 Mn 33.2 50.00 100.0 0.0 0.0 Mo NA NA NA NA NA Ni NA NA NA NA -13.8 Pb -2.3 NA NA NA NA Sb 59. ANANANA Se NA NA NA NA NA Sr -23.4 -33.33 20.0 -40.0 -60.0 V NA -33.35 -49.3 -61.4 -52.5 Zn NA 246.58 373.0 NA NA Notes: Percent Difference Relative to Baseline burns Property Raw Material Two NA - Not Applicable 3 Relative to CT3 burn 1 Relative to CT1 burn 2 Relative to CT2 burn 150 Table 4.14: ELR- Fuel Burns, Percentage change in Raw Material Three composition from each burn relative to its baseline burn C burn 1 CTP burn 2 CTB burn 3 CTW burn 3 CTS burn 3 Al 2 O 3 -39.3 153.71 42.9 -13.0 24.9 CaO 19.4 -38.94 -25.6 -39.5 -47.9 Fe 2 O 3 -31.4 58.06 148.8 -29.0 -0.6 K 2 O -16.2 36.33 39.4 49.4 97.0 MgO -1.2 -23.44 140.4 86.8 6.2 Na 2 O -100.0 189.78 59.3 -70.3 100.4 P 2 O 5 -43.5 216.12 73.5 -79.2 -37.6 SiO 2 -28.0 112.40 30.4 -40.9 -2.8 SO 3 20.0 -13.79 -15.7 16.4 -41.8 TiO 2 -78.4 78.86 44.6 -51.5 -16.9 Moisture 1250.9 750.37 21.2 97.5 209.1 LOI 10.2 -19.74 -29.1 0.9 -14.7 As -62.3 354.42 23.9 -38.9 -14.4 Ba 8.0 18.58 59.0 -33.3 0.0 Cd NA NA NA NA NA Cl -73.4 13.33 13.5 67.6 21.6 Co NA 7.77 54.9 -22.1 120.8 Cr 52.6 85.55 238.0 93.7 25.2 Cu NA 202.95 -18.4 NA NA Hg 33.3 NA NA -92.4 -94.7 Mn 730.2 374.31 1000 -66.7 0.0 Mo NA NA -38.0 55.9 NA Ni NA NA 71.6 -20.1 83.9 Pb -63.4 NA 135.5 -58.4 222.2 Sb 176.2 NA NA NA NA Se NA NA NA NA NA Sr -7.2 0.00 20.0 -60.0 -80.0 V -51.8 108.87 66.0 -7.2 13.2 Zn -70.3 584.93 -38.0 -54.0 -48.0 Notes: Property Percent Difference Relative to Baseline burns NA - Not Applicable 2 Relative to CT2 burn 3 Relative to CT3 burn Raw Material Three 1 Relative to CT1 burn 151 Table 4.15: ELR- Fuel Burns, Percentage change in Raw Material Four composition from each burn relative to its baseline burn C burn 1 CTP burn 2 CTB burn 3 CTW burn 3 CTS burn 3 Al 2 O 3 -6.7 -5.18 -16.0 -17.7 -54.1 CaO -82.4 -16.83 5.6 110.5 14.1 Fe 2 O 3 31.2 10.89 -2.3 -90.0 3.6 K 2 O 2465.4 586.9 1.4 1017 -82.5 MgO -86.1 -5.15 -11.0 -85.8 -5.3 Na 2 O 555.0 167.9 204.2 737.8 1156.6 P 2 O 5 -7.0 -1.17 -8.3 -91.9 30.9 SiO 2 9.3 32.00 10.0 30.6 -6.6 SO 3 253.3 -0.28 4.9 -45.0 -27.2 TiO 2 -37.8 3.04 -8.4 -5.4 -18.9 Moisture 3867 148.8 23.1 64.4 0.0 LOI NA -336.6 110.5 68.8 -85.4 As NA -58.78 30.4 94.5 4.7 Ba NA -31.03 0.0 50.0 -50.0 Cd 91.0 NA NA NA NA Cl -52.1 233.3 -24.1 0.8 -27.1 Co NA -62.53 -11.3 -54.2 24.4 Cr -89.3 56.36 -1.6 -93.3 12.2 Cu 2426 423.8 252.0 NA NA Hg -80.0 NA NA -79.2 -67.7 Mn -59.5 -11.99 5.0 -98.0 -12.5 Mo -74.3 -20.74 7.9 NA 15.9 Ni 1604 114.7 -29.9 -86.7 12143 Pb 3269.4NANANANA Sb NA NA NA NA NA Se -18. NANANAN Sr -25.1 -33.33 0.0 33.3 -33.3 V -85.8 -11.22 -12.7 -90.0 13.9 Zn 4707.4 142.88 15.6 -77.5 -40.9 Notes: Property Percent Difference Relative to Baseline burns Raw Material Four 2 Relative to CT2 burn 3 Relative to CT3 burn NA - Not Applicable 1 Relative to CT1 burn 152 Table 4.16: ELR- Fuel Burns, Percentage change in Raw Material Five composition for each burn relative to its baseline burn C burn 1 CTP burn 2 CTB burn 3 CTW burn 3 CTS burn 3 Al 2 O 3 -23.3 -27.06 32.3 25.8 69.7 CaO -48.5 -89.95 14.6 1.8 -54.7 Fe 2 O 3 -21.9 -82.92 70.0 -26.6 -64.5 K 2 O 68.8 45.41 21.9 52.8 42.6 MgO 56.3 -88.48 23.0 -61.8 -49.1 Na 2 O -100.0 88.18 228.1 1.8 1784.0 P 2 O 5 -62.5 -100.00 NA NA NA SiO 2 0.9 10.14 -0.6 -0.3 -0.6 SO 3 2263.7 -100.00 NA NA NA TiO 2 50.1 10.69 -11.2 1.8 7.2 Moisture 2.7 -32.90 -35.2 -31.6 -57.0 LOI -51.4 -15.55 37.6 -15.7 40.5 As NA -24.73 NA NA NA Ba NA NA NA NA NA Cd NA NA NA NA NA Cl -27.1 -69.05 483.3 700.0 625.0 Co NA5.91NANANA Cr NA -95.91 724.8 1081.3 409.2 Cu -23.6NA-69.2NA NA Hg 0.0 NA NA -85.3 -91.5 Mn 96.2 ANANANA Mo NA NA NA NA NA Ni NA NA NA NA NA Pb 378.4 69.36 74.1 NA 74.6 Sb NA NA NA NA NA Se NA NA NA NA NA Sr -59.2 ANANANA V NA -88.24 17.2 -4.5 -30.0 Zn 528.4 NA -78.4 NA NA Notes: Percent Difference Relative to Baseline burns Raw Material FiveProperty NA - Not Applicable 1 Relative to CT1 burn 2 Relative to CT2 burn 3 Relative to CT3 burn 153 Table 4.17: ELR- Fuel Burns, Percentage change in Raw Material Six composition from each burn relative to its baseline burn C burn 1 CTP burn 2 CTB burn 3 CTW burn 3 CTS burn 3 Al 2 O 3 61.5 391.79 -36.2 -19.6 NA CaO 7.8 -9.99 6.3 -18.5 NA Fe 2 O 3 192.0 41.44 -15.0 24.2 NA K 2 O -15.1 78.62 -9.7 -6.3 NA MgO 140.6 424.28 -5.3 57.1 NA Na 2 O -46.9 156.48 4.2 100.9 NA P 2 O 5 324.7 NA 4.2 0.4 NA SiO 2 29.6 201.08 -15.5 -11.2 NA SO 3 -7.9 -18.72 -2.7 -17.8 NA TiO 2 218.5 380.90 -47.9 50.7 NA Moisture 162.0 -79.03 76.9 -100.0 NA LOI -11.1 145.90 -49.1 24.5 NA As NA NA NA NA NA Ba NA NA NA NA NA Cd NA NA NA NA NA Cl -93.3 87.50 21.1 -42.1 NA Co NA 236.63 NA NA NA Cr NA NA NA 693.5 NA Cu NA NA NA NA NA Hg 0.0 NA NA -90.4 NA Mn 314.5 NA NA NA NA Mo NA NA NA NA NA Ni NA NA NA NA NA Pb -64.216.02NANAN Sb NA NA NA NA NA Se NA NA NA NA NA Sr 1.3NANANAN V NA 57.39 30.3 84.1 NA Zn NA NA NA NA NA Notes: Property 1 Relative to CT1 burn 2 Relative to CT2 burn 3 Relative to CT3 burn NA - Not Applicable Percent Difference Relative to Baseline burns Raw Material Six 154 155 4.3.2 Chemical Composition of Kiln Feed The kiln feed is the primary input to the production process. The chemical composition of the kiln feed, reported by the cement plant, was obtained by sampling twice a day during each burn. The average percent by weight (wt. %) and the coefficient of variation (C.V. %) for all the samples collected for each burn as reported by the cement plant are tabulated in Table 4.18. Since the number of data points for kiln feed composition was about six on average, the p-values for the test for normality of the distribution may not be valid and hence have not been reported. Nevertheless, the coefficient of variation can provide a measure of variation in the distribution and the nature of the data, i.e. the higher the C.V. value, the higher the variability of data. However, the coefficient of variation does not provide meaningful conclusions when the mean is a small number (Devore 2005), as in the case of Na 2 O or SO 3 in Table 4.18. The data for all other parameters in the kiln feed have small C.V. values, which suggest limited variability in these data. The percentage difference in the parameters of kiln feed composition as reported by the cement plant for the baseline burns relative to CT1 burn is shown in Table 4.19. The same data as reported by the external laboratory is presented in Table 4.20. The kiln feed was analyzed by the external laboratory in the form of a single composite sample collected during each burn. The cement plant results for the kiln feed composition for the baseline burns in Table 4.19 does not show much variability, despite the variation in the actual raw materials noticed in Section 4.3.1. 156 This perhaps reflects the effort of the cement plant operators that try to maintain the kiln feed composition by varying the proportions of raw material. However, the external laboratory results of the same material reported in Table 4.20 show a completely different picture. The variation in the proportions of major parameters, CaO and SiO 2 , over the baseline burns is quite significant. As observed from the percentage differences in Table 4.20, it can be seen that the kiln feed compositions were different for each baseline burn. It only validates the method of applying different baseline references for analysis of fuel burns data. The percentage differences found in the kiln feed composition of the fuel burns relative to the respective baseline burns as reported by the cement plant is presented in Table 4.21.The percentage differences in the major components in the kiln feed for the burns from Table 4.21 are plotted and presented in Figure 4.2. The high values of percentage difference in Na 2 O eq and SO 3 are not of practical significance since the mean values are so small that even a slight difference gets projected as a large percentage. The major parameters of the kiln feed, CaO and SiO 2 , from fuel burns showed less than 5% variation relative to their respective baseline burns. Kiln feed being the primary process input, keeping its composition fairly comparable to the control burn (baseline burn) renders the experimental setup valid for studying the effect of fuels on process outputs through comparison with the baseline burn results. The results of the XRF scan conducted by the external laboratory, along with the percent differences relative to respective baseline burns are shown in Table 4.22. 157 Average (wt. %) C.V. (%) Average (wt. %) C.V. (%) Average (wt. %) C.V. (%) Average (wt. %) C.V. (%) Average (wt. %) C.V. (%) Average (wt. %) C.V. (%) Average (wt. %) C.V. (%) Average (wt. %) C.V. (%) Al 2 O 3 3.11 2.4 3.23 2.6 3.02 2.1 3.07 2.1 3.12 0.8 2.97 2.4 2.97 2.6 3.11 2.6 CaO 43.95 0.5 43.05 0.8 43.74 0.6 43.71 0.2 43.42 0.4 43.41 0.6 43.03 0.2 42.70 0.4 Fe 2 O 3 2.04 3.9 2.02 3.2 1.90 4.0 2.01 3.2 1.88 1.0 1.98 3.8 1.91 2.5 2.03 0.9 K 2 O 0.33 2.9 0.30 5.3 0.29 1.7 0.32 6.7 0.40 4.0 0.29 5.7 0.34 7.1 0.38 3.3 MgO 1.92 2.4 2.51 6.6 2.07 2.9 2.09 4.6 1.96 5.8 1.93 4.0 1.96 2.2 1.89 0.9 Na 2 O 0.05 14.4 0.10 18.6 0.04 17.8 0.03 15.0 0.05 18.6 0.03 0.0 0.16 7.7 0.05 16.3 Na 2 O eq 0.27 4.2 0.30 5.3 0.23 3.9 0.25 6.5 0.31 3.2 0.23 12.5 0.39 3.9 0.30 5.4 SiO 2 13.67 1.1 14.38 1.7 13.67 1.4 13.18 1.5 13.04 1.2 13.09 1.2 13.44 1.3 13.70 0.5 SO 3 0.29 12.4 0.29 12.1 0.12 18.3 0.17 12.9 0.22 5.3 0.26 7.5 0.21 3.6 0.21 2.8 LOI 36.59 0.4 35.05 1.2 34.73 0.7 NR NA 36.21 0.7 35.04 0.3 35.00 0.0 35.00 0.0 Notes: NR - Not Reported NA - Not Applicable Parameter C burn CT1 burn CTP burn CTS burnCT2 burn CTB burn CT3 burn CTW burn Table 4.18: CPR- All burns, kiln feed composition These results are comparable to the cement plant results except for the results from CTW and CTS burns. Kiln feed from CTW burn and CTS burn, tested at the external laboratory, seem to have lowered content for almost all the parameters except moisture. Table 4.19: CPR- Baseline Burns, Percentage difference in kiln feed composition relative to CT1 burn CT1 burn Average (wt. %) Average (wt. %) Percent Difference Average (wt. %) Percent Difference Al 2 O 3 3.23 3.07 -5.09 2.97 -8.01 CaO 43.05 43.71 1.54 43.41 0.83 Fe 2 O 3 2.02 2.01 -0.29 1.98 -1.64 K 2 O 0.30 0.32 9.60 0.29 -3.15 MgO 2.51 2.09 -16.94 1.93 -22.96 Na 2 O 0.10 0.03 -67.74 0.03 -70.97 Na 2 O eq 0.30 0.25 -16.76 0.23 -22.52 SiO 2 14.38 13.18 -8.39 13.09 -8.99 SO 3 0.29 0.17 -40.91 0.26 -11.85 LOI 35.05 NR NA 35.04 -0.04 CT2 burn Parameter CT3 burn 158 Table 4.20: ELR- Baseline Burns, Percentage difference in kiln feed composition relative to CT1 burn CT1 burn Value (wt. %) Value (wt. %) % Diff. Value (wt. %) % Diff. Al 2 O 3 2.75 4.09 48.4 4.46 62.0 CaO 40.23 64.08 59.3 63.62 58.1 Fe 2 O 3 1.92 3.11 61.9 3.03 57.8 K 2 O 0.29 0.46 57.5 0.42 45.2 MgO 2.08 3.18 52.6 3.41 63.4 Na 2 O 0.03 0.08 134.2 0.08 129.6 P 2 O 5 0.04 0.05 7.1 0.07 60.7 SiO 2 17.00 24.18 42.2 23.84 40.2 SO 3 0.24 0.26 9.9 0.53 121.4 TiO 2 0.21 0.26 28.3 0.27 29.1 Moisture 0.19 0.31 66.3 0.14 -23.5 LOI 35.19 33.30 -5.4 34.70 -1.4 Value (ppm) Value (ppm) % Diff. Value (ppm) % Diff. As 13 23 78.4 23 76.0 Ba 257 200 -22.0 300 17.0 Cd ND ND NA ND NA Cl 76 97 27.6 105 38.2 Co 21 14 -33.1 10 -52.2 Cr 60 96 60.6 106 77.1 Cu ND 28 NA 56 NA Hg 0.10 ND NA 1 430.0 Mn 317 1800 469 2000 532 Mo ND ND NA ND NA Ni 15 5 -68.5 16 8.0 Pb 9 ND NA 17 77.4 Sb 88 NR NA NR NA Se ND 3 NA ND NA Sr 229 500 118.3 500 118.3 V 48 61 26.7 72 49.6 Zn 106 21 -80.6 300 182.3 Notes: ND - Not Detected NA - Not Applicable Parameter CT2 burn CT3 burn 159 160 Table 4.21: CPR- Fuel Burns, Percentage difference in kiln feed composition relative to baseline burns C burn CTP burn CTB burn CTW burn CTS burn Percent Difference 1 Percent Difference 2 Percent Difference 3 Percent Difference 3 Percent Difference 3 Al 2 O 3 -3.72 -1.53 18.38 0.00 4.75 CaO 2.09 0.07 3.75 -0.87 -1.63 Fe 2 O 3 1.10 -5.33 -10.07 -3.46 2.13 K 2 O 13.22 -11.19 2.80 20.50 33.88 MgO -23.45 -0.54 0.41 1.40 -2.16 Na 2 O -54.52 32.86 0.08 428.57 66.67 Na 2 O eq -9.15 -5.75 2.50 69.17 31.25 SiO 2 -4.95 3.74 -4.36 2.66 4.68 SO 3 -0.11 -32.42 -0.70 -19.89 -20.72 LOI 4.38 NA NA -0.11 -0.11 Notes: 3 Relative to CT3 burn Parameter NA - Not Applicable 1 Relative to CT1 burn 2 Relative to CT2 burn 161 Figure 4.2: CPR-Fuel Burns, Percentage difference in kiln feed composition relative to baseline burns Table 4.22: ELR- Fuel Burns, Percentage difference in kiln feed composition relative to baseline burns Value (wt %) % Diff. 1 Value (wt %) % Diff. 2 Value (wt %) % Diff. 3 Value (wt %) % Diff. 3 Value (wt %) % Diff. 3 Al 2 O 3 3.05 10.6 4.91 20.1 4.41 -1.2 2.96 -33.6 3.26 -26.9 CaO 44.18 9.8 65.27 1.9 67.86 6.7 41.36 -35.0 42.69 -32.9 Fe 2 O 3 2.15 12.1 3.01 -3.3 3.05 0.5 1.83 -39.7 2.00 -34.1 K 2 O 0.33 12.5 0.50 8.9 0.57 35.0 0.32 -24.4 0.37 -12.6 MgO 1.90 -8.7 3.35 5.3 3.15 -7.6 2.04 -40.1 2.07 -39.2 Na 2 O 0.01 -70.9 0.02 -76.4 0.05 -35.5 0.05 -36.5 0.20 153.9 P 2 O 5 0.05 22.4 0.07 52.4 0.05 -26.3 0.02 -71.0 0.05 -27.5 SiO 2 13.38 -21.3 21.87 -9.6 19.97 -16.2 13.26 -44.4 13.95 -41.5 SO 3 0.35 47.6 0.34 28.8 0.37 -30.7 0.21 -60.5 0.33 -37.9 TiO 2 0.17 -17.1 0.24 -9.1 0.24 -9.2 0.15 -43.6 0.14 -47.3 Moisture 0.06 -67.8 0.10 -67.8 0.27 89.6 0.23 61.2 0.18 26.2 LOI 34.44 -2.1 34.67 4.1 32.72 -5.7 37.63 8.4 34.81 0.3 Value (ppm) % Diff. 1 Value (ppm) % Diff. 2 Value (wt %) % Diff. 3 Value (ppm) % Diff. 3 Value (ppm) % Diff. 3 As 3 -79.6 18 -21.6 23 0.9 17 -24.9 26 14.8 Ba 192 -25.3 400 100.0 400 33.3 200 -33.3 200 -33.3 Cd ND NA NR NA ND NA ND NA ND NA Cl 111 46.1 63 -35.1 84 -20.0 192 82.9 182 73.3 Co ND NA 14 1.6 11 16.1 8 -18.8 14 42.2 Cr 51 -14.7 86 -10.8 108 1.5 159 49.5 107 0.6 Cu 43 NA 41 48.8 18 -68.3 ND NA ND NA Hg 0.02 -80.0 NR NA ND NA 0.30 -43.4 0 -89.4 Mn 664 109.9 1700 -5.6 1700 -15.0 1100 -45.0 1000 -50.0 Mo ND NA 16 NA ND NA 3 NA 15 NA Ni ND NA 12 161.3 8 -51.6 ND NA 1640 NA Pb 24 150.5 ND NA 4 -77.2 12 -28.3 ND NA Sb 3 -62.5NRNANDNA NR NANRNA Se 1 NANRNANDNA ND NANDNA Sr 261 13.8 500 0.0 500 0.0 200 -60.0 300 -40.0 V 39 -18.0 73 20.0 70 -2.8 61 -15.1 66 -8.2 Zn 113 6.2 37 79.0 118 -60.7 33 -89.0 34 -88.7 1 Relative to CT1 burn 2 Relative to CT2 burn 3 Relative to CT3 burn C burn CTP burn Parameter Notes: NA - Not Applicable NR - Not Reported ND - Not Detected CIP-Collection in Progress CTS burn CTW burnCTB burn 162 163 4.3.3 Fuels Fuels samples were collected by Auburn University and tested at the external laboratory. Coal was the only fuel tested at both the cement plant and the external laboratory. In this section, the chemical composition and properties of the fuels used in the burns will be discussed in detail. Firstly, the composition and properties of coal will be discussed followed by that of scrap tires, waste plastics, broiler litter, woodchips, and switchgrass. At the specific cement plant where the 3-day trials were conducted, the following specifications were targeted for the as-received alternative fuels: ? energy value ? 5,000 BTUs/lb (11.6 MJ/kg), ? chlorine content ? 0.2 percent, ? sulfur content ? 2.0 percent, ? nitrogen content ? 1.4 percent, ? moisture content ? 14 percent, and ? ash content ? 18 percent. The average heat values of all the fuels used in the burns are shown in Figure 4.3. These values were determined by combustion analysis and reported by the external laboratory. It must be noted that these values for all the fuels are in the expected range based on the review of literature, presented in Section 2.3.4. 164 Figure 4.3: ELR: Dry Heat Values of the fuels 165 4.3.3.1 Coal Pulverized coal is the primary fuel used to produce clinker from the kiln feed at the cement plant. Proximate, ultimate, and combustion analyses were conducted by the cement plant. These analyses were conducted on a dry basis, which means the tests were done after all moisture had been removed. Additionally, the standard cement plant parameters were determined. These parameters were determined on the ash from the fuels. This was done because it is the ash from the fuels which is actually incorporated into the clinker. Each of these tests was conducted on a single sample during each burn. The results of these tests, along with the percent differences for all the burns relative to CT1 burn are presented in Table 4.23. Unfortunately, the coal sources have been changed from time to time, during the course of the project. This decision was made with production and economic issues in mind. It is reflected in Table 4.23. The percentage differences of parameters of coal from all the fuel burns relative to CT1 burn have inconsistently wide ranges, making it difficult to group results for any particular baselines burns. For instance, the Fe 2 O 3 content in coal from CTP burn was 481 percent higher while the CaO content in coal from CTW burn was 92 percent lower. In addition, the baseline burns have less than 15 percent variation in Fe 2 O 3 and less than 10 percent variation in CaO content. Similar observations can be made for different parameters in different burns. This is the reason why the coal compositions from all burn are presented together and compared to that from CT1 burn as a single reference base. It can be seen that the weight percentage of volatile matter was fairly similar for all burns, with less than 14 percent difference which is also reflected in the heat values, 166 which is, in fact, helpful in comparison of fuel replacement rates of alternative fuels based on total energy replacement. Similar trends can be found in the coal data from the external laboratory based on composite samples of coal. These data are presented in Tables 4.24 and 4.25. The results from the proximate and ultimate analyses are shown in Table 4.24. The standard parameters in chemical composition of coal are shown in Table 4.25. 4.3.3.2 Scrap tires The scrap tires as fuel in combination with coal have been used at the cement plant for quite some time. The initial investments in setting up the conveying and feeding system for scrap tires and the favorable results found from CT1 burn have encouraged the cement plant to use the fuel combination on a regular basis. Scrap tires are not tested for their chemical composition by the cement plant. However, they were sampled by Auburn University, and tested by the external laboratory. The samples were collected by randomly removing eight tires from the feed stream, removing a radial section of each tire, reducing each section to one inch squares, and making a single composite specimen from the pieces. One composite sample per burn, prepared in this manner, was tested by the external laboratory. A proximate, ultimate, and combustion analysis were conducted on this sample. Additionally, a XRF scan was used to determine the standard external laboratory parameters. The results from the proximate, ultimate, and combustion analyses, as conducted by the external laboratory for all burn samples, are shown in Table 4.26. The percent differences relative to CT1 burn are also shown. Table 4.23: CPR ?All Burns, Chemical analysis of coal and percent difference relative to CT1 burn CT1 burn Value (wt. %) % Diff. Value (wt. %) Value (wt. %) % Diff. Value (wt. %) % Diff. Value (wt. %) % Diff. Value (wt. %) % Diff. Value (wt. %) % Diff. Value (wt. %) % Diff. Ash 18.9 6.1 17.8 23.4 31.5 16.2 -9.3 18.8 5.4 23.3 30.6 18.8 5.4 17.8 -0.2 Fixed Carbon 50.2 -3.6 52.1 48.4 -7.0 54.9 5.4 53.9 3.5 55.7 7.1 53.5 2.7 54.5 4.7 Volatile Matter 30.9 2.7 30.1 28.1 -6.6 29.0 -3.9 27.4 -9.2 26.0 -13.7 27.7 -7.9 27.7 -8.0 Carbon 69.1 -3.0 71.2 64.4 -9.5 72.6 2.1 70.3 -1.3 59.9 -15.9 53.5 -24.9 72.5 1.9 Hydrogen 4.3 -2.1 4.3 4.0 -7.6 4.4 0.9 4.3 -1.2 4.1 -6.5 4.4 1.2 4.4 0.7 Nitrogen 1.5 4.1 1.5 1.3 -9.7 1.4 -4.1 1.4 -4.8 1.3 -12.4 1.3 -9.7 1.3 -8.3 Oxygen 5.2 41.5 3.7 3.1 -17.3 3.6 -3.5 3.6 -2.2 3.3 -9.9 3.2 -12.5 2.7 -28.2 Sulfur 1.1 -30.7 1.5 3.8 147.7 2.7 77.8 2.6 69.9 2.6 67.5 1.4 -7.8 1.4 -11.1 Al 2 O 3 24.7 5.2 23.5 15.4 -34.2 21.6 -7.9 24.0 2.5 23.3 -0.8 28.9 23.3 22.7 -3.0 CaO 13.3 4.6 12.7 3.2 -74.6 7.8 -38.5 6.3 -50.5 6.9 -45.5 1.0 -92.5 8.2 -35.9 Fe 2 O 3 5.8 -6.6 6.2 36.2 480.8 15.7 152.2 9.9 58.0 7.7 22.7 7.5 19.9 7.9 27.2 K 2 O 2.0 -8.8 2.2 1.9 -10.2 2.1 -5.1 2.3 7.9 2.8 30.2 3.3 50.9 2.7 23.1 MgO 1.2 -20.8 1.5 1.0 -30.2 1.0 -30.9 1.1 -26.2 1.1 -24.6 1.2 -19.5 1.1 -28.2 Na 2 O 0.4 25.8 0.3 0.4 16.1 0.2 -51.6 0.2 -45.2 0.1 -55.9 0.4 38.7 0.2 -48.4 SiO 2 42.9 -7.2 46.2 36.2 -21.7 43.4 -6.2 48.1 4.1 50.3 8.9 55.6 20.2 48.8 5.7 SO 3 8.4 12.8 7.4 4.4 -40.6 6.8 -8.2 6.5 -12.1 6.4 -13.5 1.0 -86.4 7.0 -5.3 12102 -3.2 12506 11255 -10.0 12864 2.9 12169 -2.7 11481 -8.2 12321 -1.5 12495 -0.1 Notes: 1 Value is Reported as BTU/lb CT2 burn CTB burn Prox i m at e An al y s i s Ul ti ma te An a l ys is Test Parameter Heat Value 1 C burn Stan d a rd Par a meters CTP burn CTS burnCT3 burn CTW burn 167 Table 4.24: ELR ?All Burns, Proximate and Ultimate analyses of coal and percent difference relative to CT1 burn 168 CT1 burn Value (wt. %) % Diff. Value (wt. %) Value (wt. %) % Diff. Value (wt. %) % Diff. Value (wt. %) % Diff. Value (wt. %) % Diff. Value (wt. %) % Diff. Value (wt. %) % Diff. Ash 22.45 34.1 16.74 24.54 46.6 14.51 -13.3 17.65 5.4 26.2 56.5 17.59 -21.6 16.45 -1.7 Fixed Carbon 49.58 -9.5 54.81 47.68 -13.0 30.19 -44.9 53.61 -2.2 47.39 -13.5 53.8 8.5 55.19 0.7 Volatile Matter 27.97 -1.7 28.45 27.78 -2.4 55.3 94.4 28.73 1.0 26.41 -7.2 28.61 2.3 28.36 -0.3 Carbon 67.61 -7.5 73.09 64.68 -11.5 72.24 -1.2 69.84 -4.4 63.96 -12.5 71.06 5.1 71.33 -2.4 Hydrogen 3.61 -22.5 4.66 3.93 -15.7 3.71 -20.4 3.59 -23.0 3.57 -23.4 4.16 15.2 3.75 -19.5 Nitrogen 1.1 -9.8 1.22 1.08 -11.5 0.5 -59.0 0.59 -51.6 1.45 18.9 1.48 34.5 0.96 -21.3 Oxygen 3.95 25.8 3.14 4.11 30.9 7.49 138.5 6.77 115.6 3.55 13.1 4.57 15.7 6.41 104.1 Sulfur 1.28 11.3 1.15 1.66 44.3 1.55 34.8 1.55 34.8 1.27 10.4 1.14 -10.9 1.1 -4.3 11698 -7.3 12624 11369 -9.9 12864 1.9 12431 -1.5 11204 -11.2 12445 6.4 12664 0.3 Notes: 1 Value is Reported as BTU/lb Heat Value 1 Parameter Ul t i ma t e Ana l y s i s Pr oximate A n alysis Test C burn CT2 burn CTB burn CT3 burnCTP burn CTW burn CTS burn Table 4.25: ELR ?All burns, Chemical analysis of coal and percent difference relative to CT1 burn CT1 burn Value (wt. %) % Diff. Value (wt. %) Value (wt. %) % Diff. Value (wt. %) % Diff. Value (wt. %) % Diff. Value (wt. %) % Diff. Value (wt. %) % Diff. Value (wt. %) % Diff. Al 2 O 3 25.1 -1.8 25.5 21.0 -17.6 22.9 -10.5 24.3 -5.0 25.2 -1.1 24.6 -3.6 23.9 -6.5 CaO 7.5 -5.6 8.0 8.3 3.5 5.6 -29.3 7.2 -9.5 4.7 -40.5 9.3 16.7 12.8 60.7 Fe 2 O 3 7.6 3.5 7.4 15.2 106.2 18.7 153.8 9.0 22.9 6.6 -10.8 7.5 1.6 7.8 5.7 K 2 O 2.6 -3.5 2.7 2.5 -6.7 1.8 -33.3 2.4 -10.1 3.3 21.8 2.2 -15.9 2.6 -4.0 MgO 1.4 0.6 1.3 1.3 -7.0 1.0 -24.7 1.1 -19.9 1.3 -0.4 1.1 -19.9 1.3 -2.5 Na 2 O 0.2 -48.6 0.4 0.4 -15.8 0.2 -42.5 0.2 -61.1 0.2 -59.2 0.2 -53.4 0.6 33.3 P 2 O 5 0.2 -11.6 0.2 0.2 12.9 0.4 73.8 0.2 -13.5 0.1 -33.3 0.2 -16.8 0.1 -41.1 SiO 2 47.4 3.0 46.0 43.4 -5.6 42.4 -7.9 47.2 2.6 53.4 16.0 47.2 2.5 49.4 7.4 SO 3 7.0 -5.2 7.3 6.5 -11.3 5.5 -24.4 7.2 -1.7 4.0 -45.9 6.4 -12.8 0.3 -95.5 TiO 2 1.1 -2.3 1.2 1.0 -16.6 1.0 -11.1 1.0 -10.7 4.0 244.9 1.2 0.5 1.0 -9.6 Value (ppm) % Diff. Value (ppm) Value (ppm) % Diff. Value (ppm) % Diff. Value (ppm) % Diff. Value (ppm) % Diff. Value (ppm) % Diff. Value (ppm) % Diff. As 325 304 80 316 292 200 148.3 94 16.8 72 -10.5 86 6.9 114 41.7 Ba 1274 18 1083 1300 20 1500 38.5 1200 10.8 1100 1.5 1096 1.2 1100 1.5 Cd ND NA ND 5 1 NA ND NA ND NA ND NA ND NA ND NA Cl 125 1 -31 182 134 1 -26 94 -48.4 101 -44.5 89 -51.1 105 -42.3 236 29.7 Co ND NA 30 44 49 61 105.6 41 39.3 29 -1.8 54 82.9 43 45.6 Cr 109 -14 127 117 -8 107 -16.2 114 -10.8 109 -14.4 190 49.3 132 3.7 Cu 150 29 116 103 -11 116 -0.5 114 -2.2 81 -30.2 70 -39.7 103 -11.3 Hg 0.23 1 NA ND 0.022 1 NA 0 NA 0 NA 0 NA 0.2 NA 0.08 NA Mn 221 -38 355 1500 322 2900 716 300 -15.6 300 -15.6 498 40.1 500 40.7 Mo ND NA 9 39 326 37 306.0 35 284.6 24 161.9 31 238.3 29 216.5 Ni 81 -19 100 92 -8 107 6.9 86 -13.7 68 -31.9 79 -20.8 78 -21.8 Pb 42 -13 48 45 -6 39 -18.2 49 2.3 43 -10.1 47 -1.8 ND NA Sb ND NA ND NR NA NR NA NR NA NR NA NR NA NR NA Se ND NA 81 1 -88 7 -14.1 5 -38.6 7 -14.1 6 -26.3 7 -14.1 Sr 487 -17 591 500 -15 900 52.4 700 18.5 500 -15.3 598 1.3 400 -32.3 V 226 0 225 214 -5 210 -6.9 213 -5.2 226 0.4 214 -4.9 228 1.3 Zn 68 -49 133 197 48 179 34.3 73 -45.0 81 -39.3 63 -52.8 9 -93.3 Notes: 1 Dry Basis ND - Not Detected NR - Not Reported NA - Not Applicable CIP - Collection in Progress St an dard Pa ram e t e r s Test CTW burnCTP burn Parameter C burn CTS burnCT2 burn CTB burn CT3 burn 169 170 Overall, there are relatively large differences in many of the parameters. Some of the oxygen, moisture, and volatile matter values showed the greatest decreases, while some nitrogen and sulfur values showed the greatest increases. These changes are most likely due to the variable nature of the tires being used in the fuel feed stream. Many different tire types and sources are used, and these differences in results may simply be an indication of the actual variability in the stream. Similar trends can be observed in the standard external laboratory parameters for the tires presented in Table 4.27. The high content of Fe 2 O 3 is due to the steel belts used in the tires, which act as an iron source for portland cement production. The final aspect of the tires that is pertinent to this study is the rate of substitution of tires relative to the total fuel consumption rate. The ranges of fuel replacement rates for tires for each burn are listed in Table 4.1. This percentage was calculated using the average heat value of the fuels (reported from each burn) as determined by the external laboratory. The heat values used in this calculation were 11,897 BTU/lb for the coal, and 14,577 BTU/lb for the tires. The feed rate data (in tons per hour) were collected at the cement plant every five minutes. A 30-minute rolling average, reported over each of the 72-hour burns in which tires were used, was calculated to report the feed rates. The average tire-to-fuel replacement rates in percentages for CT1, CTP, CT2, CTB, CT3, CTW, and CTS burns are 6.5 %, 4.8 %, 1.7 %, 1.7 %, 1.0 %, 5.7 % and 16.3 % respectively. The value for the CTS burn was unusually high, which is considered an anomaly that may have arisen due to malfunctioning of the weighing scale, as reported by the cement plant personnel. Table 4.26: ELR ?All Burns, Proximate, Ultimate, and Combustion Analyses for tires, and percent difference relative to CT1burn 171 CT1 burn Value (wt. %) Value (wt. %) % Diff. Value (wt. %) % Diff. Value (wt. %) % Diff. Value (wt. %) % Diff. Value (wt. %) % Diff. Value (wt. %) % Diff. Ash 13.7 14.6 6.1 14.5 6.0 12.2 -11.0 18.9 37.7 15.0 9.3 24.4 77.8 Fixed Carbon 24.6 26.4 7.2 46.9 90.7 49.4 100.9 41.9 70.3 23.6 -4.2 19.8 -19.4 Moisture 1 0.14 0.07 -50.0 0.09 -33.7 0.09 -33.7 0.07 -49.8 0.4 157.1 1.0 610.9 Volatile Matter 61.7 59.1 -4.2 38.5 -37.7 38.3 -37.9 39.2 -36.5 61.5 -0.4 55.8 -9.6 Carbon 72.3 75.9 5.0 77.9 7.6 79.0 9.2 69.5 -3.9 77.6 7.3 72.6 0.4 Hydrogen 7.1 6.5 -7.4 5.6 -21.0 5.4 -22.9 5.0 -29.6 5.9 -16.3 0.2 -96.8 Nitrogen 0.36 0.5 44.4 0.07 -79.4 0.06 -84.5 1.74 383.2 0.1 -72.2 0.4 9.1 Oxygen 5.0 0.5 -90.8 0.7 -86.9 1.8 -63.0 1.8 -64.5 0.3 -93.8 1.1 -78.8 Sulfur 1.54 2.00 29.9 1.31 -15.0 1.47 -4.8 3.15 104.3 1.1 -28.6 1.3 -16.1 14467 16754 15.8 15456 6.8 15501 7.1 14972 3.5 15098 4.4 13239 -8.5 Notes: 1 As Received 2 Values Reported as BTU/lb CIP- Collection in Progress NA- Not Applicable CTB burn CT3 burn CTW burn CTS burnCT2 burnCTP burn Heat Value 2 Test Parameter U l ti m a te An alysis P r ox imat e An alysis CT1 burn Value (wt. %) Value (wt. %) % Diff. Value (wt. %) % Diff. Value (wt. %) % Diff. Value (wt. %) % Diff. Value (wt. %) % Diff. Value (wt. %) % Diff. Al 2 O 3 1.2 1.2 -2.5 0.8 -33.7 6.2 423.0 0.2 -86.1 4.4 274.2 0.5 -54.9 CaO 2.4 1.7 -28.8 3.8 62.0 3.2 34.2 1.6 -31.6 3.0 27.2 2.9 24.7 Fe 2 O 3 68.6 84.7 23.4 57.4 -16.3 46.8 -31.8 85.9 25.1 57.7 -15.9 77.1 12.3 K 2 O 0.3 0.2 -48.5 0.3 -12.0 0.3 -13.3 0.2 -43.6 0.5 44.8 0.3 -23.0 MgO 0.4 0.3 -5.7 0.0 -87.2 0.0 -91.6 0.1 -78.2 0.4 2.7 0.2 -41.7 Na 2 O 0.3 0.2 -38.7 0.5 51.3 0.6 104.5 0.2 -31.9 1.5 380.6 0.1 -58.7 P 2 O 5 0.2 0.1 -42.9 0.2 3.7 0.2 0.1 0.1 -68.2 0.4 106.3 0.2 -6.7 SiO 2 16.9 4.9 -70.9 25.1 48.9 27.1 60.6 2.8 -83.6 12.9 -23.6 5.4 -68.1 SO 3 2.6 0.5 -80.7 0.8 -67.8 0.5 -81.9 0.3 -88.5 4.2 57.4 2.3 -14.7 TiO 2 0.2 0.0 -95.0 0.4 98.1 6.8 3309.5 0.3 69.9 3.7 1772.0 0.1 -50.0 Value (ppm) Value (ppm) % Diff. Value (ppm) % Diff. Value (ppm) % Diff. Value (ppm) % Diff. Value (ppm) % Diff. Value (ppm) % Diff. As (ppm) NR NR NA ND NA ND NA 4 NA ND NA ND NA Ba (ppm) 300 300 0.0 1135 278.3 1134 278.0 0 -100.0 ND NA 0 -100.0 Cd (ppm) 1 6 3 -50. NDNANDNANDNA NDNANDNA Cl (ppm) 1 405 NR NA 1174 189.9 568 40.2 946 133.6 515 27.2 1696 318.8 Co (ppm) 616 536 -13.0 852 38.3 759 23.2 1191 93.3 642 4.2 724 17.5 Cr (ppm) 118 178 50.8 94 -20.6 56 -52.6 260 120.4 133 13.0 129 9.5 Cu (ppm) 1398 900 -35.6 546 -61.0 408 -70.8 1068 -23.6 3762 169.1 0 -100.0 Hg (ppm) 1 0.38 ND NA 0.16 -58.2 0.21 -45.2 ND NA 0.1 -73.9 NR NA Mn (ppm) 4100 5200 26.8 3600 -12.2 2900 -29.3 3900 -4.9 3754 -8.4 4300 4.9 Mo (ppm) 28 23 -17.9 31 9.8 11 -60.3 21 -25.6 8 -71.3 11 -59.3 Ni (ppm) 367 239 -34.9 91 -75.3 70 -80.8 215 -41.5 8 -97.8 332 -9.5 Pb (ppm) 11 13 18.2 17 58.3 ND NA 10 -5.6 30 168.9 8 -27.3 Sb (ppm) NR NR NA NR NA NR NA NR NA NR NA NR NA Se (ppm) 1 ND ND NA ND NA ND NA ND NA ND NA ND NA Sr (ppm) 200 100 -50.0 0 -100.0 0 -100.0 0 -100.0 36 -82.0 20 -90.0 V (ppm) 37 50 35.1 50 34.4 214 477.5 20 -47.1 117 216.8 10 -74.1 Zn (ppm) 0.05 0.10 85.2 0.07 33.3 0.06 16.1 0.07 20.9 0.09 69.1 0.07 35.6 Notes: 1 Dry Basis NR - Not Reported NA - Not Applicable ND - Not Detected CIP - Collection in Progress CTP burn Test Parameter CTS burnCT2 burn CTB burn CT3 burn CTW burn S ta n d a rd P a r a m et er s Table 4.27: ELR ?All Burns, Chemical analysis for tires and percent difference relative CT1 burn 172 4.3.3.2 Waste Plastics The waste plastics used in CTP burn were derived from automotive trim scrap material, i.e. the discarded interior carpet and lining of cars. The material was not tested for any chemical parameters by the cement plant. However, samples of the plastics were collected by Auburn University and tested by the external laboratory. Discrete samples were collected every three hours, and each of them was tested. In addition, every fourth sample was tested in duplicate. The tests conducted on each of these specimens were the same as for each of the other fuels. The complete set of summary statistics for the proximate, ultimate, and combustion analyses is shown in Table 4.28. The summary statistics applicable to the standard external laboratory parameters for the plastics are shown in Table 4.29. Perhaps the most interesting result was the extremely high concentration of CaO in the plastics, which composed 92 percent of the total weight. The plastics were substituted at an average rate of 16.9 percent, which was significantly higher than the replacement rate of the tires. This percentage was based on an average energy content of 12,754 BTU/lb for the plastics, 16754 BTU/lb for tires and 11,369 BTU/lb for the coal, as determined by the external laboratory. The fuel feed rates (in tons per hour) was supplied by the cement plant. One final property of the plastics which is pertinent to this study is the material?s density. The density of each of the 24 samples of plastics collected at the cement plant was determined by researchers at Auburn University. Each of the 24 results can be found in Appendix B.3. The average of these values was 5.26 lb/ft 3 which is very low 173 compared to other fuels. The low density material created feed problems during the cement production and hence affected the fuel feed rates. Table 4.30 shows the proximate and ultimate analysis of all the fuels used in CTP burn and Table 4.31 shows the chemical composition the fuels used in CTP burn, as reported by the external laboratory. Although the data presented have been shown previously, presentation in this manner allows the reader to easily see the differences in composition of each of the fuels relative to one another. This table will serve as the basis for determining if the changes in chemical composition of the output materials can be attributed in any way to the fuels. Additionally, Table 4.30 shows the heat value for each of the fuels. The plastics had a higher heat value than any of the coal samples tested for any of the burns, which is very encouraging. Table 4.28: ELR ? Proximate, Ultimate, and Combustions Analysis of Plastics from CTP burn Test Parameter Average C.V. (%) P-Value 2 Ash (wt. %) 0.32 40.5 1 0.026 Fixed Carbon (wt. %) 8.75 40.8 1 0.013 Moisture (wt. %) 3 88.30 2.7 1 <0.005 Volatile Matter (wt. %) 2.95 43.9 1 0.026 Carbon (wt. %) 8.06 18.4 1 <0.005 Hydrogen (wt. %) 64.23 13.1 1 <0.005 Nitrogen (wt. %) 1.27 31.6 0.888 Oxygen (wt. %) 0.22 185.6 1 <0.005 Sulfur (wt. %) 17.46 49.3 1 <0.005 12754 7.9 0.313 Notes: 1 Not Normally Distributed 3 As Received 2 Based on Anderson-Darling Statistics Proximate An alysis Ul ti mate Analysis Heat Value (BTU/lb) 174 Table 4.29: ELR - Standard Parameters of Plastics from CTP burn 175 ND- Not Detected 3 Dry Basis Test Parameter Average C.V. (%) P-Value 2 Al 2 O 3 (wt. %) 0.48 59.8 1 <0.005 CaO (wt. %) 92.00 2.0 1 0.034 Fe 2 O 3 (wt. %) 0.54 25.8 1 0.041 K 2 O (wt. %) 0.13 40.4 1 <0.005 MgO (wt. %) 1.75 4.2 0.727 Na 2 O (wt. %) 0.17 91.9 1 <0.005 P 2 O 5 (wt. %) 0.14 41.3 0.429 SiO 2 (wt. %) 2.12 34.6 1 <0.005 SO 3 (wt. %) 0.41 30.5 0.116 TiO 2 (wt. %) 1.77 46.8 0.177 As (ppm) 62 62.7 1 0.067 Ba (ppm) 4100 47.1 0.518 Cd (ppm) 3 7 9.3 1 <0.005 Cl (ppm) 3 54 25.8 1 <0.005 Co (ppm) 142 27.8 0.113 Cr (ppm) 356 33.0 0.504 Cu (ppm) 369 28.4 0.279 Hg (ppm) 3 ND NA NA Mn (ppm) 300 20.9 1 <0.005 Mo (ppm) 6 172.3 0.144 Ni (ppm) 50 165.2 1 <0.005 Pb (ppm) 628 59.6 1 0.009 Sb (ppm) NR NA NA Se (ppm) 3 ND NA NA Sr (ppm) 600 8.8 1 <0.005 V (ppm) 66 83.8 1 <0.005 Zn (ppm) 283 50.0 0.275 Notes: NR - Not Reported 1 Not Normally Distributed NA - Not Applicable 2 Based on Anderson-Darling Statistics S tan d a rd Parameters Many differences between the fuels are shown in Table 4.31. The tires and the plastics contained very little Al 2 O 3 , but each of the coal samples was approximately 21 percent Al 2 O 3 . The plastics were over 90 percent CaO, whereas the coal and tires contained less than two percent. The Fe 2 O 3 was much higher in the tires than in the coal or plastics. This can be attributed to the steel belts present in the tires. The final primary parameter that showed a large difference was the SiO 2 . Each coal sample was made up of approximately 40 percent SiO 2 , while the tires and the plastics contained much less. A number of the less prominent parameters showed pronounced differences. Ba, V, and Zn levels were reasonably lower in the tires than the other fuels. Co, Cu, Mn, and Ni all showed appreciably higher concentrations in tires than the other fuels. The plastics showed higher concentrations of Ba, Cr, Pb, and Zn than the other fuels. Cl and Ni were lower in the plastics than in the other fuels. Table 4.30: ELR ? Proximate and Ultimate analyses of all fuels from CTP burn Coal Tires Plastics Ash (wt. %) 24.54 14.56 0.32 Fixed Carbon (wt. %) 47.68 26.38 8.75 Volatile Matter (wt. % 27.78 59.06 2.95 Carbon (wt. %) 64.68 75.94 8.06 Hydrogen (wt. %) 3.93 6.53 64.23 Nitrogen (wt. %) 1.08 0.52 1.27 Oxygen (wt. %) 4.11 0.46 0.22 Sulfur (wt. %) 1.66 2.00 17.46 11369 16754 12754 CTP burn Parameter Heat Value (BTU/lb) Test Pr oxima te A n alysis Ult i mate Analysis 176 Table 4.31: ELR ? Chemical composition of all fuels from CTP burn 177 1 Dry Basis Coal Tires Plastics Al 2 O 3 (wt. %) 21.04 1.15 0.48 CaO (wt. %) 8.25 1.68 92.00 Fe 2 O 3 (wt. %) 15.16 84.72 0.54 K 2 O (wt. %) 2.49 0.17 0.13 MgO (wt. %) 1.25 0.33 1.75 Na 2 O (wt. %) 0.36 0.19 0.17 P 2 O 5 (wt. %) 0.23 0.12 0.14 SiO 2 (wt. %) 43.44 4.91 2.12 SO 3 (wt. %) 6.5 0.51 0.41 TiO 2 (wt. %) 0.96 0.01 1.77 As (ppm) 316 NR 62 Ba (ppm) 1300 300 4100 Cd (ppm) 1 537 Cl (ppm) 1 134 NR 54 Co (ppm) 44 536 142 Cr (ppm) 117 178 356 Cu (ppm) 103 900 369 Hg (ppm) 1 0.02 0 0 Mn (ppm) 1500 5200 300 Mo (ppm) 39 23 6 Ni (ppm) 92 239 50 Pb (ppm) 45 13 628 Sb (ppm) NR NR NR Se (ppm) 1 1NDND Sr (ppm) 500 100 600 V (ppm) 214 50 66 Zn (ppm) 197 0 283 Notes: ND - Not Detected NR - Not Reported S tan d a rd Parameters CTP burn Test Parameter 4.3.3.3 Broiler Litter Broiler litter used in CTB burn was obtained from a local broiler producer. The material was not tested for any chemical parameters by the cement plant. However, samples of the broiler litter were collected by Auburn University staff and tested by the external laboratory. Discrete samples were collected every three hours, and each of them was tested. In addition, every fourth sample was tested in duplicate. The tests conducted on each of these specimens were the same as for each of the other fuels. The complete set of summary statistics for the proximate, ultimate, and combustion analyses is shown in Table 4.32. The summary statistics applicable to the standard external laboratory parameters for the broiler litter are shown in Table 4.33. Table 4.32: ELR ? Proximate, Ultimate and Combustion analyses of Broiler litter from CTB burn Test Parameter Average C.V. (%) P-Value 2 Ash (wt. %) 20.61 8.5 1 0.045 Fixed Carbon (wt. %) 33.75 11.5 1 0.023 Moisture (wt. %) 3 29.06 7.6 1 <0.005 Volatile Matter (wt. %) 45.64 5.7 1 <0.005 Carbon (wt. %) 40.89 6.1 1 <0.005 Hydrogen (wt. %) 4.86 7.5 1 <0.005 Nitrogen (wt. %) 4.30 8.6 0.188 Oxygen (wt. %) 28.66 10.2 1 <0.005 Sulfur (wt. %) 0.68 16.6 1 <0.005 6875 2.9 0.113 Notes: 1 Not Normally Distributed 3 As Received 2 Based on Anderson-Darling Statistics Pr oximate A n alysis Ul ti mate Analysis Heat Value (BTU/lb) 178 Table 4.33: ELR - Standard Parameters of Broiler Litter from CTB burn 179 Notes: NR - Not Reported 1 Not Normally Distributed NA - Not Applicable 2 Based on Anderson-Darling Statistics 3 Dry Basis Test Parameter Average C.V. (%) P-Value 2 Al 2 O 3 (wt. %) 0.84 28.6 1 <0.005 CaO (wt. %) 23.52 8.0 1 0.024 Fe 2 O 3 (wt. %) 0.85 25.4 1 <0.005 K 2 O (wt. %) 20.44 7.2 1 <0.005 MgO (wt. %) 7.73 5.5 0.727 Na 2 O (wt. %) 7.02 6.42 1 <0.005 P 2 O 5 (wt. %) 24.54 7.2 0.429 SiO 2 (wt. %) 7.44 43.1 1 <0.005 SO 3 (wt. %) 6.58 4.0 0.116 TiO 2 (wt. %) 0.07 41.0 0.177 As (ppm) 13 49.3 1 0.067 Ba (ppm) 468 19.7 0.518 Cd (ppm) 3 ND NA NA Cl (ppm) 3 5843 5.4 1 <0.005 Co (ppm) 3 36.4 0.113 Cr (ppm) 29 52.0 0.504 Cu (ppm) 2505 3.9 0.279 Hg (ppm) 3 0.2 NA NA Mn (ppm) 8870 8.1 1 <0.005 Mo (ppm) 43 8.3 0.144 Ni (ppm) 44 20.5 1 <0.005 Pb (ppm) 32 91.6 1 0.010 Sb (ppm) NA NA NA Se (ppm) 3 ND NA NA Sr (ppm) 379 13.8 1 <0.005 V (ppm) 18 18.3 1 <0.005 Zn (ppm) 2685 4.5 0.275 S tan d a rd Parameters 180 Broiler Litter was found to be high in CaO, K 2 O and P 2 O 5. It is interesting to note that the nitrogen content in broiler litter exceeds the plant target of 1.4, mentioned in Section 4.3.3. It also had high volatile matter content. Its average heat value as determined at the external laboratory was about 6875 BTU/lb which is lower than that of coal. The broiler litter was substituted at an average rate of 6.5 percent, which was higher than the replacement rate of the tires. This percentage was based on an average as-received energy content of 6875 BTU/lb for the broiler litter, 15501 BTU/lb for scrap tires and 12,481BTU/lb for the coal. The fuel feed rates (in tons per hour) was supplied by the cement plant. The average density of Broiler Litter was measured to be 41.7 lb/ft 3 . Though it has low energy value, it did not cause any feeding problems and handled easily. The odor of the litter was noticeable but the plant personnel were informed of it in advance. The proximate and ultimate analyses of all the fuels used in CTB burn are shown in Table 4.34. The chemical compositions of all the fuels used in CTB burn are presented in Table 4.35. These tables provide a basis to draw comparisons between all the fuels from CTB burn. The high content of CaO, K 2 O and P 2 O 5 makes broiler litter completely unique and different from coal and scrap tires which mostly contain SiO 2 and Fe 2 O 3 , respectively. The lower sulfur and higher oxygen content than coal and tires may be reflected in lower sulfur emissions which will be discussed in Section 4.3.8. The higher alkali content (K 2 O and Na 2 O) of broiler litter than that of coal or tires may affect the kiln condition. Broiler litter has very little Al 2 O 3 and Fe 2 O 3 compared to coal or tires. This may take away the advantage of fuels contributing as raw materials. Broiler litter is rich in manganese and copper, but has lower content of toxic elements such as arsenic and lead than coal. It has very high chlorine content compared to coal or tires and is also rich in zinc. Table 4.34: ELR ? Proximate and Ultimate analyses of all fuels from CTB burn Coal Tires Broiler Litter Ash (wt. %) 17.65 12.21 20.61 Fixed Carbon (wt. %) 53.61 49.41 33.75 Volatile Matter (wt. %) 28.73 38.28 29.06 Carbon (wt. %) 69.84 78.98 40.89 Hydrogen (wt. %) 3.59 5.44 4.86 Nitrogen (wt. %) 0.59 0.06 4.30 Oxygen (wt. %) 6.77 1.84 28.66 Sulfur (wt. %) 1.55 1.47 0.68 12431 15501 6875 CTB burn Heat Value (BTU/lb) Test Parameter Proximate An a l ysis Ul ti mate Analysis 181 Table 4.35: ELR ? Standard parameters of all fuels from CTB burn Coal Tires Broiler Litter Al 2 O 3 (wt. %) 24.27 6.17 0.84 CaO (wt. %) 7.22 3.17 23.52 Fe 2 O 3 (wt. %) 9.04 46.84 0.85 K 2 O (wt. %) 2.40 0.29 20.44 MgO (wt. %) 1.08 0.03 7.73 Na 2 O (wt. %) 0.17 0.63 7.02 P 2 O 5 (wt. %) 0.18 0.21 24.54 SiO 2 (wt. %) 47.21 27.09 7.44 SO 3 (wt. %) 7.21 0.48 6.58 TiO 2 (wt. %) 1.03 6.82 0.07 As (ppm) 94 ND 13 Ba (ppm) 1200 1134 468 Cd (ppm) 1 ND ND ND Cl (ppm) 1 101 568 5843 Co (ppm) 41 759 3 Cr (ppm) 114 56 29 Cu (ppm) 114 408 2505 Hg (ppm) 1 0.17 0.21 0.18 Mn (ppm) 300 2900 8870 Mo (ppm) 35 11 43 Ni (ppm) 86 70 44 Pb (ppm) 49 ND 32 Sb (ppm) NR NR NA Se (ppm) 1 5ND ND Sr (ppm) 700 0 379 V (ppm) 213 214 18 Zn (ppm) 73 0 2685 Notes: ND - Not Detected NR - Not Reported 1 Dry Basis S tan d a rd Parameters Test Parameter CTB burn 182 183 4.3.3.3 Woodchips Woodchips were obtained from a local timber company near the cement plant. Like other alternative fuels, they were not tested for composition or properties at the cement plant. Woodchips samples were collected by Auburn University and tested for fuel characteristics and composition at the external laboratory. Discrete samples were collected every three hours, and each sample was tested individually. In addition, every fourth sample was tested in duplicate. The tests conducted on each of these specimens were the same as for each of the other fuels. The complete set of summary statistics for the proximate, ultimate, and combustion analyses is shown in Table 4.36. The summary statistics applicable to the standard external laboratory parameters for the woodchips are shown in Table 4.37. In Tables 4.36 and 4.37, it is observed that the coefficient of variation (C.V. %) values are unusually high for some of the data. It suggests that there is a lot of variation in the data obtained from testing of the discrete samples, which indicates that the woodchips samples are not uniform and consistent in composition. This could be a result of the woodchips coming from different kinds of wood used at the timber company. Woodchips are discussed in detail in Section 2.3.4.4. From Table 4.36, it is observed that the volatile matter content of woodchips is very high and in turn, the ash content is very low which is an excellent property for any fuel. However the moisture content of woodchips is on the higher side for a fuel (> 14 percent), which can directly affect the heating value. More information about woodchips can be found in Section 2.3.4.4. The nitrogen and sulfur content of the woodchips is found to be low and it can directly lower the emissions, as will be discussed in Section 4.3.8. From the averages listed in Table 4.37, it can be inferred that woodchips are very high in CaO, K 2 O and MgO. They have a low content of the heavy metals, except for barium, manganese and strontium. Woodchips were substituted for coal at an average woodchips-to-fuel replacement rate of 6.9 percent on an energy replacement basis, determined by using an average as-received heating value of 8388 BTU/lb for woodchips, 15098 BTU/lb for scrap tires and 12,445 BTU/lb for the coal. The fuel feed rates (tons per hour) were provided by the cement plant. The average density of the woodchips samples was measured by Auburn University staff and was determined to 16.40 lb/ft 3 . Woodchips, like broiler litter, did not cause any feed problems. The CTW burn was conducted for three days without any interruptions. Table 4.36: ELR ? Proximate, Ultimate and Combustion analyses of woodchips from CTW burn 184 Test Parameter Average C.V. (%) P-Value 2 Ash (wt. %) 0.82 33.5 1 <0.005 Fixed Carbon (wt. %) 16.94 8.0 0.126 Moisture (wt. %) 3 36.46 4.3 0.206 Volatile Matter (wt. %) 82.24 1.7 0.105 Carbon (wt. %) 52.64 0.6 1 <0.005 Hydrogen (wt. %) 5.83 4.7 1 <0.005 Nitrogen (wt. %) 0.15 63.3 1 <0.005 Oxygen (wt. %) 40.53 1.3 0.13 Sulfur (wt. %) 0.02 41.2 1 <0.005 8388 1.2 0.305 Notes: 1 Not Normally Distributed 3 As Received 2 Based on Anderson-Darling Statistics Proxim a te An alysis Ul ti ma te A n alysis Heat Value (BTU/lb) Table 4.37: ELR - Standard Parameters of woodchips from CTW burn 185 ND - Not Detected 3 Dry Basis Test Parameter Average C.V. (%) P-Value 2 Al 2 O 3 (wt. %) 0.93 33.3 1 <0.005 CaO (wt. %) 54.61 16.1 1 0.042 Fe 2 O 3 (wt. %) 1.79 59.7 1 <0.005 K 2 O (wt. %) 17.28 32.1 1 <0.005 MgO (wt. %) 9.83 18.0 1 <0.005 Na 2 O (wt. %) 0.38 56.6 1 <0.005 P 2 O 5 (wt. %) 2.80 29.1 1 <0.005 SiO 2 (wt. %) 3.27 51.1 1 <0.005 SO 3 (wt. %) 3.33 80.2 1 <0.005 TiO 2 (wt. %) 0.02 139.1 1 <0.005 As (ppm) 12 53.9 1 <0.005 Ba (ppm) 9692 21.7 1 <0.005 Cd (ppm) 3 ND NA NA Cl (ppm) 3 425 96.0 1 <0.005 Co (ppm) 64 192.4 1 <0.005 Cr (ppm) 16 117.87 1 <0.005 Cu (ppm) 126 25.4 1 <0.005 Hg (ppm) 3 0.1 51.4 1 <0.005 Mn (ppm) 43581 45.6 1 <0.005 Mo (ppm) 65 181.8 1 <0.005 Ni (ppm) 169 117.0 1 <0.005 Pb (ppm) 60 150.7 1 <0.005 Sb (ppm) NR NA NA Se (ppm) 3 ND NA NA Sr (ppm) 4230 27.9 1 <0.005 V (ppm) 172 123.7 1 <0.005 Zn (ppm) 959 39.9 1 <0.005 Notes: NR - Not Reported 1 Not Normally Distributed NA - Not Applicable 2 Based on Anderson-Darling Statistics St andar d Par a m e t e r s The proximate and ultimate analyses of all the fuels used in CTW burn are shown in Table 4.38. The chemical compositions of all the fuels used in CTW burn are presented in Table 4.39. From these tables, composition and properties of woodchips can be compared to those of coal and tires. It is observed that the ash content is much lower and volatile matter is much higher in woodchips than in both coal and tires. Sulfur content is also very low compared to both coal and tires. Woodchips are rich in CaO and K 2 O, unlike both coal and tires, and have low contents of SiO 2 , Al 2 O 3 and Fe 2 O 3 , which in contrast are the major parameters of coal and tires. Woodchips are found to have an average of 4.35 percent by weight of MnO 2 (43581 ppm of Mn in Table 4.37) which is much higher than the value for both coal and tires. The heating value is also low compared to both coal and tires. The arsenic content is lower than the value for coal but the lead content is found to be higher than the value for coal. Table 4.38: ELR ? Proximate and Ultimate analyses of all fuels from CTW burn Coal Tires Woodchips Ash (wt. %) 17.59 14.99 0.82 Fixed Carbon (wt. %) 53.80 23.56 16.94 Volatile Matter (wt. %) 28.61 61.45 82.24 Carbon (wt. %) 71.06 77.60 52.64 Hydrogen (wt. %) 4.16 5.90 5.83 Nitrogen (wt. %) 1.48 0.10 0.15 Oxygen (wt. %) 4.57 0.31 40.53 Sulfur (wt. %) 1.14 1.1 0.02 12445 15098 8388 Parameter CTW burn Pr oximate A n alysis Ult i mate Analysis Test Heat Value (BTU/lb) 186 Table 4.39: ELR ? Standard parameters of all fuels from CTW burn 187 Zn (ppm) 63 0 959 Notes: ND - Not Detected NR - Not Reported 1 Dry Basis Coal Tires Woodchips Al 2 O 3 (wt. %) 24.62 4.42 0.93 CaO (wt. %) 9.30 3.00 54.61 Fe 2 O 3 (wt. %) 7.47 57.72 1.79 K 2 O (wt. %) 2.24 0.48 17.28 MgO (wt. %) 1.08 0.36 9.83 Na 2 O (wt. %) 0.20 1.49 0.38 P 2 O 5 (wt. %) 0.17 0.43 2.80 SiO 2 (wt. %) 47.18 12.89 3.27 SO 3 (wt. %) 6.39 4.15 3.33 TiO 2 (wt. %) 1.16 3.74 0.02 As (ppm) 86 ND 12 Ba (ppm) 1096 ND 9692 Cd (ppm) 1 ND ND ND Cl (ppm) 1 105 515 425 Co (ppm) 54 642 64 Cr (ppm) 190 133 16 Cu (ppm) 70 3762 126 Hg (ppm) 1 0.2 0 0 Mn (ppm) 498 3754 43581 Mo (ppm) 31 8 65 Ni (ppm) 79 8 169 Pb (ppm) 47 30 60 Sb (ppm) NR NR NR Se (ppm) 1 6ND ND Sr (ppm) 598 36 4230 V (ppm) 214 117 172 CTW burn Parameter S tan d a rd Parameters Test 188 4.3.3.4 Switchgrass Switchgrass was obtained from a local farm and was delivered to the cement plant in form of bales. However, because of the severe drought experienced in Alabama during 2007, there was a shortage of supply and the stockpiled switchgrass lasted for two days only. Accordingly, the CTS burn was conducted for two days only. The bales of the switchgrass had to be shredded before this fuel could be fed into the system for easy flow of the stream. Discrete samples of these shreds were collected every three hours for two days by Auburn University. The cement plant did not test the switchgrass properties and composition of the switchgrass. Auburn University staff sent the collected samples to the external laboratory to be analyzed. Discrete samples were collected every three hours, and each of them was tested. In addition, every fourth sample was tested in duplicate. The tests conducted on each of these specimens were the same as for each of the other fuels. The complete set of summary statistics for the proximate, ultimate, and combustion analyses is shown in Table 4.40. The summary statistics applicable to the standard external laboratory parameters for the switchgrass are shown in Table 4.41. From Tables 4.40 and 4.41, it is observed that the coefficients of variation values are high for some parameters, suggesting high variation in the chemical composition of the switchgrass samples. However, the average values indicate that switchgrass is low in ash content and high in volatile matter. The sulfur content in the switchgrass is also found to be low. The average heat value is determined to be 8,162 BTU/lb, with a low coefficient of variation suggesting a uniform heat value among the switchgrass samples. From Table 4.41, it can be concluded that switchgrass mainly consists of SiO 2 , K 2 O, CaO, MgO and P 2 O 5 . Switchgrass also has high manganese and zinc contents. Table 4.40: ELR ? Proximate, Ultimate and Combustion analyses of switchgrass from CTS burn Test Parameter Average C.V. (%) P-Value 2 Ash (wt. %) 5.27 28.3 1 <0.005 Fixed Carbon (wt. %) 17.02 10.1 1 <0.005 Moisture (wt. %) 3 9.87 23.3 1 <0.005 Volatile Matter (wt. %) 77.72 1.7 0.2 Carbon (wt. %) 50.25 1.4 0.13 Hydrogen (wt. %) 5.70 4.1 0.215 Nitrogen (wt. %) 1.22 20.4 1 <0.005 Oxygen (wt. %) 37.37 2.6 0.15 Sulfur (wt. %) 0.19 7.3 1 <0.005 8162 1.8 0.323 Notes: 1 Not Normally Distributed 3 As Received 2 Based on Anderson-Darling Statistics Proxim a te Analysis Ul ti mate A n alysis Heat Value (BTU/lb) Switchgrass was substituted for coal at an average switchgrass-to-fuel replacement rate of 6.8 percent on an energy replacement basis, determined by using an average as-received heating value of 8162 BTU/lb for switchgrass, 13,239 BTU/lb for scrap tires and 12,664 BTU/lb for the coal. The fuel feed rates (tons per hour) were provided by the cement plant. The average density of the switchgrass shreds samples was measured by Auburn University staff and was determined to 4.57 lb/ft 3 . The shredding system installed for switchgrass at the cement plant was not efficient enough and hence, the shredding of switchgrass bales into manageable sizes involved a great deal of labor from cement plant personnel. But, once shredded, the switchgrass was easily conveyed into the system, though feed rates were low because of its low density. 189 Table 4.41: ELR - Standard parameters of switchgrass from CTS burn Test Parameter Average C.V. (%) P-Value 2 Al 2 O 3 (wt. %) 1.57 58.1 <0.005 CaO (wt. %) 13.99 11.0 1 <0.005 Fe 2 O 3 (wt. %) 1.06 84.7 1 <0.005 K 2 O (wt. %) 24.72 21.8 1 <0.005 MgO (wt. %) 9.02 14.7 1 <0.005 Na 2 O (wt. %) 0.96 77.4 1 <0.005 P 2 O 5 (wt. %) 8.49 17.9 1 <0.005 SiO 2 (wt. %) 34.86 13.1 1 <0.005 SO 3 (wt. %) 4.53 47.7 1 <0.005 TiO 2 (wt. %) 0.14 84.9 1 <0.005 As (ppm) 11.00 58.6 1 <0.005 Ba (ppm) 739 16.2 1 <0.005 Cd (ppm) 3 ND NA NA Cl (ppm) 3 819 20.2 1 <0.005 Co (ppm) 6 69.4 1 <0.005 Cr (ppm) 22 68.1 1 <0.005 Cu (ppm) 56 70.9 1 <0.005 Hg (ppm) 3 0.1 56.9 1 <0.005 Mn (ppm) 5511 35.2 1 <0.005 Mo (ppm) 146 121.6 1 <0.005 Ni (ppm) 145 96.9 1 <0.005 Pb (ppm) 47 67.9 1 <0.005 Sb (ppm) NR NA NA Se (ppm) 3 ND NA NA Sr (ppm) 267 34.0 1 <0.005 V (ppm) 82 132.8 1 <0.005 Zn (ppm) 1118 77.6 1 <0.005 Notes: NR - Not Reported 1 Not Normally Distributed NA - Not Applicable 2 Based on Anderson-Darling Statistics ND - Not Detected 3 Dry Basis S tand a rd Parameters 190 The proximate and ultimate analyses of all the fuels used in CTS burn are shown in Table 4.42. The chemical compositions of all the fuels used in CTS burn are shown in Table 4.43. From these tables, composition and properties of switchgrass can be compared to those of coal and tires. It is observed that the ash content is much lower and volatile matter is much higher in switchgrass than in both coal and tires. Sulfur content is also very low compared to both coal and tires. Switchgrass, like coal, is rich in SiO 2 and CaO but has lower Al 2 O 3 and Fe 2 O 3 contents than both coal and tires. The P 2 O 5 and MgO contents of switchgrass are higher than that of both coal and tires. Switchgrass has a low heating value as compared to both coal and tires. The arsenic content is lower than the value for coal but the lead content is higher than that of tires. Table 4.42: ELR ? Proximate and Ultimate analyses of all fuels from CTS burn Coal Tires Switchgrass Ash (wt. %) 16.5 24.4 5.3 Fixed Carbon (wt. %) 55.2 19.8 17.0 Volatile Matter (wt. %) 28.4 55.8 77.7 Carbon (wt. %) 71.3 72.6 50.2 Hydrogen (wt. %) 3.8 0.2 5.7 Nitrogen (wt. %) 1.0 0.4 1.2 Oxygen (wt. %) 6.4 1.1 37.4 Sulfur (wt. %) 1.1 1.3 0.2 12664 13239 8162 Pr oximate A n alysis Ult i mate Analysis Heat Value (BTU/lb) Test Parameter CTS burn 191 Table 4.43: ELR ? Standard parameters of all fuels from CTS burn 192 Zn (ppm) 9 0 1118 Notes: ND - Not Detected NR - Not Reported 1 Dry Basis Coal Tires Switchgrass Al 2 O 3 (wt. %) 23.87 0.53 1.57 CaO (wt. %) 12.81 2.94 13.99 Fe 2 O 3 (wt. %) 7.77 77.06 1.06 K 2 O (wt. %) 2.56 0.25 24.72 MgO (wt. %) 1.31 0.20 9.02 Na 2 O (wt. %) 0.57 0.13 0.96 P 2 O 5 (wt. %) 0.12 0.20 8.49 SiO 2 (wt. %) 49.44 5.38 34.86 SO 3 (wt. %) 0.33 2.25 4.53 TiO 2 (wt. %) 1.04 0.10 0.14 As (ppm) 114 ND 11 Ba (ppm) 1100 0 739 Cd (ppm) 1 ND ND ND Cl (ppm) 1 236 1696 819 Co (ppm) 43 724 6 Cr (ppm) 132 129 22 Cu (ppm) 103 0 56 Hg (ppm) 1 0.076 NR 0 Mn (ppm) 500 4300 5511 Mo (ppm) 29 11 146 Ni (ppm) 78 332 145 Pb (ppm) ND 8 47 Sb (ppm) NR NR NR Se (ppm) 1 7ND ND Sr (ppm) 400 20 267 V (ppm) 228 10 82 S tan d a rd Parameters Test Parameter CTS burn 4.3.4 Chemical Composition of Cement Kiln Dust (CKD) The cement plant collected two cement kiln dust samples every day during each of the burns. Each of these samples was tested once for the standard cement plant parameters, except for moisture and loss on ignition. Since only six data points of results of CKD were available for each burn, complete summary statistics are not presented. CKD, like emissions, can be sensitive to changes in the raw materials? composition and it was decided to analyze the data using different baselines for different fuel burns, as discussed in Section 4.3. Table 4.44 shows the results of the tests for the baseline burns, along with the percent differences relative to CT1 burn. Table 4.44: CPR ?Baseline burns, Chemical analysis and percent difference for cement kiln dust Burn CT1 Value (wt. %) Value (wt. %) % Diff. Value(wt. %) % Diff. Al 2 O 3 4.00 3.71 -7.1 3.77 -5.6 CaO 44.69 45.06 0.8 45.49 1.8 Fe 2 O 3 2.01 1.96 -2.9 1.89 -6.4 K 2 O 0.42 0.44 5.1 0.38 -8.9 MgO 1.65 1.30 -21.6 1.29 -22.2 Na 2 O 0.09 0.04 -58.3 0.07 -19.8 SiO 2 12.05 11.99 -0.5 11.06 -8.2 SO 3 0.95 0.17 -82.1 0.29 -69.1 Burn CT2 S tan d a rd Parameters Parameter Burn CT3 Test It is observed that there is less than 2 percent variation in CaO content and less than 9 percent variation in SiO 2 , the major constituents of CKD, as reported by the cement plant. This result is consistent with the chemical compositions of kiln feed reported in Section 4.3.2 and Table 4.19. However, as found in case of kiln feed, some of 193 the results for CKD, reported by the external laboratory in Table 4.45, are quite different from those reported by the cement plant. Table 4.45: ELR ?Baseline burns, Chemical composition of cement kiln dust 194 Se (ppm) 2 NANANANA Sr (ppm) 293 493 68.2 591 101.4 V (ppm) 50 73 45.8 75 50.3 Zn (ppm) 101 28 -72.3 215 113.5 Notes: ND - Not Detected NA - Not Applicable CT1 burn Value Value % Diff. Value % Diff. Al 2 O 3 (wt. %) 3.72 5.46 46.9 5.75 54.6 CaO (wt. %) 46.78 69.91 49.4 69.46 48.5 Fe 2 O 3 (wt. %) 2.10 2.99 42.3 2.85 35.8 K 2 O (wt. %) 0.57 0.65 15.1 0.55 -3.6 MgO (wt. %) 1.53 2.16 40.9 2.20 43.8 Na 2 O (wt. %) 0.02 0.07 251.2 0.08 313.8 P 2 O 5 (wt. %) 0.05 0.06 28.2 0.09 85.5 SiO 2 (wt. %) 11.08 17.87 61.3 17.61 59.0 SO 3 (wt. %) 1.26 0.32 -74.3 0.89 -29.4 TiO 2 (wt. %) 0.22 0.34 55.6 0.33 52.4 Moisture (wt. %) 0.22 0.28 27.5 0.17 -23.0 LOI (wt. %) 32.55 35.60 9.4 36.06 10.8 As (ppm) 18 28 53.9 27 51.4 Ba (ppm) 309 452 46.1 394 27.5 Cd (ppm) ND ND NA ND NA Cl (ppm) 60 205 245.1 155 159.9 Co (ppm) 17 13 -24.5 10 -39.6 Cr (ppm) 45 57 28.3 66 47.9 Cu (ppm) 15 21 40.7 31 107.8 Hg (ppm) ND 0.46 NA ND NA Mn (ppm) 168 697 314 1000 494.2 Mo (ppm) ND 3 NA NA NA Ni (ppm) 15 10 -31.3 14 -7.6 Pb (ppm) 18 14 -25.6 17 -6.2 Sb (ppm) 58 NA NA NA NA CT3 burnCT2 burn Parameter 195 The high percentage differences of CaO and SiO 2 in CKD over the three baseline burns, as reported by the external laboratory, show exactly the same trend as in the case of kiln feed, observed in Table 4.20. Similarly, the trend of increase in chlorine and manganese content in CKD over the baseline burns in Table 4.45 can be correlated to the increase of the same in kiln feed, as observed in Table 4.19. This again validates the data and confirms that the chemical composition of the process inputs was indeed different for different baselines. The differences in the chemical composition of CKD between the fuel burns relative to their respective baseline burns as reported by the cement plant are presented in Table 4.46. It can be seen that there is less than 7 percent difference in CaO content and about 10 percent difference in SiO 2 content, the major constituents of CKD based on the cement plant results. The average values of other parameters are small and hence even a slight and practically insignificant change appears as a large percentage difference. The percentage difference values for all the parameters of CKD determined by the cement plant are plotted in Figure 4.4. Table 4.47 presents the variation in chemical composition of CKD between the fuel burns relative to their respective baseline burn based on the results from the external laboratory. The trends from the external laboratory for CKD compositions are similar to those from the cement plant except for the CTW and CTS burns. The percentage differences in major parameters are much higher for the CTW and CTS burns for results from the external laboratory as compared to the results from the cement plant. 196 Table 4.46: CPR ?Fuel Burns, Chemical composition of cement kiln dust relative to baseline burns Value (wt. %) % Diff. 1 Value (wt. %) % Diff. 2 Value (wt. %) % Diff. 3 Value (wt. %) % Diff. 3 Value (wt. %) % Diff. 3 Al 2 O 3 3.69 -7.6 3.65 -1.6 3.85 2.0 4.12 9.3 3.97 5.1 CaO 47.55 6.4 47.63 5.7 44.78 -1.6 44.59 -2.0 44.35 -2.5 Fe 2 O 3 1.82 -9.7 1.74 -11.2 1.88 -0.1 2.07 9.6 2.00 5.9 K 2 O 0.48 14.7 0.38 -12.9 0.51 33.3 0.53 38.2 0.58 51.6 MgO 1.66 0.2 1.81 39.4 1.39 8.0 1.34 3.8 1.33 3.4 Na 2 O 0.07 -18.3 0.05 44.0 0.05 -27.3 0.04 -48.1 0.05 -27.3 SiO 2 11.68 -3.0 11.57 -3.5 11.50 4.0 12.17 10.0 12.15 9.9 SO 3 1.13 18.9 0.85 397.5 0.27 -6.6 0.26 -10.5 0.20 -31.1 Notes: NA - Not Applicable 2 Relative to Burn CT2 1 Relative to Burn CT1 3 Relative to Burn CT3 Burn C Test Parameter Burn CTP Burn CTB Burn CTW Burn CTS S t a n d a rd Parameters 4.3.5 Chemical Composition of Clinker Clinker is the primary output of the kiln process. For that reason, more clinker samples were collected for chemical analysis than any other material. Twelve samples of clinker were collected per day by the cement plant. Each of these samples was tested to determine chemical composition. The results shown in Tables 4.48 and 4.49 are the summary statistics from at least 36 discrete samples collected for each burn at the cement plant. The coefficient of variation (C.V. %) represents the measure of deviation from the mean of the data. From Tables 4.48 and 4.49, it can be observed that most of the data for clinker provided by the cement plant have low C.V. values, indicating that the sample mean (given average) is close to the true value (idealistic mean of an infinite number of data points) .Whenever the P-value is less than 0.1, the data is not normally distributed. 197 Figure 4.4: CPR-Fuel Burns, Percentage difference in CKD composition relative to baseline burns Table 4.47: ELR ?Fuel Burns, Chemical composition of cement kiln dust relative to baseline burns Value % Diff. 1 Value % Diff. 2 Value % Diff. 3 Value % Diff. 3 Value % Diff. 3 Al 2 O 3 (wt. %) 3.77 1.3 5.12 -6.3 6.00 4.4 3.86 -32.9 3.89 -32.3 CaO (wt. %) 56.33 20.4 72.01 3.0 69.60 0.2 43.64 -37.2 44.02 -36.6 Fe 2 O 3 (wt. %) 2.01 -4.3 2.58 -13.8 2.99 5.0 1.99 -30.1 2.00 -29.8 K 2 O (wt. %) 0.43 -24.5 0.47 -28.6 0.84 53.4 0.42 -23.9 0.58 6.0 MgO (wt. %) 1.90 23.9 2.54 18.0 2.16 -2.0 1.32 -40.2 1.37 -37.9 Na 2 O (wt. %) 0.01 -49.5 0.08 14.7 0.08 2.7 0.06 -33.1 0.09 9.5 P 2 O 5 (wt. %) 0.06 20.2 0.07 2.2 0.09 -4.3 0.04 -62.0 0.07 -26.7 SiO 2 (wt. %) 11.32 2.2 15.71 -12.1 17.19 -2.4 11.95 -32.1 11.58 -34.3 SO 3 (wt. %) 1.43 14.0 1.01 213.0 0.56 -36.8 0.25 -71.7 0.29 -67.4 TiO 2 (wt. %) 0.22 0.3 0.25 -25.4 0.31 -7.6 0.20 -40.5 0.17 -50.1 Moisture (wt. %) 0.07 -70.1 0.14 -51.9 0.24 41.9 3.17 NA 0.24 37.0 LOI (wt. %) 22.54 -30.7 33.25 -6.6 35.42 -1.8 36.19 0.4 35.85 -0.6 As (ppm) 4 -79.4 29 5.8 33 21.5 16 -42.6 22 -21.2 Ba (ppm) 278 -9.9 333 -26.3 500 26.9 217 -45.0 250 -36.5 Cd (ppm) ND NA NR NA ND NA ND NA ND NA Cl (ppm) 483 711 131 -36.2 734 375 538 248 303 95.9 Co (ppm) 15 -9.6 13 3.8 15 47.3 10 -1.9 16 59.6 Cr (ppm) 33 -26.4 54 -6.0 59 -11.4 114 71.8 70 4.9 Cu (ppm) 49 229 47 122 35 12.7 12 -63.2 19 -39.1 Hg (ppm) 0NANRNA2NA1NA0NA Mn (ppm) 315 87.2 883 26.6 NA NA 517 -48.3 550 -45.0 Mo (ppm) ND NA 16 381.4 3 NA 7 NA 11 NA Ni (ppm) 11 -25.5 14 38.1 15 9.4 11 -19.4 586 4193 Pb (ppm) 20 10.9 22 60.7 18 2.9 22 26.4 17 -3.4 Sb (ppm) 55 -5.2 NR NA NA NA NR NA NR NA Se (ppm) 1 -41.8 NR NA NA NA ND NA ND NA Sr (ppm) 321 9.3 533 8.0 NA NA 300 -49.2 300 -49.2 V (ppm) 55 10.0 64 -12.0 75 0.6 66 -11.9 67 -11.3 Zn (ppm) 91 -9.2 38 36.1 66 -69.1 38 -82.3 34 -84.3 1 Relative to Burn CT1 2 Relative to Burn CT2 3 Relative to Burn CT3 CTW burn CTS burn Parameter CTP burn CTB burn Notes: ND - Not Detected NR- Not Reported NA- Not Applicable CIP- Collection in Progess C burn . 198 Table 4.48 CPR - Summary statistics of chemical composition of clinker for C, CT1, CTP and CT2 burns 199 Average (wt. %) C.V. (%) P-Value Average (wt. %) C.V. (%) P-Value Average (wt. %) C.V. (%) P-Value Average (wt. %) C.V. (%) P-Value Al 2 O 3 5.30 3.2 1 0.033 5.08 2.0 0.840 5.15 2.0 1 <0.005 5.08 2.13 1 <0.005 CaO 64.97 0.4 0.116 64.49 0.2 0.908 64.56 0.6 1 0.039 64.62 0.75 1 0.022 Fe 2 O 3 3.41 6.6 1 0.012 3.36 4.7 0.289 3.57 6.1 1 <0.005 3.41 3.4 0.204 K 2 O 0.56 4.1 1 0.022 0.48 3.8 0.118 0.47 4.6 1 0.077 0.50 8.2 1 0.011 MgO 2.93 2.3 0.453 3.48 5.4 1 <0.005 3.25 3.3 0.589 3.38 4.7 0.345 Na 2 O 0.07 6.8 1 <0.005 0.10 9.6 1 <0.005 0.07 5.8 1 <0.005 0.06 4.6 1 <0.005 Na 2 O eq 0.44 3.7 1 0.022 0.42 3.7 1 0.069 0.38 4.4 1 0.053 0.39 7.6 1 <0.005 SiO 2 21.38 0.9 0.391 21.23 0.9 0.869 21.31 1.2 1 <0.005 21.52 1.4 1 <0.005 SO 3 0.85 12.1 0.323 0.67 12.1 0.117 0.92 21.1 1 <0.005 0.70 14.2 1 <0.005 Free CaO 1.10 37.1 0.605 1.06 38.8 1 <0.005 1.24 41.0 0.374 0.78 49.6 1 0.084 C 3 A 8.28 6.8 1 0.043 7.78 4.9 0.416 7.62 5.4 1 0.021 7.70 2.9 1 0.021 C 4 AF 10.38 6.7 1 0.009 10.22 4.7 0.206 10.86 6.2 1 <0.005 10.39 3.4 1 <0.005 C 3 S 61.49 4.4 0.362 62.24 2.8 0.544 61.15 3.9 1 0.033 60.47 2.0 1 0.055 C 2 S 14.91 16.6 0.742 13.92 13.2 0.602 14.97 16.4 1 0.007 16.08 10.1 1 0.001 Notes: 1 Data Not Normally Distributed Parameter C burn CT1 burn CT2 burnCTP burn 200 Average (wt. %) C.V. (%) P-Value Average (wt. %) C.V. (%) P-Value Average (wt. %) C.V. (%) P-Value Average (wt. %) C.V. (%) P-Value Al 2 O 3 5.27 1.9 0.416 5.29 2.2 1 <0.005 5.04 2.1 1 0.032 5.09 2.4 1 <0.005 CaO 64.32 0.6 1 <0.005 64.49 0.5 0.303 64.76 0.4 0.311 64.74 0.2 1 0.093 Fe 2 O 3 3.13 2.6 0.542 3.39 4.9 0.121 3.21 4.1 1 <0.005 3.39 1.8 0.177 K 2 O 0.63 5.4 1 0.077 0.52 4.9 1 0.011 0.57 14.7 0.177 0.64 7.1 0.412 MgO 3.18 3.7 0.612 3.31 3.4 0.685 3.26 2.0 0.572 3.15 2.1 0.625 Na 2 O 0.08 11.8 1 <0.005 0.08 13.8 1 <0.005 0.06 17.8 1 <0.005 0.09 5.3 0.179 Na 2 O eq 0.49 5.3 0.413 0.42 4.3 1 0.035 0.43 11.6 0.253 0.51 6.4 1 <0.005 SiO 2 21.45 1.3 0.323 21.34 0.8 1 <0.005 21.51 0.7 0.304 21.48 0.4 0.226 SO 3 0.79 5.4 0.202 0.79 9.8 1 0.080 0.84 42.5 1 <0.005 0.64 18.3 1 <0.005 Free CaO 0.98 34.2 0.374 1.08 34.3 0.374 1.20 40.5 0.374 1.01 58.3 1 <0.005 C 3 A 8.67 2.3 0.721 8.29 3.5 1 0.012 7.91 2.8 1 0.031 7.77 3.6 1 0.021 C 4 AF 9.52 2.6 1 <0.005 10.31 4.9 1 <0.005 9.76 4.1 0.102 10.30 1.9 1 <0.005 C 3 S 58.94 3.3 1 0.033 59.97 2.7 0.213 61.76 2.7 <0.005 61.26 2.6 0.143 C 2 S 17.03 12.7 0.807 15.96 9.9 1 <0.005 15.09 9.3 0.007 15.36 8.9 0.107 Notes: CT3 burn Parameter 1 Data Not Normally Distributed CTW burn CTS burnCTB burn Table 4.49 CPR - Summary statistics of chemical composition of clinker for CTB, CT3, CTW and CTS burns Table 4.50 shows the percent difference of the means for Baseline Burns CT2 and CT3 relative to the mean of CT1 burn. This table also shows whether or not the difference in each mean is statistically significant, along with the P-value, which is the indicator of significance. Table 4.50 CPR ?Baseline Burns, Percent difference and statistical significance for clinker relative to CT1 burn Percent Difference P-Value Significant Percent Difference P-Value Significant Al 2 O 3 0.06 0.350 No 4.13 0.005 Yes CaO 0.21 0.250 No 0.01 0.300 No Fe 2 O 3 1.66 0.411 No 0.97 0.000 Yes K 2 O 4.39 0.000 Yes 6.96 0.000 Yes MgO -2.79 0.000 Yes -5.06 0.105 No Na 2 O -39.82 0.000 Yes -17.48 0.000 Yes Na 2 O eq -6.49 0.000 Yes 1.11 0.000 Yes SiO 2 1.37 0.105 No 0.52 0.130 No SO 3 4.94 0.000 Yes 17.42 0.000 Yes Free CaO -26.20 0.000 Yes 1.65 0.000 Yes C 3 A -1.10 0.000 Yes 6.51 0.086 Yes C 4 AF 1.69 0.000 Yes 0.91 0.200 No C 3 S -2.85 0.000 Yes -3.66 0.031 Yes C 2 S 15.49 0.055 Yes 14.67 0.042 Yes Burn CT3 Parameter Burn CT2 In most of the parameters, there was a statistically significant difference between the means of the baseline burns. However, this does not mean that the difference is of practical significance. The major parameters, CaO and SiO 2 , showed little percentage difference in means and they are not statistically different either. However, the Bogue compounds showed statistically significant differences. The percentage difference for fuel burns relative to the respective baseline burns based on the cement plant results are 201 202 shown in Table 4.51. Also, whether or not the difference in each mean is statistically significant, along with the P-value, which is the indicator of significance are shown. Most of the parameters from the fuel burns showed statistically significant differences in means relative to their respective baseline burns. However, the actual percentage differences in CaO and SiO 2 , the major parameters, are small and not of practical significance. The percentage differences in standard parameters based on cement plant results are graphically presented in Figure 4.5. The major differences were found in SO 3 content at 27 percent in Burn C and 31 percent in CTP burn. However, the total SO 3 content of the cement is regulated by the controlled addition of gypsum prior to grinding. The Free CaO content was increased for CTP burn, which perhaps can be correlated to the high content of CaO in waste plastics in Table 4.29. It is interesting to note that the content of Bogue compounds was not altered much by introduction of alternative fuels with less than 8 percent change at its worst. K 2 O and Na 2 O contents were altered by considerable percentages; their impact on cement performance can best be evaluated by looking at the equivalent alkali content, Na 2 O eq (Na 2 O + 0.658 ? K 2 O). Most of the other parameters for fuel burns saw less than 5 percent change relative to the respective baseline burn. The external laboratory results of chemical analysis on composite samples are presented in Table 4.52. The major parameters followed the same trend as found in the cement plant results. The arsenic content was found to be increased by about 73 percent for CTP burn and 30 percent for CTB burn but was much lower for C burn. The lead content was lowered whenever alternative fuels were used. The zinc content was increased for the CTP burn but was lowered for all other trial burns. Table 4.51 CPR ? Percent differences and statistical significance for clinker 203 % Diff. 1 P-Value Significant % Diff. 2 P-Value Significant % Diff. 3 P-Value Significant % Diff. 3 P-Value Significant % Diff. 3 P-Value Significant Al 2 O 3 4.40 0.000 Yes 1.31 0.005 Yes -0.34 0.000 Yes -4.81 0.000 Yes -3.71 0.001 Yes CaO 0.74 0.000 Yes -0.10 0.310 No -0.27 0.000 Yes 0.41 0.125 No 0.38 0.000 Yes Fe 2 O 3 1.60 0.241 No 4.49 0.000 Yes -7.74 0.100 No -5.42 0.000 Yes -0.14 0.037 Yes K 2 O 16.00 0.000 Yes -7.77 0.000 Yes 21.95 0.000 Yes 9.37 0.201 No 23.37 0.000 Yes MgO -15.81 0.000 Yes -3.83 0.000 Yes -3.80 0.000 Yes -1.22 0.005 Yes -4.76 0.102 No Na 2 O -26.47 0.000 Yes 15.98 0.000 Yes -6.04 0.000 Yes -33.07 0.000 Yes 12.51 0.000 Yes Na 2 O eq 5.92 0.000 Yes -4.03 0.000 Yes 15.97 0.000 Yes 0.86 0.000 Yes 20.72 0.000 Yes SiO 2 0.70 0.001 Yes -0.99 0.135 No 0.49 0.001 Yes 0.77 0.000 Yes 0.64 0.120 No SO 3 27.00 0.000 Yes 30.88 0.000 Yes 0.90 0.000 Yes 6.57 0.189 No -18.48 0.000 Yes Free CaO 3.80 0.647 No 58.45 0.000 Yes -9.06 0.000 Yes 11.43 0.000 Yes -6.48 0.000 Yes C 3 A 6.43 0.000 Yes -0.99 0.086 Yes 4.65 0.000 Yes -4.51 0.071 Yes -6.23 0.212 No C 4 AF 1.56 0.253 No 4.54 0.000 Yes -7.64 0.090 Yes -5.35 0.212 No -0.11 0.000 Yes C 3 S -1.20 0.166 No 1.13 0.031 Yes -1.71 0.000 Yes 2.99 0.035 Yes 2.16 0.010 Yes C 2 S 7.10 0.055 Yes -6.88 0.042 Yes 6.68 0.005 Yes -5.47 0.043 Yes -3.74 0.024 Yes Notes: 1 Relative to Burn CT1 2 Relative to Burn CT2 3 Relative to Burn CT3 CTS burnCTP burn CTB burn CTW burn C burn Parameter Figure 4.5: CPR- Fuel Burns, Percentage difference in clinker composition relative to baseline burns 204 205 The most important results from Tables 4.51 and 4.52 and Figure 4.5 are the percent changes in Al 2 O 3 , CaO, Fe 2 O 3 , and SiO 2 . Each showed very little change between the burns from both the cement plant and the external laboratory results. These results are significant because these four parameters are the primary compounds in the clinker, and are the ones that have the most effect on cement and concrete properties. Based on these results, it can be concluded that the cement plant is capable of maintaining consistent concentrations of the primary parameters in the clinker, regardless of the fuels that are used. The final result concerning the chemical composition of clinker is from Rietveld analysis conducted at cement plant?s specialty laboratory. This test determines the principal cement compounds in the clinker more accurately than the Bogue formulae used in ASTM C 150. These results, along with the percent difference of baseline burns relative to CT1 burn, are shown in Table 4.53. The results for the fuel burns relative to the respective baseline burn are presented in Table 4.54. From Table 4.54, it can be observed that the percentage differences for Bogue compounds from all the alternative fuel burns were small except for C 3 A (aluminate) in CTP , CTB and CTS burns, and C 2 S (belite) in CTW and CTS burns. Table 4.52: ELR ?Fuel Burns, Percent differences for clinker relative to baseline burn Value (wt %) % Diff. 1 Value (wt %) % Diff. 2 Value (wt %) % Diff. 3 Value (wt %) % Diff. 3 Value (wt %) % Diff. 3 Al 2 O 3 5.27 4.60 4.96 0.5 5.06 -5.8 5.1 -5.9 4.83 -10.3 CaO 65.15 1.36 64.71 -0.1 64.73 0.8 64.4 0.4 65.34 1.8 Fe 2 O 3 3.34 2.38 3.33 2.7 2.93 -10.2 3.1 -6.0 3.34 2.3 K 2 O 0.60 16.49 0.42 -21.8 0.66 44.8 0.5 18.6 0.59 29.8 MgO 2.88 -18.43 3.40 -2.3 3.34 -1.5 3.3 -1.3 3.35 -1.4 Na 2 O 0.01 -69.86 0.10 63.2 0.08 -5.2 0.1 -13.8 0.12 41.4 P 2 O 5 0.08 19.33 0.07 27.8 0.10 49.7 0.1 -28.7 0.07 3.4 SiO 2 21.24 -2.92 21.51 -0.4 21.80 -0.3 22.1 1.2 21.03 -3.9 SO 3 0.97 37.34 0.98 27.7 0.81 8.3 0.6 -14.9 0.71 -5.8 TiO 2 0.30 14.07 0.26 -2.1 0.24 -11.9 0.3 -8.1 0.22 -21.5 Moisture 0.01 -59.87 0.00 -100.0 0.06 -65.0 0.0 -81.8 0.00 -100.0 LOI 0.15 -60.31 0.13 -41.9 0.33 42.1 0.1 -40.3 0.21 -12.6 Value (ppm) % Diff. 1 Value (ppm) % Diff. 2 Value (ppm) % Diff. 3 Value (ppm) % Diff. 3 Value (ppm) % Diff. 3 As 9 -59.25 36 72.9 23 29.5 18 2.6 26 44.8 Ba 366 79.84 367 -18.7 453 15.8 317 -19.1 325 -16.9 Cd ND NA NR NA NA NA NA NA ND NA Cl 239 -43.75 177 22.6 303 98.3 292 90.5 399 160.6 Co 15 NA 12 21.9 10 2.5 9 -7.5 16 60.8 Cr 72 -7.58 90 4.2 93 -21.9 98 -17.6 104 -12.1 Cu 65 154.43 28 61.8 29 18.0 15 -39.5 67 171.6 Hg 0.02 -41.67 NR NA 0 -81.3 0 -47.7 0 -74.7 Mn 959 81.75 1683 141.3 781 -58.0 2100 13.0 1525 -18.0 Mo 12 NA 19 303.1 4 28.7 5 34.6 18 417.1 Ni 43 142.23 15 63.4 13 12.7 8 -32.8 137 1116 Pb 36 6.55 12 -40.8 15 -25.8 17 -16.0 18 -11.3 Sb 57 15.79 NR NA NA NA NA NA NR NA Se 1 -50.24 NR NA 3 50.0 NA NA ND NA Sr 402 1.43 500 1.3 513 4.8 400 -18.2 400 -18.2 V 64 -1.52 66 4.0 67 -3.1 66 -4.2 71 3.0 Zn 135 -28.01 68 82.7 99 -69.0 75 -76.7 81 -74.8 1 Relative to Burn CT1 2 Relative to Burn CT2 3 Relative to Burn CT3 CTB burn Notes: ND- Not Detected NR- Not reported NA-Not Applicable CIP- Collection in progress CTW burn Parameter CTS burn C burn CTP burn . 206 Table 4.53: SLR ?Baseline Burns, Rietveld analysis of clinker relative to CT1 burn CT1 burn Value (wt. %) Value (wt. %) % Diff. Value (wt. %) % Diff. Alite (C 3 S) 62.52 55.69 -10.93 59.33 -5.11 Belite (C 2 S) 18.54 22.10 19.20 21.11 13.86 Ferrite (C 4 AF) 10.63 10.78 1.44 11.36 6.90 Aluminate (C 3 A) 4.28 3.14 -26.71 3.63 -15.26 CT2 Burn CT3 Burn Parameter Table 4.54: SLR ?Fuel Burns, Rietveld analysis of clinker relative to the baseline burns Value (wt. %) Diff. 1 Value (wt. %) % Diff. 2 (wt. %) % Diff. 3 (wt. %) % Diff. 3 (wt. %) % Diff. 3 Alite (C 3 S) 65.11 4.1 56.67 1.75 60.00 1.13 66.16 11.51 64.40 8.55 Belite (C 2 S) 17.12 -7.7 23.91 8.17 20.99 -0.57 15.38 -27.13 16.35 -22.57 Ferrite (C 4 AF) 6.36 -40.2 11.47 6.40 10.06 -11.44 10.87 -4.34 11.31 -0.44 Aluminate (C 3 A) 5.67 32.5 2.94 -6.16 5.23 44.30 3.62 -0.28 3.40 -6.39 Notes: 1 Relative to Burn CT1 2 Relative to Burn CT2 3 Relative to Burn CT3 C burn CTP burn CTB burn CTW burn CTS burn Parameter 4.3.6 Portland Cement Portland cement is the primary output from the overall production process. Because of this, it was sampled very frequently at the cement plant. The samples that were collected were tested for their chemical composition by both the cement plant and the external laboratory. Discrete samples were tested at the cement plant and one-day composite samples were sent to the external laboratory for testing. As discussed earlier in Section 4.1, CT1 burn will be considered as the baseline reference for the fuel burns. 4.3.6.1 Chemical Composition of Cement The tests at the cement plant were conducted on eight discrete specimens each day during all the burns. The complete set of summary statistics, based on the results 207 208 collected by the cement plant, is shown in Table 4.55. All parameters are presented as percentage weights except for the Blaine specific surface area (SSA) which is given in m 2 /kg. Table 4.56 shows the percent difference relative to CT1 burn between all the parameters tested at cement plant. Almost every parameter showed a statistically significant change relative to CT1 burn. SO 3 and Blaine specific surface area did not show any significant difference for all burns. None of the alternative fuel burns showed any significant differences in CaO and MgO contents. The percentage differences for the major parameters for all the fuel burns relative to CT1 burn are plotted in Figure 4.6. The percent differences in Bogue compounds in cement for all fuel burns relative to CT1 burn are plotted in Figure 4.7. It must be remembered that just because many parameters showed a statistically significant difference, it does not mean that these same parameters have shown a practically significant difference. Practical significance, as mentioned earlier, is determined by the performance of the cement, and whether a statistically significant difference in a parameter significantly alters the behavior of the cement. The portland cement that was sampled at the cement plant was prepared into daily composite samples each day by personnel from Auburn University. It was these composite samples that were tested by the external laboratory. The external laboratory determined the standard parameters using XRF. Additionally, the total organic carbon (TOC) was determined using a total organic carbon analyzer, and the Bogue Compounds were calculated in accordance with ASTM C 150. The results of these tests, along with the percent difference relative to CT1 burn, are shown in Tables 4.57 and 4.58. Table 4.55: CPR ?All Burns, Summary statistics of cement composition 209 Average (wt. %) C.V. (%) P-Value Average (wt. %) C.V. (%) P-Value Average (wt. %) C.V. (%) P-Value Average (wt. %) C.V. (%) P-Value Average (wt. %) C.V. (%) P-Value Average (wt. %) C.V. (%) P-Value Al 2 O 3 4.98 2.8 1 0.065 4.66 2.1 0.331 4.85 2.2 0.164 4.87 0.6 1 0.045 4.64 0.9 0.216 4.79 0.4 0.123 CaO 63.49 0.5 0.843 62.56 0.7 1 0.008 62.79 0.8 1 0.009 62.13 0.7 0.305 63.66 0.3 0.150 63.20 0.2 0.100 Fe 2 O 3 3.11 3.2 1 0.056 3.02 3.0 0.297 3.22 3.8 1 <0.005 2.94 0.7 0.315 3.15 1.4 1 <0.005 3.18 0.3 0.165 K 2 O 0.52 1.9 1 <0.005 0.45 3.4 1 0.023 0.44 2.5 1 0.021 0.48 6.5 1 <0.005 0.51 2.0 0.100 0.56 1.1 1 0.052 MgO 2.88 2.9 1 <0.005 3.28 5.5 1 <0.005 3.22 1.8 1 0.095 3.22 1.8 1 0.025 3.13 0.7 1 <0.005 3.25 0.7 0.352 Na 2 O 0.09 7.8 1 <0.005 0.12 12.0 1 <0.005 0.09 8.0 1 <0.005 0.09 8.6 1 <0.005 0.06 5.0 1 <0.005 0.08 7.3 1 <0.005 Na 2 O eq 0.44 1.6 <0.005 0.41 2.9 1 <0.005 0.38 2.1 1 <0.005 0.41 6.0 1 <0.005 0.40 2.5 1 <0.005 0.45 2.4 1 <0.005 SiO 2 20.57 0.5 0.646 19.97 1.4 0.810 20.60 1.0 1 0.049 20.39 0.7 0.464 20.40 0.5 0.148 20.31 0.5 0.192 SO 3 2.62 6.2 1 0.075 2.63 7.5 0.751 2.68 8.8 0.126 2.57 1.7 1 0.065 2.65 2.2 0.126 2.64 1.6 0.224 Free CaO 0.94 23.3 1 <0.005 0.99 21.5 0.751 1.39 19.6 0.183 1.07 21.3 0.381 1.07 11.5 0.139 1.11 7.5 0.341 LOI 1.04 17.4 0.859 1.22 13.1 0.270 1.25 18.0 0.347 0.89 12.7 1 <0.005 1.20 12.6 1 <0.005 1.10 14.2 1 <0.005 C 3 S 56.75 4.7 0.738 59.76 5.6 0.623 54.26 4.0 0.330 53.69 0.9 0.738 60.89 2.3 0.310 58.67 0.7 0.412 C 2 S 16.15 13.5 0.380 12.15 26.2 0.281 18.11 10.4 0.732 17.96 0.6 0.380 12.55 1.4 0.251 13.96 0.3 0.278 C 3 A 7.94 3.3 0.118 7.24 3.3 1 0.030 7.44 4.7 0.413 7.96 3.5 0.201 6.96 1.2 0.323 7.33 0.9 0.524 C 4 AF 9.45 3.2 1 0.016 9.21 3.0 0.109 9.79 3.8 1 <0.005 8.96 9.5 0.200 9.60 6.1 1 <0.005 9.67 4.8 1 <0.005 Blaine SSA 2 377 2.9 1 <0.005 380.00 3.0 0.376 369.00 5.9 0.927 366 4.7 1 <0.005 383.50 1.3 0.143 375.33 2.3 0.729 Notes: 2 Units are m 2 /kg Burn CTB Burn CTW 1 Data Not Normally Distributed Burn CTS Parameter Burn C Burn CT Burn CTP Table 4.56: CPR ?All Burns, Percentage difference in cement composition relative to CT1 burn % Diff. P-Value Significant % Diff. P-Value Significant % Diff. P-Value Significant % Diff. P-Value Significant % Diff. P-Value Significant Al 2 O 3 6.90 0.000 Yes 4.08 0.000 Yes 4.60 0.000 Yes -0.51 0.345 No 2.83 0.000 Yes CaO 1.48 0.000 Yes 0.37 0.158 No -0.69 0.226 No 1.75 0.232 No 1.02 0.432 No Fe 2 O 3 2.81 0.003 Yes 6.31 0.000 Yes -2.65 0.000 Yes 4.23 0.689 No 5.03 0.000 Yes K 2 O 16.89 0.000 Yes -1.36 0.231 No 7.36 0.000 Yes 14.94 0.000 Yes 25.54 0.000 Yes MgO -12.17 0.000 Yes -1.87 0.123 No -1.69 0.324 No -4.36 0.123 No -0.74 0.143 No Na 2 O -21.05 0.000 Yes -27.71 0.000 Yes -22.93 0.000 Yes -48.48 0.000 Yes -36.56 0.000 Yes Na 2 O eq 5.97 0.000 Yes -8.76 0.000 Yes -1.41 0.123 No -3.47 0.000 Yes 7.88 0.000 Yes SiO 2 3.00 0.000 Yes 3.14 0.000 Yes 2.09 0.000 Yes 2.16 0.302 No 1.70 0.512 No SO 3 -0.55 0.787 No 1.78 0.531 No -2.47 0.205 No 0.71 0.501 No 0.17 0.237 No Free CaO -5.06 0.000 Yes 40.08 0.000 Yes 7.96 0.000 Yes 7.63 0.000 Yes 11.86 0.000 Yes LOI -15.07 0.000 Yes 2.14 0.698 No -27.58 0.000 Yes -2.11 0.434 No -10.39 0.000 Yes C 3 S -5.04 0.000 Yes -9.20 0.000 Yes -10.17 0.000 Yes 1.88 0.258 No -1.83 0.457 No C 2 S 32.94 0.000 Yes 49.05 0.000 Yes 47.78 0.000 Yes 3.31 0.000 Yes 14.88 0.000 Yes C 3 A 9.77 0.000 Yes 2.77 0.046 Yes 9.95 0.046 Yes -3.85 0.263 No 1.26 0.046 Yes C 4 AF 2.66 0.005 Yes 6.34 0.000 Yes -2.73 0.000 Yes 4.23 0.000 Yes 5.06 0.000 Yes Blaine SSA -0.98 0.271 No -3.19 0.103 No -3.68 0.103 No 0.92 0.214 No -1.23 0.229 No CTB burn CTW burn CTS burn Parameter C burn CTP burn 210 211 Figure 4.6: CPR- Fuel Burns, Percentage difference in cement composition relative to CT1 burn Figure 4.7: CPR- Fuel Burn, Percentage difference in Bogue compounds in cement relative to CT1 burn 212 213 The percentage differences determined from the external laboratory results are similar to that from the cement plant. The percentage difference for CaO content is less than 2 percent for all the fuel burns. The change in SiO 2 content too is less than 3 percent for all the fuel burns. SO 3 content seems to have slightly decreased for all the burns involving alternative fuels. Differences in percentages of Bogue compounds can be noticed; the C 3 S content was decreased for CTP and CTW burns and was increased for C and CTB burns. The change in C 2 S was highest for CTS burn. Total organic carbon (TOC) was not detected within the detection limits set by the external laboratory except for the CTP and CTS burns. The arsenic content was lowest for C burn and highest for CTP burn. Lead and zinc contents were lowered for all the fuel burns. The percentage differences in Barium, Manganese and Strontium are high for all the burns relative to the CT1 burn. In addition to the tests conducted at the cement plant and the external laboratory, cement samples, like clinker, were tested for the principle cement compounds using Rietveld analysis at the cement plant?s specialty laboratory. The results from the Rietveld analysis are tabulated in Table 4.59. 4.3.6.2 Physical Properties of Cement The physical properties of the cement were determined by tests performed at the cement plant and at Auburn University. Both testing entities conducted the same tests; the one exception was that the drying shrinkage development of paste prisms was also determined by staff at Auburn University. The results of the physical properties conducted by the cement plant are shown in Table 4.60. Table 4.57: ELR ?All Burns, Percentage difference in major parameters of cement relative to CT1 burn CT1 burn Value (wt. %) % Diff. Value (wt. %) Value (wt. %) % Diff. Value (wt. %) % Diff. Value (wt. %) % Diff. Value (wt. %) % Diff. Al 2 O 3 5.05 4.8 4.82 4.93 2.3 4.92 2.0 4.80 -0.5 4.46 -7.4 CaO 64.00 1.5 63.06 63.18 0.2 63.79 1.2 62.85 -0.3 64.38 2.1 Fe 2 O 3 3.20 4.3 3.07 3.11 1.4 2.86 -6.8 2.91 -5.1 3.20 4.3 K 2 O 0.49 3.2 0.48 0.41 -14.4 0.61 28.9 0.53 10.9 0.58 22.1 MgO 2.89 -14.6 3.39 3.47 2.6 3.29 -2.7 3.26 -3.6 3.16 -6.7 Na 2 O 0.02 -78.5 0.08 0.13 63.1 0.12 48.6 0.06 -18.5 0.12 48.0 P 2 O 5 0.08 32.3 0.06 0.06 4.7 0.10 63.2 0.05 -17.4 0.07 7.4 SiO 2 20.53 -2.5 21.06 21.51 2.2 21.16 0.5 21.14 0.4 19.93 -5.4 SO 3 2.78 -4.3 2.91 2.71 -6.6 2.69 -7.3 2.80 -3.7 2.75 -5.3 TiO 2 0.27 8.4 0.25 0.26 5.7 0.22 -9.1 0.24 -3.8 0.21 -16.7 Moisture 0.29 -40.5 0.48 0.39 -19.0 0 -100 0.20 -59.2 0.23 -53.3 LOI 0.69 -18.3 0.85 0.91 7.3 0.92 8.7 1.09 28.9 0.95 12.0 C 3 S 58.07 12.5 51.63 48.40 -6.3 54.12 4.8 50.81 -1.6 68.28 32.3 C 2 S 15.06 -29.7 21.42 25.17 17.5 19.83 -7.5 22.29 4.0 5.61 -73.8 C 3 A 7.96 5.1 7.58 7.80 3.0 8.19 8.0 7.79 2.8 6.40 -15.5 C 4 AF 9.74 4.3 9.34 9.46 1.4 8.70 -6.8 8.86 -5.1 9.74 4.3 TOC ND NA ND 0.05 NA ND NA NR NA 1.20 NA CTS burn C burn CTP burn Notes: ND - Not Detected NR- Not Reported NA- Not Applicable CTB burn CTW burn Parameter 214 CT1 burn Value (ppm) % Diff. Value (ppm) Value (ppm) % Diff. Value (ppm) % Diff. Value (ppm) % Diff. Value (ppm) % Diff. As (ppm) 8 -56.0 18 27 48.3 17 -4.1 16 -13.3 22 20.8 Ba (ppm) 321 133.5 138 300 118.2 400 191 333 142.4 350 154.5 Cd (ppm) ND NA ND NR NA ND NA NA NA ND NA Cl (ppm) 80 -85.2 541 57 -89.5 138 -74.5 76 -86.0 82 -84.9 Co (ppm) 14 NA ND 13 NA 12 NA 9 NA 15 NA Cr (ppm) 82 3.5 80 92 15.7 90 13.7 97 21.6 104 30.1 Cu (ppm) 64 105.4 31 14 -55.1 9 -70.5 ND NA 28 -11.8 Hg (ppm) 0.01 -33.3 0.02 NR NA 1 6233 0 266.7 0 155.0 Mn (ppm) 958 91.0 502 1600 219 1577 214.4 2033 305.3 1450 189.1 Mo (ppm) 9 NA ND 2 NA 4 NA 3 NA 30 NA Ni (ppm) ND NA ND 12 NA 10 NA NA NA 174 NA Pb (ppm) 33 -10.7 37 27 -27.7 15 -59.6 12 -67.0 13 -65.2 Sb (ppm) 51 -19.2 63 NR NA NR NA NR NA NR NA Se (ppm) 1 -12.5 2 NR NA ND NA ND NA ND NA Sr (ppm) 410 1.9 402 500 24.4 500 24.4 400 -0.5 400 -0.5 V (ppm) 62 17.7 53 69 30.9 66 26.1 62 17.3 68 29.0 Zn (ppm) 126 -30.9 183 62 -66.0 89 -51.3 83 -54.6 75 -59.2 Notes: ND - Not Detected NR- Not Reported NA- Not Applicable CTS burn Parameter C burn CTP burn CTB burn CTW burn Table 4.58: ELR ?All Burns, Percentage difference in minor parameters of cement relative to CT1 burn 215 Table 4.59: SLR ?All Burns, Rietveld analysis of cement CT1 burn (wt. %) % Diff. Value (wt.%) Value (wt.%) % Diff. Value (wt.%) % Diff. Value (wt.%) % Diff. Value (wt.%) % Diff. Alite (C 3 S) 68.23 17.75 57.94 47.63 -17.80 55.81 -3.69 60.86 5.03 61.97 6.94 Belite (C 2 S) 13.17 -28.15 18.33 28.75 56.86 21.87 19.29 16.84 -8.13 14.97 -18.36 Ferrite (C 4 AF) 10.23 -0.10 10.24 10.66 4.14 9.99 -2.41 10.60 3.52 11.03 7.75 Aluminate (C 3 A) 5.17 23.19 4.20 3.11 -25.89 4.68 11.60 2.71 -35.5 2.69 -35.90 Note: All percentage differences relative to Burn CT1 Parameter C burn CTP burn CTB burn CTW burn CTS burn The results from the physical property tests conducted by Auburn University are shown in Table 4.61. The properties of cement that showed practically significant changes relative to CT1 burn, when tested at Auburn University, are graphically presented in Figure 4.8. The compressive strength and drying shrinkage results were plotted on their own, and are discussed later in this section. As shown in Figure 4.8, the autoclave expansion of paste prisms was found to be increased when alternative fuels were used. An increase in autoclave expansion can be found for all fuel burns from Auburn University results, while an increase for Burns C and CTB only is reported by the cement plant. All the fuel burns except CTP burn showed a retarded initial and final setting times in both Gillmore and Vicat setting test, as found by Auburn University. Cement plant results too report that the CTP burn has retarded setting times in both the tests. The normal consistency and cube flow did not show any practically significant changes as reported by both testing agencies. The final property that showed noticeable change relative to CT1 burn is the air content in mortar, as shown in Table 4.60. This test was only conducted by the cement plant. All fuel burns showed a percentage change (increase or decrease) of more than 10 216 217 percent; CTS burn showed a decrease while all other fuel burns showed an increase. However, this change may be attributed to laboratory conditions and mixing procedure as much as anything else. Therefore, this property cannot be directly attributed to the chemical composition of cement, and is not practically significant to this study. The compressive strength of mortar cubes was tested by staff at both Auburn University and the cement plant. The most notable aspect of these results is that the results reported by the cement plant are all higher than those obtained by Auburn University. This result may be simply attributed to differences in laboratory practices and/or conditions at the time of mixing and placement. However, the aspect worth noting is the relative difference between each burn from both testing entities. The acceptable range of test results, based on ASTM C 109, within a single laboratory is approximately 11 percent, for mortar ages of three and seven days, and for multiple laboratories is about 19 percent. Based on those criteria, none of the results presented by the cement plant are unacceptably different between burns. However, the results presented by Auburn University show that the compressive strength of especially the three- and seven-day cubes for CT1 burn are considerably higher than all the fuel burns. The compressive strength results from Auburn University are graphically presented in Figure 4.9. These results will be compared with the compressive strength results associated with concrete in Section 4.3.8. Table 4.60: CPR ?All Burns, Physical properties and percentage change for cement CT1 burn Value % Diff. Value Value % Diff. Value % Diff. Value % Diff. Value % Diff. Air in Mortar (%) 6.7 15.5 5.8 6.6 13.8 6.6 13.8 6.4 10.0 5.2 -11.2 Blaine Specific Surface Area (m 2 /kg) 366 -3.9 381 374 -1.8 367 -3.7 372 -2.4 373 -2.2 Autoclave Expansion (% Exp.) 0.06 -40.0 0.10 0.18 80.0 0.15 50.0 0.06 -42.0 0.06 -41.5 Cube Flow (%) 125.7 2.2 123.0 122.5 -0.4 127.0 3.3 130.0 5.7 105.0 -14.6 Compressive Strength (MPa) 1 day 15.3 -0.6 15.4 13.6 -11.7 14.9 -3.2 14.3 -7.3 15.4 -0.3 3 days 24.3 -2.8 25.0 22.2 -11.2 23.5 -6.0 23.9 -4.5 24.6 -1.8 7 days 31.9 -2.1 32.6 30.7 -5.8 31.1 -4.6 30.6 -6.1 31.6 -3.1 28 days 42.7 -3.0 44.0 42.8 -2.7 42.0 -4.5 43.3 -1.5 41.3 -6.3 Normal Consistency (%) 25.6 -0.4 25.7 25.9 0.8 25.7 0.0 25.2 -2.1 25.0 -2.7 Gillmore Initial Set (Min.) 105 -8.7 115 98 -15.2 131 13.9 NR NA 120.0 4.3 Gillmore Final Set (Min.) 275 3.0 267 263 -1.5 225 -15.7 NR NA 240 -10.1 Vicat Initial Set (Min.) 80 9.6 73 62 -15.1 74 1.4 71 -2.7 66 -10.3 Vicat Final Set (Min.) 180 -23.4 235 225 -4.3 199 -15.3 228 -3.0 225 -4.3 Notes: NR- Not Reported NA - Not Applicable Property C burn CTP burn CTB burn CTW burn CTS burn 218 Table 4.61: AUR ?All Burns ? Physical properties and percentage change for cement 219 CT1 burn Value % Diff. Value Value % Diff. Value % Diff. Value % Diff. Value % Diff. Autoclave Expansion (% Exp.) 0.05 66.7 0.03 0.04 33.3 0.06 100.0 0.05 66.7 0.05 66.7 Cube Flow (%) 91 -7.1 98 111 13.3 101 3.1 106 8.2 106 8.2 Compressive Strength (MPa) 1 day 9.30 -15.5 11.0 11.5 4.5 12.0 9.1 10.9 -0.9 10.5 -4.5 3 days 17.2 -25.5 23.1 17.1 -26.0 21.5 -6.9 22.8 -1.3 21.3 -7.8 7 days 25.8 -13.4 29.8 24.8 -16.8 26.5 -11.1 28.3 -5.0 26.3 -11.7 28 days 35.1 -11.1 39.5 38.8 -1.8 32.9 -16.7 35.1 -11.1 32.7 -17.2 Normal Consistency (%) 25.4 -3.1 26.2 26.2 0.0 26.2 0.0 26.2 0.0 26.2 0.0 Gillmore Initial Set (Min.) 150 108.3 72 72 0.0 102 41.7 108 50.0 110 52.8 Gillmore Final Set (Min.) 238 64.1 145 105 -27.6 202 39.3 205 41.4 210 44.8 Vicat Initial Set (Min.) 106 53.6 69 66 -4.3 75 8.7 84 21.7 94 36.2 Vicat Final Set (Min.) 236 72.3 137 115 -16.1 180 31.4 150 9.5 180 31.4 Drying Shrinkage (%) 7 days -0.042 -17.6 -0.051 -0.045 -11.8 -0.035 -30.9 -0.045 -11.8 -0.047 -7.8 14 days -0.068 -5.6 -0.072 -0.069 -4.2 -0.073 1.4 -0.070 -2.8 -0.071 -1.4 21 days -0.079 -4.8 -0.083 -0.081 -2.4 -0.080 -3.6 -0.080 -3.6 -0.082 -1.2 28 days -0.087 -7.4 -0.094 -0.089 -5.3 -0.082 -13.3 -0.088 -6.4 -0.090 -4.3 CTW burn CTS burn Property C burn CTP burn CTB burn Figure 4.8: AUR- Fuel Burns, Percentage difference in physical properties of cement relative to CT1 burn 220 221 Another property measured at Auburn University was drying shrinkage of mortar prisms. Cement plant did not test for the property. The results from Auburn University are plotted in Figure 4.10. The ages associated with these results are drying ages. The specimens were cured for three days prior to exposure to drying conditions. In Figure 4.10, these results are presented with a shrinkage value reported as a positive percentage of the original length. From the graph, it can be seen that the results obtained are not too different. The CTB burn had the least 28-day shrinkage while CT1 burn had the most 28- day shrinkage, the difference being about 13 percent. The results from rest of the burns are all interspersed in the difference gap. The 7-day and 14-day shrinkages are nearly the same for all burns with about 5 percent or less variation. These results will be compared with the drying shrinkage results exhibited by concrete in Section 4.3.8. The final physical property determined for cement was the particle size distribution. This result is truly independent of the fuels used, but completely based on the grinding process. This fineness of the cement is adjusted by the cement plant to achieve the desired setting and strength gain behavior in the cement. However, the results in Figure 4.11 may help to explain some of the differences in some of the physical properties of the cement and concrete. From this result, it can be deduced that the particle distribution of CTS burn is on the coarser side compared to the other burns, with that of cement from CT1 burn being the finest of all. However, the particle distribution curves of cement from C, CTP, CTB, CTW, and CTS burns are nearly identical. The increased fineness of the cement produced in the CT1 burn may explain why it set earlier and exhibited higher strength gains. The finer the cement, the more rapid is the rate of hydration, which will accelerate setting and strength development. 222 Figure 4.9: AUR- All Burns, Compressive strength of mortar cubes 223 Figure 4.10: AUR- All Burns- Drying shrinkage of mortar prisms Figure 4.11: SLR- All Burns- Particle size distribution of Cement 224 225 4.3.7 Properties of Concrete Concrete was produced using the cement collected during each trial burn. There were two different concrete mixtures that were produced from the cement collected during each trial burn. The results for each type of mixture are discussed individually due to the fact that proportions of the mixtures were different and therefore, results cannot be compared with one another. This was done to observe the behavior of concrete in both high and low water-to-cement (w/c) ratio conditions. 4.3.7.1 Concrete with moderate water-to-cement ratio (Mix A) The first mixture, Mix A, was a conventional mixture with a water-to-cement ratio of 0.44, and it only utilized an air-entraining admixture. This mixture was made at Auburn University for all burns and at the concrete laboratory of the cement plant for Burns C, CT1, CTP and CTB. The setting time and splitting tensile strength data were not determined by the cement plant?s laboratory. The percent difference for each concrete property reported in Table 4.62 is calculated relative to the concrete mixture produced at Auburn University using cement from the CT1 burn. These differences for all properties except for compressive strength and splitting tensile strength are shown in Figure 4.12. The development of compressive and splitting tensile strength is shown in Figures 4.13 and Figure 4.14, respectively. It can be observed that the slump for all burns with alternative fuels is lower than that for Burns C, CT and CTP. Also, accelerated setting times and higher early-age (1-day and 3-day) compressive strength can be observed for burns with alternative fuels from Figure 4.13. There is a slight difference in air content too. All the burns except CTW burn tend to have lower air content than CT1 burn. Even though a difference in permeability can be 226 noticed, it is not practically significant since the acceptable within-test repeatability for permeability from ASTM C 1202 is on the order of 1000 Coulombs. In Table 4.63, the concrete data from the concrete laboratory of the cement plant is presented. Concrete was mixed and tested by the concrete laboratory of the cement plant for only four burns, C, CT1, CTP and CTB burns. It is observed that the cement plant results are somewhat different from the Auburn University results. The slump at the cement plant laboratory is much lower than that at Auburn University. This difference can most likely be attributed to differences in laboratory practices and/or conditions between the cement plant laboratory and Auburn University. Therefore, it is not a property attributable to only the cement used, and these results can only be used to evaluate the effect of the different cements on the relative strength differences. The concrete made at the cement plant also seems to have lower air content and higher unit weight for CTP and CTB burns, which can be attributed to variation in concrete mixing methods. However, the compressive strength, setting times and permeability from both the testing agencies are fairly comparable. Compressive strength is the primary property of concrete, and the most often specified by engineers. Because of that, it is a high priority of this project to determine if the utilization of alternative fuels in the production of portland cement has any effect on the compressive strength of concrete produced from that cement. The compressive strength development results of Mix A are shown in Table 4.62. These results are plotted relative to one another in Figure 4.13. The concrete from CT1 burn has the least compressive strength followed by C Burn. The compressive strength of concrete was observed to be higher when alternative 227 fuels were used. Concrete from CTB burn is found to have the highest early-age compressive strength of all the burns. This observation seems reasonable since the slump and setting time were found to be least for CTB burn among all the burns. The 91-day compressive strength of concrete from the CTP and CTB burns were recorded the highest for all ages. Table 4.62: AUR ?All Burns, Physical properties and percentage change for concrete Mix A CT1 burn AUR % AUR AUR % Diff. AUR % Diff. AUR % Diff. AUR % Diff. Total Air Content (%) 4.0 -5.9 4.25 4.0 -5.9 3.5 -17.6 5 17.6 4 -5.9 Slump (mm) 100 11.1 90 90 0.0 50 -44.4 80 -11.1 60 -33.3 Unit Weight (kg/m 3 ) 2394 -1.8 2439 2464 1.0 2460 0.9 2370 -2.8 2441 0.1 Initial Set (Min.) 211 -3.2 218 216 -0.9 154 -29.4 216 -0.9 154 -29.4 Final Set (Min.) 298 9.2 273 266 -2.6 231 -15.4 269 -1.5 227 -16.8 Compressive Strength (MPa) 1 day 12.3 -11.5 13.9 14.0 0.7 16.8 20.9 14.8 6.5 16.5 18.7 3 days 22.7 9.7 20.7 23.1 11.6 25.1 21.3 22.4 8.2 20.9 1.0 7 days 25.2 -11.3 28.4 28.5 0.4 34.7 22.2 32.5 14.4 30.1 6.0 28 days 35.0 -5.7 37.1 39.0 5.1 42.5 14.6 42.4 14.3 40.1 8.1 91 days 41.6 0.5 41.4 50.4 21.7 49.6 19.8 47.2 14.0 48.5 17.1 Splitting Tensile Strength (MPa) 1 day 1.7 -15.0 2.0 1.7 -15.0 2.2 10.0 1.8 -10.0 1.7 -15.0 3 days 2.4 4.3 2.3 2.3 0.0 2.8 21.7 2.1 -8.7 2.0 -13.0 7 days 2.6 -7.1 2.8 2.8 0.0 3.3 17.9 2.7 -3.6 2.5 -10.7 28 days 3.2 -3.0 3.3 3.5 6.1 3.9 18.2 3.1 -6.1 3.4 3.0 91 days 3.7 -7.5 4.0 4.3 7.5 4.2 5.0 3.9 -2.5 4.0 0.0 Permeability @ 91 days (Coulombs) 2650 -9.6 2930 2600 -11.3 2730 -6.8 2550 -13.0 2750 -6.1 CTP burn CTB burn C burn Property CTW burn CTS burn 228 Figure 4.12: AUR- All Burns, Percentage difference in Mix A concrete results relative to CT1 burn 229 Table 4.63: CPR ?All Burns, Physical properties and percentage change for concrete Mix A Property CT1 burn CPR % Diff. CPR CPR % Diff. CPR % Diff. Total Air Content (%) 3.6 12.5 3.2 3.3 3.12 3.4 6.25 Slump (mm) 30 0.0 30 40 33.33 40 33.33 Unit Weight (kg/m 3 ) 2450 0.1 2448 2454 0.25 2448 0.00 Initial Set (Min.) 218 -11.7 247 NC NA NC NA Final Set (Min.) 322 NA NC 263.0 NA 273.0 NA Compressive Strength (MPa) 1 day 15.8 4.6 15.1 11 -27.15 6.1 -59.60 3 days 23.3 6.4 21.9 20.7 -5.48 23.1 5.48 7 days 33.3 1.5 32.8 29.4 -10.37 30.9 -5.79 28 days 43.3 2.6 42.2 43 1.90 43.8 3.79 91 days 48.2 -2.8 49.6 49.3 -0.60 49.8 0.40 Permeability @ 91 days (Coulombs) 2530 -4.9 2660 2460 -7.52 2500 -6.02 C burn CTP burn CTB burn A similar trend is found in the cement plant results as well, where the concrete from alternative fuel burns was found, in general, to be higher in strength than that from the C or CT1 burns. However, the gain in strengths cannot be conclusively attributed to the use of alternative fuels, as many of the plant conditions were changed between these burns. Another important property tested is the splitting tensile strength. The Auburn University results are listed in Table 4.62 and are graphically presented in Figure 4.14. The trend among the burns is quite similar to the one found for compressive strength. The Burns CTP and CTB exhibited the highest splitting tensile strengths among all the burns, while Burn C had the least. Again, the tensile strength tends to be higher when alternative fuels are used to produce cement. However, it must be noted that according to ASTM C 496, the acceptable range of results of splitting tensile strength tests within a single laboratory is 14 percent. Based on this criterion, there were no appreciable changes in the 91-day splitting tensile strength between any of the burns. 230 231 The drying shrinkage development of concrete Mix A is shown in Table 4.64. The results are presented with drying shrinkage values reported as positive numbers. All values are given as a percent length change relative to the original length. The concrete was exposed to drying conditions after seven days of saturated curing after concrete placement. Due to the timing of the burns, all shrinkage results for the concrete mixture ages could not be reported for all burns. The results in Table 4.64 are presented graphically in Figure 4.15, where shrinkage values are reported as a positive percent length change. According to ASTM C 157, the allowable percent length change difference between results is 0.0266. This value is percentage of length change, not relative difference between the results for each burn. Based on this allowable value, there was no significant difference in drying shrinkage between any of the burns. Another test conducted by personnel at Auburn University was to measure the degree of hydration development with semi-adiabatic conditions. The results of this test for concrete Mix A can be seen in Figure 4.16. This plot shows the degree of hydration experienced by the concrete relative to concrete equivalent age. The concrete equivalent age is a property that quantifies the maturity of concrete, and is a measurement that includes both actual concrete age, and a multiplication factor to account for the effect of temperature. The equivalent age is shown on a logarithmic scale. It can be seen in Figure 4.15 that the degree of hydration for concrete at early age (up to equivalent age of about 100 hours) from all the burns is reasonably similar, which perhaps explains the similar setting times and early age strengths for the concrete. 232 Figure 4.13: AUR- All Burns, Compressive strength of concrete Mix A Figure 4.14: AUR- All Burns, Splitting tensile strength of concrete Mix A 233 Table 4.64: AUR ?All Burns, Drying shrinkage development for Mix A CT1 burn Length Chang e (%) % Diff Length Change (%) Length Change (%) % Diff Length Chage (%) % Diff Length Change (%) % Diff Length Change (%) % Diff 4 0.009 -50.0 0.018 0.008 -55.6 0.010 -44.4 0.010 -44.4 0.009 -50.0 7 0.018 -33.3 0.027 0.011 -59.3 0.013 -51.9 0.018 -33.3 0.012 -55.6 14 0.028 -17.6 0.034 0.020 -41.2 0.020 -41.2 0.025 -26.5 0.019 -44.1 28 0.029 -17.1 0.035 0.029 -17.1 0.028 -20.0 0.032 -8.6 0.024 -31.4 56 0.038 5.6 0.036 0.035 -2.8 0.034 -5.6 0.038 5.6 0.032 -11.1 112 0.045 2.3 0.044 0.046 4.5 0.043 -2.3 0.045 2.3 CIP NA 224 0.049 4.3 0.047 0.049 4.3 0.048 2.1 CIP NA CIP NA 448 0.050 2.0 0.049 CIP NA CIP NA CIP NA CIP NA Notes: CIP - Collection in Process NA - Not Applicable CTS burn Drying Age (days) C burn CTP burn CTB burn CTW burn 234 235 Figure 4.15: AUR- All Burns, Drying shrinkage development of concrete Mix A 236 Figure 4.16: AUR ?All Burns, Semi-adiabatic degree of hydration development for Mix A 237 However, at an equivalent age of 1,000 hours, the degree of hydration is markedly different; especially the concrete from CTW burn seems to have a low degree of hydration. 4.3.7.2 Concrete with low water-to-cement ratio (Mix B) The second mixture, Mix B, was a high-strength mixture with a water-to-cement ratio of 0.37. An air-entraining admixture and a water-reducing admixture were added to this concrete mixture. Mix B was only prepared by personnel at Auburn University. The results of tests on Mix B are shown in Table 4.65. Once again CT1 burn was considered the baseline, and therefore is used as the reference for the percent differences. The change in properties relative to that measured for the CT1 burn except compressive strength and splitting tensile strength, is presented graphically in Figure 4.17. Mix B showed an increase in total air content for all burns except the CTW burn. In fact, Burn C showed a 50 percent increase in this property over CT1 burn. However, these differences do not match with those encountered for Mix A. This is an indication that the differences are probably not caused by changes in the cement itself. The slumps for all the burns showed a decrease except for CTW burn. The maximum decrease was of about 19 percent for CTB burn. CTW burn showed an increase of about 12 percent. The final property was setting time, which showed a similar change in both initial and final times for all the burns except C burn and this effect was also detected in Mix A. Burn C showed retardation while all other burns showed acceleration in the setting times. Permeability changes for all the burns were not significant since they were all well within the repeatability limit of 1000 coulombs specified in ASTM C 1202 which matches the conclusion reached for Mix A. Table 4.65: AUR ?All Burns, Physical properties and percentage change for concrete Mix B CT1 burn Value % Diff. Value Value % Diff. Value % Diff. Value % Diff. Value % Diff. Total Air Content (%) 6.0 50.0 4.0 5.0 25.0 5.0 25.0 3.0 -25.0 5.0 25.0 Slump (mm) 150 -6.3 160 150 -6.3 130 -18.8 180 12.5 150 -6.3 Unit Weight (kg/m 3 ) 2374 -2.2 2427 2413 -0.6 2410 -0.7 2440 0.5 2395 -1.3 Initial Set (Min.) 318 33.1 239 229 -4.2 199 -16.7 230 -3.8 200 -16.3 Final Set (Min.) 405 39.7 290 291 0.3 262 -9.7 288 -0.7 259 -10.7 Compressive Strength (MPa) 1 day 20.8 -19.7 25.9 22.3 -13.9 29.9 15.4 23.3 -10.0 23.0 -11.2 3 days 31.9 -11.6 36.1 33.1 -8.3 34.8 -3.6 32.5 -10.0 31.2 -13.6 7 days 37.7 -5.7 40.0 38.0 -5.0 45.2 13.0 37.2 -7.0 38.2 -4.5 28 days 44.3 -10.9 49.7 51.0 2.6 52.7 6.0 48.8 -1.8 49.8 0.2 91 days 51.5 -12.9 59.1 58.0 -1.9 59.0 -0.2 53.8 -9.0 CIP NA Splitting Tensile Strength (MPa) 1 day 2.5 -16.7 3.0 2.7 -10.0 3.0 0.0 2.6 -13.3 2.8 -6.7 3 days 3.3 -10.8 3.7 3.4 -8.1 3.1 -16.2 3.1 -16.2 3.3 -10.8 7 days 3.7 -5.1 3.9 3.5 -10.3 3.4 -12.8 3.4 -12.8 3.8 -2.6 28 days 4.1 -4.7 4.3 4.0 -7.0 4.0 -7.0 3.8 -11.6 4.2 -2.3 91 days 4.3 -12.2 4.9 4.6 -6.1 4.3 -12.2 4.2 -14.3 CIP NA Permeability @ 91 days (Coulombs) 2650 3.9 2550 2670 4.7 2700 5.9 2350 -7.8 CIP NA Notes: CIP - Collection in Process NA - Not Applicable CTS burn CTB burn CTW burn Property C burn CTP burn 238 Figure 4.17: AUR ?All-Burns, Percent difference in concrete properties for Mix B 239 240 The compressive strengths for different batches of Mix B, as reported by Auburn University, are shown in Figure 4.18. Based on the acceptable range of results presented in ASTM C 39, the concrete made from C burn was significantly weaker than the concrete made from all other burns at all ages except for seven days. Based on this result, it is fairly conclusive that Burn C produced concrete with appreciably lower compressive strengths. This is mostly in agreement with the compressive strength results from Mix A, which showed a decrease in compressive strength at most ages. CTB burn showed the highest compressive strength, as also observed for Mix A. A graphical presentation of the splitting tensile strength of Mix B, conducted by Auburn University, can be seen in Figure 4.19. Just as with the splitting tensile strength results presented in Mix A, Burn C produced lower strengths than CT1 burn. However, it is interesting to note that CTB burn had a lower 91-day splitting tensile strength than all the burns except C and CTW burn, which is different from the expected result, given the high compressive strength for CTB burn in both Mixes A and B, and high splitting tensile strength in Mix A. But again, based on the acceptable range of results provided by ASTM C 496, there is no significant difference in 91-day splitting tensile strength results for Mix B. The results of the drying shrinkage development test conducted at Auburn University on Mix B concrete can be seen in Table 4.66. Just as with the Mix A results, shrinkage values are reported as a positive percentage length change. Some of the results of drying shrinkage of the recent burns are yet to be collected. The drying shrinkage development data for concrete Mix B is shown in Figure 4.20. 241 Figure 4.18: AUR ?All Burns, Compressive strength for concrete Mix B 242 Figure 4.19: AUR ? All- Burns, Splitting tensile strength for concrete Mix B Table 4.66: AUR ?All Burns, Drying Shrinkage development for Mix B CT1 burn Length Chang e (%) % Diff Length Change (%) Length Change (%) % Diff Length Change (%) % Diff Length Change (%) % Diff Length Change (%) % Diff 4 0.013 18.2 0.011 0.016 45.5 0.010 -9.1 0.009 -18.2 0.010 -9.1 7 0.019 -5.0 0.020 0.018 -10.0 0.016 -20.0 0.013 -35.0 0.018 -10.0 14 0.032 28.0 0.025 0.023 -8.0 0.022 -12.0 0.019 -24.0 0.022 -12.0 28 0.037 23.3 0.030 0.036 20.0 0.033 10.0 0.026 -13.3 0.030 0.0 56 0.043 10.3 0.039 0.042 7.7 0.039 0.0 0.032 -17.9 0.036 NA 112 0.051 27.5 0.040 0.045 12.5 0.043 7.5 CIP NA CIP NA 224 0.053 17.8 0.045 0.047 4.4 0.046 2.2 CIP NA CIP NA 448 0.054 14.9 0.047 CIP NA CIP NA CIP NA CIP NA C burn CTP burn CTW burn CTS burn Drying Age (days) CTB burn 243 Figure 4.20: AUR- All Burns, Drying shrinkage development of concrete Mix B 244 245 Based on the criteria given in ASTM C 157, none of the drying shrinkage results showed significant changes. This result was also found for Mix A. Therefore, it seems as though the drying shrinkage properties of the concrete were not significantly altered by use of alternative fuels to produce these cements. Figure 4.21 shows the results of the degree of hydration development measured under semi-adiabatic conditions test for concrete Mix B. It is evident from the plot that the degree of hydration development for concrete at early-age (up to equivalent age of about 30 hours) from all the burns is the same, which perhaps explains the similar setting times and early age strengths for the concrete. However, at an equivalent age of 1,000 hours, the degree of hydration is markedly different; the concrete from CTW burn seems to have an especially low degree of hydration. These results are similar to those found for Mix A in Figure 4.16. 4.3.8 Emissions The emissions from the process are one of the primary outputs with which the cement plant is concerned. Due to the fact that the emissions are pollutants, they must be closely monitored, and maintained within certain limits. The emissions are collected on a real-time basis by an instrument called the ?Continuous Emissions Monitoring System? (CEMS). The CEMS is a certified device that measures various pollutants in accordance with Environmental Protection Agency (EPA) requirements. The results were reported by the cement plant as five-minute averages. Table 4.67 shows the summary statistics for these data. 246 Figure 4.21: AUR ?All Burns, Semi-adiabatic degree of hydration development for Mix B 247 The emissions were reported in terms of tons per hour released. In order to account for variations in production rates between the burns, Auburn University researchers normalized these results so that they are presented in terms of tons per ton of clinker produced. In Table 4.67, the allowable limits set by Alabama Department of Environmental Management specified in ADEM (2006) are shown to provide some means to evaluate these data. These are the limits set for the specific cement plant where the three-day trials were performed. It is important to note that all the emissions from all the burns were well within ADEM limits. As discussed in Section 4.1, emissions from each burn will be studied with reference to the individual baseline burns as shown in Figure 4.1. This is done because emissions are sensitive to changes in raw material and fuel composition. Hence it would only be appropriate to compare the results of a fuel with the baseline burn that is similar to the burn in most aspects except for the use of alternative fuel itself. In Table 4.68, the three baseline burns are compared for any significant differences in the emissions. As shown in the Table 4.68, the emissions are significantly different for all the baselines burns. Hence statistical comparisons were made between the fuel burns and their respective baseline burns, and are presented in Table 4.69. The percentage differences are plotted in Figure 4.22. From Table 4.69 and Figure 4.22, many interesting conclusions can be drawn. NO x emissions were lowered for the C, CTP and CTB burns, while they were increased by about 5 percent for CTW burn and by about 59 percent for CTS burn. Table 4.67: CPR - Summary statistics for emissions Average (10 -6 ) 166 81.79 120.99 105.12 112.80 81.00 90.00 93.71 142.9 Coefficient of Variation (%) 8.3 8.0 9.4 9.8 11.0 6.4 16.7 0.21 P-Value 1 0.064 2 0.015 2 0.035 2 0.105 0.269 0.431 0.011 0.169 Average (10 -6 ) 152 0.04 1.12 0.04 0.09 0.63 2.51 0.37 0.62 Coefficient of Variation (%) 218.9 145.6 163.7 49.8 189.5 34.9 73.4 29.0 P-Value 1 <0.005 2 <0.005 2 <0.005 2 0.201 <0.005 2 <0.005 2 <0.005 2 <0.005 2 Average (10 -6 ) 3.6 2.31 3.42 2.61 2.18 3.55 3.35 2.61 2.06 Coefficient of Variation (%) 64.5 35.8 22.4 17.0 48.9 64.3 29.1 10.1 P-Value 1 <0.005 2 0.008 2 0.023 2 0.073 2 <0.005 2 0.095 2 0.065 2 0.09 2 Average (10 -6 ) 200 76.77 54.14 56.72 37.95 50.08 52.10 58.88 36.63 Coefficient of Variation (%) 9.9 10.8 22.0 11.6 10.2 14.5 19.7 9.1 P-Value 1 0.060 2 0.214 0.375 0.774 0.378 <0.005 2 0.278 0.314 Notes: 1 Based on Anderson-Darling Statistics 2 Not Normally Distributed 3 ADEM(2006) Burn CT1 Burn CTP CO (ton s / t on cli n k er) Burn CTW Burn CTS NO x (ton s / t on cli n k er) SO 2 (ton s / t on cli n k er) Burn CT2 Burn CTB ADEM Limit 3 Burn CT3 Emissions Burn C VO C (ton s / t on cli n k er) 248 Table 4.68: CPR ? Emissions, Significant difference between baseline burns Percent Difference -6.8 -26.0 Statistically Different Yes Yes P-Value 0.000 0.000 Percent Difference -92.3 123.6 Statistically Different Yes Yes P-Value 0.000 0.000 Percent Difference -36.5 -2.2 Statistically Different Yes Yes P-Value 0.000 0.000 Percent Difference -29.9 -3.7 Statistically Different Yes Yes P-Value 0.000 0.000 Note: 1 Relative to CT1 burn. Burn CT2 1 Burn CT3 1 CO NO x SO 2 VO C Emissions The results for NO x emissions being lower than the ADEM limits is noteworthy, considering the concerns about the NO x emissions being substantially increased when tires were used an fuel, reported by Martinez (1996) based on a study in California (see Section 2.3.3). The NO x emissions collected for the one burn that did not use scrap tires were the lowest and this in agreement with the findings of Martinez (1996). The NO x emissions were increased when switchgrass was used as alternative fuel. SO 2 emissions were reduced for all the burns by more than 50 percent. This is a significant reduction in SO 2 , but the measured SO 2 values are already very low at this plant. At other plants where a reduction in SO 2 is required, one could consider the use of some of these alternative fuels that are locally available to reduce the SO 2 emissions. Volatile organic compounds (VOC) have been problematic because of the narrow gap between the emissions measured and the allowable ADEM limits (as small as 5 249 percent in case of the baseline CT1 burn). Hence it is an objective to reduce the VOC levels at this plant. The VOC levels were lowered for both CTW and CTP burns, by 22 percent and 38 percent, respectively. However they were increased for Burns CTP and CTB, by 20 percent and 6 percent, respectively. The CO emissions showed mixed results as they increased for CTP and CTW burns by 49 percent and 13 percent, respectively. However, the CO emissions decreased by 30 percent and 4 percent for CTS and CTB burns, respectively. Table 4.69: CPR ? Emissions, Significant difference between fuel burns relative to their respective baseline burns Percent Difference -32.4 -6.8 -9.3 4.6 58.7 Statistically Different Yes Yes Yes No No P-Value 0.000 0.000 0.000 0.542 0.542 Percent Difference -96.4 -52.9 -74.3 -84.7 -75.4 Statistically Different Yes Yes Yes Yes Yes P-Value 0.000 0.000 0.000 0.000 0.000 Percent Difference -32.5 20.0 5.9 -22.0 -38.5 Statistically Different Yes Yes No Yes Yes P-Value 0.000 0.000 0.542 0.000 0.000 Percent Difference 41.8 49.5 -3.9 13.0 -29.7 Statistically Different Yes Yes Yes Yes Yes P-Value 0.000 0.000 0.061 0.000 0.000 Note: 1 Relative to CT1 burn 2 Relative to CT2 burn 3 Relative to CT3 burn Fuel Burns C burn 1 CTW burn 3 CTS burn 3 CTP burn 2 CTB burn 3 CO NO x SO 2 VO C Emissions The emission results for all alternative fuel burns are below the ADEM limits, and this addresses the concerns generally associated with high emission levels for the non- biodegradable waste-fuels such as plastics. Maker (2004) observed that Woodchips 250 251 produce little SO x gases and their combustion creates NO x , CO and VOC emissions at levels comparable to fossil fuels ( Section 2.3.4.4). The emission results for the CTW burn are in agreement with the results reported by Maker (2004) 4.5 Conclusions The production of portland cement utilizes many complex materials, facilities, and processes. The nature of the production process results in numerous variables that have an effect on both the chemical and physical properties of the cement that is manufactured. Therefore, it is very difficult to conclusively attribute any changes in these properties directly to the utilization of alternative fuels. Regardless, this study has provided many conclusions regarding the use of alternative fuels in the portland cement production process. One aspect of the utilization of alternative fuels that the cement plant was acutely concerned with was the ability of the facilities to maintain production while consuming these fuels. In this regard, it was found that the maximum allowable rate that tires could be utilized was controlled by sulfur build-ups inside the calciner system. These build-ups were primarily composed of sulfur-derived compounds, and were directly responsible for limiting the air flow through the kiln, which reduced oxygen levels necessary for good combustion in the kiln. The feed rate of the plastics was also limited by the feed equipment used. In this case, the feed system had problems conveying the low-density (5.26 lb/ft 3 ) plastic fuels that were being used. Broiler litter and Woodchips did not cause any feed problems. The bales of switchgrass had to be shredded before feeding into the system which proved to be labor-intensive. In spite of the limitations associated with 252 these fuels, the results shown in Section 4.3.3 showed some promising results. The most prominent of these was the energy content of the alternative fuels. The range of heat values of each of the fuels were determined to be as follows: 1. Coal: 11,157 to 12,476 BTU/lb, 2. Tires: 14,467 to 14,687 BTU/lb, 3. Plastics: 11,327 to 14,446 BTU/lb, 4. Broiler litter: 6,484 to 7,188 BTU/lb, 5. Woodchips: 8,170 to 8549 BTU/lb, and 6. Switchgrass: 7,888 to 8393 BTU/lb. These results indicate that the tires and plastics have good combustion properties as they produce more heat per pound than the coal. Broiler litter and woodchips, despite the low heat values, are available in abundance and are sustainable bio-fuels. Most of the proximate and ultimate analyses of these fuels provided desirable results as per the fuel requirements of the cement plant stated in Section 4.3.3. The chemical and combustion properties, along with the costs associated with acquisition, imply that the cement plant may consider the use of these fuels in the future. The second goal of this study was to determine if the utilization of alternative fuels has a direct impact on the chemical composition of the product. Based on the results presented in Sections 4.3.5 and 4.3.6, statistically significant changes in the chemical composition of the clinker and the cement did occur between burns. However, based on the results shown in Sections 4.3.1 and 4.3.2, there were also significant changes in the chemical composition of the raw materials and the kiln feed. 253 Figure 4.22: CPR ? Emissions, Percent difference between fuel burns relative to respective baseline burn 254 These results, along with an understanding of the inherent variability of the portland cement production process itself, make it impossible to conclude that the changes in chemical composition of the final product were directly related to the type of fuel that was used. Additionally, the primary compounds in the clinker and cement, Al 2 O 3 , CaO, Fe 2 O 3 , and SiO 2 , showed no practically significant changes. These results suggest that the cement plant is able maintain consistent concentrations in these parameters when burning each of the fuels used in this study. These are significant results, because these parameters are those that have the greatest effect on the properties of the cement and concrete. The third and fourth goals of this study were to determine if the utilization of alternative fuels directly impacts the physical properties of the cement, and concrete produced from that cement. Again, based on the chemical composition results, it was not possible to conclude that the alternative fuels directly impacted the composition of the cement. Therefore, it was not possible to conclude that use of the alternative fuels directly impacted any of the physical properties of the cement or concrete. Additionally, many of these physical properties showed no practically significant change between burns. The air content in mortar, Blaine specific surface area, mortar cube flow, and the normal consistency were all minor physical properties of cement that showed no practically significant change between burns. For the concrete, the air content, slump, and unit weight were all properties that were not consistently affected in the same way between the two types of mixtures made from the same cement. Another property of 255 concrete, permeability, showed no significant change between burns. This is a significant result. Because there was no significant change, it can be concluded that the same degree of permeability can be obtained using the cement from each of these burns. Another property that is important to cement and concrete is how susceptible it is to length change when it dries. Drying shrinkage tests were conducted on mortar, as well as on two different water-to-cement ratio concrete mixtures. In each case, no significant change was measured between each of the burns. This shows conclusively that each of the cements used in this study behaved similarly when exposed to drying conditions. The splitting tensile strength of concrete also showed no significant difference between burns. Some of the results did show minor differences, but none of these exceeded the acceptable range of results inherent to the test. Although the fuels used cannot be conclusively attributed with affecting the properties of cement or concrete, there were a number properties that did show significant changes between burns. First, the autoclave expansion of paste prisms determined at Auburn University showed an increase relative to CT1 burn in all cases. The setting times for cement and concrete showed some significant changes. In the Gillmore and Vicat setting tests of cement pastes, the cement of CTP burn showed significant acceleration relative to that of CT1 burn, while cement from all other burns showed retardation. The concrete made from all burns except Burn C showed acceleration for both Mix A and Mix B. However, this result was not corroborated by the cement paste results. In both the concrete mixtures, Burn C showed a trend in that it consistently produced the lowest compressive strengths. Similar results were also found for the early age strengths of mortar cubes. This is a significant result because it implies that 256 compressive strengths are likely to improve for cement produced using tires or other alternative fuels when compared to cement produced using coal as the only fuel (C Burn); however, to establish this as a direct impact of using alternative fuels, further research is necessary. The final goal of this study was to determine whether the utilization of alternative fuels directly impacts the emissions released by the cement plant. Just as found for the chemical composition of the cement, it is difficult to say that the fuels used were directly responsible for any changes that may have been seen in emission characteristics. Many variables within the production process have an effect on the emissions. However, each of the emissions monitored showed changes between burns. The NO x emissions were lowered for Burns C, CTP and CTB, but increased for Burns CTW and CTS. The NO x emissions were the lowest for the burn condition that did not use scrap tires which agrees with the findings of Martinez (1996). The SO 2 emissions were reduced for all the burns by more than 50 percent. The VOC levels were reduced for both Burns CTW and CTS, but were increased for Burns CTP and CTB. The CO emissions decreased for Burns CTS and CTB, but were increased for Burns CTP and CTW. However, it is important to note that despite all the changes in the emission levels, all the emissions monitored were below the allowable limits set by the Alabama Department of Environmental Management (ADEM 2006). Unfortunately, the variable nature of the cement production process makes it very difficult to conclusively state that the use of alternative fuels has a significant effect on cement and concrete properties, or on emissions characteristics. Although there were 257 changes in some of these properties between burns, further research is necessary to determine whether these changes are a direct result of the use of only the alternative fuels. 258 CHAPTER 5 SUMMARY, CONCLUSIONS, AND RECOMMENDATIONS 5.1 Summary In the production of portland cement, a variety of raw materials are chemically fused in the presence of temperatures on the order of 1500 ?C to produce a product known as clinker. Clinker is ground down, with sulfates, to produce portland cement. Large quantities of fuels are required to maintain the high temperatures involved in the process. Historically, the fuel sources used have been nonrenewable fossil fuels such as coal and oil. The idea of supplementing some of these traditional fuels with alternative fuels may be both economically profitable and environmentally beneficial. Many of the alternative fuels that can be used in the portland cement industry are waste products from some other industry. In this study, whole tires, waste post-industrial plastics, broiler litter, woodchips, and switchgrass were examined to determine their viability as alternatives to traditional fuels. Tires have been used in the cement industry for some years, particularly in European cement plants. Recycled industrial plastics are waste products from many different industries. Typically, they would be either disposed of in a landfill, or incinerated. Their consumption by a cement plant both decreases the amount of landfill space occupied, and makes use of the heat generated through the 259 incineration process. Typical incineration does not use the heat generated, and is therefore not as efficient. Broiler litter is a byproduct of the broiler farming industry. Traditionally, broiler litter is applied to land as a fertilizer. However, due to the over application of broiler litter in regions where broiler production is high, the land and groundwater are suffering from over-saturation of phosphorus and nitrogen (D?valos et al. 2002). The use of broiler litter as fuel in a cement plant gives the broiler industry another option to dispose of this material and it may release some of the pressure that the environment may feel from land application. Woodchips are solid waste fuels obtained while processing lumber. Woodchip prices are relatively stable. They can be transported and unloaded by dump trucks. Because they are available locally, long distance haulage and packaging costs can be reduced. Woodchips have primarily been used as fuel in commercial heating systems, manufacturing plants, and power plants. The low ash content of woodchips is particularly suitable for the cement kiln. Switchgrass is considered to be one of the most valuable native bio-fuels in the United States. It requires little fertilization and herbicide, and can be harvested twice a year with existing farm equipment. The grass is tough and has high productivity (Boylan et al. 2000). It is also valuable for soil stabilization, erosion control and as a windbreak. It has been co-fired successfully with coal in power generating plants before, but the high content of potassium, sodium, chlorine and silica caused problems when burned due to erosion, slagging and fouling, which can be avoided in cement kilns by incorporating the ash into the clinker (Sami et al. 2001). 260 In this study, a full-scale, operational cement plant was used as the testing site. During normal production, the aforementioned alternative fuels were burned in eight different test periods. Each of these test periods was called a trial burn, and each utilized different combinations of these fuels. They are as follows: 1. C burn utilized only coal as fuel. 2. CT1 burn utilized coal and tires. This is the standard fuel combination used at the cement plant, and was therefore considered the baseline for comparison purposes. This is the first baseline burn. 3. CTP burn used coal, tires, and waste plastics. These plastics were considered alternative fuel one. 4. CT2 burn utilized coal and tires. Again, the standard fuel combination was used and this is the second baseline burn. 5. CTB burn used coal, tires, and broiler litter. Broiler litter was the second alternative fuel tested. 6. CT3 burn utilized coal and tires. Again, the standard fuel combination was used and this is the third baseline burn. 7. CTW burn used coal, tires, and woodchips. Woodchips was the third alternative fuel tested. 8. CTS burn used coal, tires, and switchgrass. Switchgrass was the fourth alternative fuel tested. Due to the timing of the last trial burn, some of the long-term results have not been collected and only the available data are reported in this document. However, the rest of the results will be presented in future work. 261 Within each trial burn, samples of each material involved in the production process were collected, including the traditional and alternative fuels. The chemical composition of each of these materials was determined by two testing agencies. The composition of the clinker and cement were then compared between burns. Due to the fact that most of the incombustible material is incorporated into the clinker, an attempt was made to determine if the chemical composition of the fuels had a direct effect on the composition of the clinker and cement. The cement was then tested for various physical properties. Concrete was then made with the cement collected from each burn, and various concrete properties were tested. These physical properties of cement and concrete were compared between burns in order to determine if the fuels had any impact. Finally, the emissions released by the cement plant were monitored during each trial burn. These emissions were then compared between trial burns in order to determine if any correlations could be made between the alternative fuels and the emissions profiles. 5.2 Conclusions The first objective of this study was to determine if the utilization of alternative fuels had an impact on the ability of a full-scale cement plant to maintain productive operations. Some problems did occur when the fuels other than coal were used. The quantity of tires that could be burned was limited by the development of sulfur-based build-ups within the calciner system. These build-ups limited the amount of airflow, and effectively choked the system. The quantity of plastics that could be burned was limited by the ability of the fuel equipment to move the low-density material into the kiln. The 262 shredding of switchgrass bales before feeding into the kiln proved to be quite labor- intensive. Despite the limiting factors, all of these fuels showed potential, in that they both had low acquisition costs and high energy content. The range of heat values of each of the fuels were determined to be as follows: 1. Coal: 11,157 to 12,476 BTU/lb, 2. Tires: 14,467 to 14,687 BTU/lb, 3. Plastics: 11,327 to 14,446 BTU/lb, 4. Broiler litter: 6,484 to 7,188 BTU/lb, 5. Woodchips: 8,170 to 8549 BTU/lb, and 6. Switchgrass: 7,888 to 8393 BTU/lb. Broiler litter and woodchips, though low in energy content, burnt well and did not cause any problems during production. Based on the energy content, local availability, and the cost of acquisition relative to the coal, the cement plant may in the future consider the use of these alternative fuels. The second objective of this study was to determine if the utilization of alternative fuels had an impact on the chemical composition of the clinker and/or cement. Based on the results presented in Chapter Four, the chemical composition of both of these materials showed significant differences between each of the trial burns in many of the parameters that were measured. However, the kiln feed and raw materials also showed significant changes in chemical composition. Additionally, the process of producing portland cement is inherently variable. Therefore, it is not possible to conclude that the changes in 263 chemical composition of the clinker and cement were directly affected by the use of these alternative fuels. The most significant results concerning the chemical composition of clinker and cement were that the concentrations of Al 2 O 3 , CaO, Fe 2 O 3 , and SiO 2 showed no practically significant changes. This is important because these compounds are the primary components of the clinker and cement, and they have the greatest effect on the properties of cement and concrete. These results suggest that the cement plant is capable of maintaining consistent concentrations of these compounds while using raw materials with different composition and while burning any of the fuels used in this study. The third goal of this study was to determine if the utilization of alternative fuels directly impacted the physical properties of the cement it produced. Many of the physical properties of cement that were tested did not show a significant difference between trial burns. Drying shrinkage of paste prisms were the most prominent results that showed no practically significant change. These results revealed that the drying shrinkage behavior of these cements was not altered by the use of alternative fuels. However the autoclave expansion of paste prisms was found to be increased when alternative fuels were used One property that did show a significant change in the cement was the setting time. The cement produced using coal, tires, and plastics showed acceleration in final setting times of as much as 27 percent relative to the cement produced using coal plus tires. The cements produced using other alternative fuels showed retardation in initial and final setting times. The final result that showed a significant change was the mortar cube compressive strength. The cement produced in the CT1 burn showed a trend of higher strengths than the other burns, at all ages, while the cement produced in the C burn 264 showed lower strengths, especially in early ages. Although differences were found in the physical properties of cement between the trial burns, it was not possible to conclude that these effects were a direct result of the use of these alternative fuels. The fourth objective of this study was to determine if the utilization of alternative fuels directly impacted the properties of concrete made from these portland cements. Two different concrete mixture designs with water-cement ratios of 0.37 and 0.44 were made from the cement produced during each trial burn. Just as with the physical properties of the cement, there were some properties that showed significant changes, and some that did not. One notable property that did not show any significant changes between burns was the permeability. The 91-day results from both concrete mixtures showed no significant change in permeability between any of the trial burns. Additionally, the drying shrinkage development of both concrete mixtures did not show any significant changes between any trial burns. This result agreed with that for the drying shrinkage development of paste prisms. The splitting tensile strength of both concrete mixtures also showed almost similar trends for the trial burns for both the mixes. The C burn produced lower strengths than the CT1 burn. The CTB burn had lower 91-day splitting tensile strength for Mix B but a higher 91-day splitting tensile strength for Mix A, relative to the results from the CT1 burn. However it is important to note that, based on the acceptable range of results provided by ASTM C 496, there is no significant difference in 91-day splitting tensile strength between the trial burns. 265 Some concrete properties did show significant difference, one of which was the setting time. The concrete made from all burns except Burn C showed acceleration for both Mix A and Mix B. However, this result was not corroborated by the cement paste results. The compressive strength of concrete cylinders is the primary property specified by engineers. This property did show a significant trend for the concrete made using the cement by only burning coal. The concrete produced from this cement had lower compressive strength at most ages, than the concrete made from the cement produced when alternative fuels were used. Based on these results, it is concluded that the compressive strengths are likely to improve for cement produced using tires or other alternative fuels when compared to cement produced using coal as the only fuel (C Burn). The final objective of this study was to determine the impact of using alternative fuels on emissions released by the cement plant. The results of this study did show conclusively that the emissions were significantly different between each of the burn phases. The NO x emissions were lowered for C, CTP and CTB burns, but increased for the CTW and CTS burns. The NO x emissions were the lowest for the burn condition that did not use scrap tires which agrees with the findings of Martinez (1996). The SO 2 emissions were reduced for all the burns by more than 50 percent. The VOC levels were reduced for both the CTW and CTS burns, but were increased for the CTP and CTB burns. The CO emissions decreased for the CTS and CTB burns, but were increased for the CTP and CTW burns. The variable nature of the production process once again limited the ability of the author to state conclusively that the fuels used were directly responsible for any changes 266 that were seen in the emissions. However, it is important to note that despite all the changes in the emission levels, all the emissions monitored were well within the allowable limits set by the Alabama Department of Environmental Management (ADEM 2006). The fact that the cement plant was able to produce cement, with the substantial use of alternative fuels, with no detrimental effects on either the production process or the final product itself and at the same time, keeping the emissions well within the permissible limits, is a significant finding for the portland cement industry. This can lay the foundation for further exploration, research, and implementation in the future. Overall, it can be concluded that scrap tires, waste plastics, broiler litter, woodchips and switchgrass have the potential to become sustainable alternative fuel sources for use in cement production. The final decision on the use of a specific alternative fuel will depend on the availability of the fuel, its cost, and its compatibility with the particular cement plant 5.3 Recommendations Although the sampling and testing plan used in this project was thorough, it was very difficult to make conclusions concerning some of the objectives that were originally developed. The use of a full-scale portland cement production facility presented a number of problems in attempting to reach these objectives. One major hurdle was the logistics of outfitting the cement plant with the facilities necessary to handle the alternative fuels that were to be studied. Obstacles in this regard resulted in a number of delays in the timing of the burns. Now that the facilities are in place to handle these 267 alternative fuels, it would be beneficial to conduct a number of trial burns using similar fuels within close proximity (time wise) to one another. Due to the delays experienced in this study, the burns were spaced months apart. These extended breaks between trial burns allowed the cement plant to make adjustments in the production process, in an attempt to optimize production. These changes removed much of the consistency in production conditions between burns. In order to satisfy some of the objectives of this project, it would be necessary to maintain consistent inputs to the process. This study found that the kiln feed differed in chemical composition from one trial burn to another. Furthermore, the fuels themselves were not consistent in their chemical composition, and in fact, the source of the coal was completely changed between some burns. Other parameters of the production process, which were not monitored in this project, were also likely altered between burns. Once again, these changes that were made rendered it virtually impossible to determine if the chemical composition of the fuels had any effect on the chemical composition of the clinker and/or cement. Despite conducting more baseline burns between the fuel burns, the effect of change in sources of raw materials and coal could not be completely addressed, since there were variations in the chemical compositions of inputs even between the fuel burns and their respective baseline burns. Ideally, the issue can be overcome, if the baseline burns were conducted immediately before the fuel burn, which may keep the chemical composition of raw materials and coal fairly consistent, while keeping the feed and production rates reasonably similar, within practical limits. However, this testing scheme 268 would require extra costs associated with the production, sampling and testing of the materials. Once an ideal baseline burn for an alternative fuel burn is established, it would be interesting to vary the chemical composition of each input and output of the process, taking the actual feed and production rates of the all the materials into consideration. This could allow a researcher to understand exactly how the variation in chemical composition of an input is affecting the chemical composition of the final output of the process. Perhaps some of this work can be conducted under controlled laboratory conditions that have been designed to accurately simulate the cement manufacturing process. Another aspect of this project that one would ideally alter is simply the number of tests conducted. Every facet, be it chemical compositions or physical properties, would benefit from increased repetitions. This was limited, however, by finances, personnel, and time. Further, collection of more cement would give an opportunity to repeat the concrete mixtures and thereby, establishing the concrete results. Also, study of effect of admixtures may provide an insight into the variation in some properties of cement compared to the properties of concrete made from the cement. The emphasis of this project was the effect that alternative fuels had on everything from the production process of cement to the physical properties of concrete made from that cement. With that in mind, it would be beneficial to continue with this study by utilizing many other materials that potentially could be used as an alternative fuel. The options are numerous, and this study would benefit from the use of additional fuels. 269 REFERENCES Abelha, P., I. Gulyurthlu, D. Boavida, J. Seabra Barros, I. Cabrita, J. Leahy, B. Kelleher, and M. Leahy. 2003. Combustion of poultry litter in a fluidised bed combustor. Fuel 82, no. 6:687-692. ADEM. 2006. Air Permit. Alabama Department of Environmental Management, Montgomery. Letter issued to the cement plant, 22 nd September. Barger, G. S. 1994. Utilization of waste solvent fuels in cement manufacturing. In Cement Manufacturing and Use. New York: American Society of Civil Engineers. Barlaz, Morton A., William E. Eleazer II, and Daniel J. Whittle. 1993. Potential to use waste tires as supplemental fuel in pulp and paper mill boilers, cement kilns, and in road pavement. Waste Management & Research 11, no. 6:463-480. Barros, A. M., J. A. S. Ten?rio, and D. C. R. Espinosa. 2004. Evaluation of the incorporation ratio of ZnO, PbO, and CdO into cement clinker. Journal of Hazardous Materials. B112:71-78. Bhatty, J. I. 2004. Minor Elements in Cement Manufacturing. Chap. 3.6 in Innovations in Portland Cement Manufacturing. Skokie, Illinois: Portland Cement Association. Bhatty, J. I., S. Bhattacharja, and H. A. Todres. 1996. Use of cement kiln dust in stabilizing clay soils. Skokie, Illinois: Portland Cement Association. Serial Number 2035. 270 Bhatty, J. I., and F.M. Miller. 2004. Application of thermal analysis in cement manufacturing. Chap. 8.4 in Innovations in Portland Cement Manufacturing. Skokie, Illinois: Portland Cement Association. Bhattacharja, S. 1999. Performance of landfill liners in the presence of CKD leachate. Skokie, Illinois: Portland Cement Association. Serial Number 2074b. Blaine, R. L., L. Bean, and E. K. Hubbard. 1965. Occurrence of minor and trace elements in portland cement. Building Science Series 2:33-36. U.S. Department of Commerce, National Bureau of Standards. Blezard, R. D. 1998. Reflections on the history of the chemistry of cement. Society of Chemical Industry. ISSN 1353-114X. LPS 0104/2000 Boylan, D., V. Bush, D.I. Bransby. 2000. Switchgrass cofiring: pilot scale and field evaluation Chatterjee, A. K. 1979. Cement raw materials and raw mixes. Pit & Quarry 72, no. 5:73- 75, 79-81. Chatterjee, A. K. 2004. Raw materials selection. Chap. 2.1 in Innovations in portland cement manufacturing. Skokie, Illinois: Portland Cement Association. Chatterjee, A. K. 2004. Materials preparation and raw milling. Chap. 2.3 in Innovations in Portland Cement Manufacturing. Skokie, Illinois: Portland Cement Association. Corti, A., and L. Lombardi. 2004. End life tyres: Alternative final disposal processes compared by LCA. Energy, 29:2089-2108. D?valos, J. Z., M. V. Roux, and P. Jim?nez. 2005. Evaluation of poultry litter as a feasible fuel. Thermochimica Acta, 394:261-266. 271 Devore, J., Farnum, N. 2005. Applied Statistics for Engineers and scientists, 2 nd Edition, Chapter 8. Eckert, James O. Jr., and Qizhong Guo. 1998. Heavy metals in cement and cement kiln dust from kilns co-fired with hazardous waste-derived fuel: Application of EPA leaching and acid-digestion procedures. Journal of Hazardous Materials 59, no. 1:55-93. Environmental Protection Agency (EPA). 1995. ?Chapter 11.6, Portland Cement Manufacturing.? Compilation of Air Pollutant Emission Factors, AP-42. Research Triangle Park, Nc.: U. S. Environmental Protection Agency. Gardeik, H. O., H. Rosemann, S. Spring, and W. Rechenberg. 1984. Behavior of nitrogen oxides in rotary kiln plants of the cement industry. Zement-Kalk-Gips 12:499- 507. Gartner, E. M. 1980. The effect of minor and trace elements on the manufacture and use of portland cement. Skokie, Illinois: Portland Cement Association. Serial Number 2064. Greer, W. L. 1989. SO 2 / NO x control compliance with environmental regulations. IEEE Transactions on Industry Applications 25, no. 3:475-485. Greco, C., G. Picciotti, R. B. Greco, and G. M. Ferreira. 2004. Fuel selection and use. Chap. 2.5 in Innovations in Portland Cement Manufacturing. Skokie, Illinois: Portland Cement Association. Hanle, L. J., K. R. Jayaraman, and J. S. Smith. 2004. CO 2 emissions profile of the U.S. cement industry. Washington D. C.: Environmental Protection Agency. 272 Hawkins, G. J., J. I. Bhatty, and A. T. O?Hare. 2004. Cement kiln dust generation and management. Chap. 6.3 in Innovations in Portland Cement Manufacturing. Skokie, Illinois: Portland Cement Association. Hughes, E. 2000. Biomass cofiring: economics, policy and opportunities, Biomass and Bio-energy, Volume 19, Issue 6. Jackson, Peter J. 1998. Chap. 2 in Lea?s Chemistry of Cement and Concrete. 4 th ed. London: Arnold. Kakali, G., and G. Parissakis. 1995. Investigation of the effect of Zn oxide on the formation of portland cement clinker. Cement and Concrete Research 25, no. 1:79-85. Kakali, G., S. Tsivilis, and A. Tsialtas. 1998. Hydration of ordinary portland cements made from raw mix containing transition element oxides. Cement and Concrete Research 28, no. 3:335-340. K??ntee, U., R. Zevenhoven, R. Backman, and M. Hupa. 2002. Modeling a cement manufacturing process to study possible impacts of alternative fuels. (paper presented at TMS Fall 2002 Extraction and Processing Division Meeting on Recycling and Waste Treatment in Mineral and Metal Processing: Technical and Economic Aspects). Kawamura, M. and H. Fuwa. 2003. Effects of lithium salts on ASR gel composition and expansion of mortars. Cement and Concrete Research 33, no. 6:913-919. Kirk, L. B. 2000. Potential dioxin release associated with tire derived fuel use in a cement kiln Gallatin County, Montana. 273 Klemm, W.A. 1980. Kiln Dust Utilization. Martin Marietta Laboratories Report MML TR 80-12, Baltimore, Maryland. Kolovos, K., S. Tsivilis, and G. Kakali. 2001. The effect of foreign ions on the reactivity of the CaO-SiO 2 -Al 2 O 3 -Fe 2 O 3 System part I: Anions. Cement and Concrete Research 31, no. 3:425-429. Kolovos, K., S. Tsivilis, and G. Kakali. 2002. The effect of foreign ions on the reactivity of the CaO-SiO 2 -Al 2 O 3 -Fe 2 O 3 system part II: Cations. Cement and Concrete Research 32, no. 3:463-469. Kosmatka, Steven H., Beatrix Kerkhoff, and William C. Panarese. 2002. Design and Control of Concrete Mixtures. Skokie, Illinois: Portland Cement Association. Konsta-Gdoutos, M. S., and S. P. Shah. 2003. Hydration and properties of novel blended cements based on cement kiln dust and blast furnace slag. Cement and Concrete Research 33, no. 8:1269-1276. Knofel, D., The incorporation of TiO 2 into the phases of portland cement clinker. Zement-Kalk-Gips 32, no. 1:35-40. Lawrence, C. D. 1998. Physiochemical and mechanical properties of portland cements. Chap. 8 in Lea?s Chemistry of Cement and Concrete. 4 th ed. London: Arnold. Maker, T. M. 2004. Wood chips heating systems. A guide for institutional and commercial biomass installations. Biomass energy resource center Manias, C. G. 2004. Kiln burning systems. Chap. 3.1 in Innovations in Portland Cement Manufacturing. Skokie, Illinois: Portland Cement Association. 274 Mantus, E. K., K. E. Kelly, and G. A. Pascoe. 1992. All fired up: Burning hazardous waste in cement kiln. Seattle, Washington: Environmental Toxicology International, and the Combustion Research Institute. Marengo, E., M. Bobba, E. Robotti, and M.C. Liparota. 2006. Modeling of the polluting emissions from a cement production plant by partial least-squares, principal component regression, and artificial neural networks. Environmental Science & Technology 40, no. 1:272-2804 McLaughlin S. , J. Bouton, D. Bransby, B. Conger, W. Ocumpaugh, D. Parrish, C. Taliaferro, K. Vogel, and, S. Wullschleger. 1999. Developing Switchgrass as a Bioenergy Crop Miller, B. B., R. Kandiyoti, and D. R. Dugwell. 2002. Trace element emissions from co- combustion of secondary fuels with coal: A comparison of bench-scale experimental data with predictions of a thermodynamic equilibrium model. Energy & Fuels 16, no. 4:956-963. Miller, F. M. 1976. Minor elements in cement clinker. Paper No. 16, PCA Cement Chemist?s Seminar. Skokie, Illinois: Portland Cement Association. Miller, F. M., and G. J. Hawkins. 2000. Formation and emission of sulfur dioxide from the portland cement industry. Skokie, Illinois: Portland Cement Association. Serial Number 2460a. Minitab. 2006. Minitab Methods and Formulas, Minitab 15.1.0.0., Minitab Inc. Mishulovich, A. 1999. Development of manufactured supplementary cementitious material for CKD utilization. Skokie, Illinois: Portland Cement Association. Serial Number 2036b. 275 Moir, G. K., and F. P. Glasser. 1992. Mineralizers, modifiers and activators in the clinkering process. 9 th International Congress of Chemistry of Cement, Delhi, India, Vol. 1. Mokrzycki, E., and A. Uliasz-Boche?czyk. 2003. Alternative fuels for the cement industry. Applied Energy 74, no. 1-2:95-100. Mokrzycki, E., A. Uliasz-Boche?czyk, and S. Mieczys?aw. 2003. Use of alternative fuels in the Polish cement industry. Applied Energy 74, no. 1-2:101-111. Murat, M., and F. Sorrentino. 1996. Effect of large additions of Cd, Pb, Cr, Zn, to cement raw meal on the composition and the properties of the clinker and the cement. Cement and Concrete Research 26, no. 3:377-385. Peray, K. E. 1986. The Rotary Cement Kiln. 2d ed. New York: Chemical Publishing Company. Peray, K. E. 1979. Cement Manufacturer?s Handbook. New York: Chemical Publishing Company. Portland Cement Association (PCA). 2004. www.cement.org.au/environment/alternative_fuels_factsheet_right.htm. Accessed April 11, 2006. Skokie, Illinois: Portland Cement Association. Portland Cement Association (PCA). 2005. Tire-derived fuel. Sustainable Manufacturing Fact Sheet. Skokie, Illinois, Portland Cement Association. Prisciandaro, M., G. Mazziotti, and F. Vegli?. 2003. Effect of burning supplementary waste fuels on the pollutant emissions by cement plants: A statistical analysis of process data. Resources, Conservation and Recycling 39, no. 2:161-184. Redmond,S. 2006. An experimental wood chip furnace, Vermont Heat Research 276 Ritzmann, H. 1971. Cyclic phenomena in rotary kiln systems. Zement-Kalk-Gips 24, no. 8:338-343. Romeu, J.L. 2003. Anderson-Darling: A Goodness of Fit Test for small samples assumptions, START Volume 10, Number 5. Sami, M. , K. Annamalai, and, M. Wooldridge. 2001. Co-firing of coal and biomass fuel blends, Progress in Energy and Combustion Science 27 (2001) 171?214 Schindler, A.K. and Folliard, K. J. 2005. Heat of hydration models for cementitious materials. ACI Materials Journal. Schmidthals, H. 2003. The pre-combustion chamber for secondary fuels ? development status of a new technology. (paper presented at Cement Industry Technical Conference, 2003). IEEE-IAS/PCA. Schuhmacher, M., J. L. Domingo, and J. Garreta. 2004. Pollutants emitted by a cement plant: Health risks for the population living in the neighborhood. Environmental Research 95, no. 2:198-206. Shoaib, M. M., M. M. Balaha, and A. G. Abdel-Rahman. Influence of cement kiln dust substitution on the mechanical properties of concrete. Cement and Concrete Research 30, no. 3:371-377. Stephan, D., R. Mallmann, D. Kn?fel, and R. H?rdtl. 2000. High intakes of Cr, Ni, and Zn in clinker Part I. Influence on burning process and formation of phases. Cement and Concrete Research 29, no. 12:1949-1957. Stephan, D., R. Mallmann, D. Kn?fel, and R. H?rdtl. 2000. High intakes of Cr, Ni, and Zn in clinker Part II. Influence on the hydration properties. Cement and Concrete Research 29, no. 12:1959-1967. 277 Steuch, H. E. 2004. Clinker Coolers. Chap. 3.8 in Innovations in Portland Cement Manufacturing. Skokie, Illinois: Portland Cement Association. Swart, D.W. 2007. The Utilization of Alternative Fuels in the Production of Portland Cement, M.S. Thesis, Auburn University, Alabama Taylor, H. F. W. 1997. Cement Chemistry. 2d ed. London: Thomas Telford. Teislev, B. ,2002, Harboore ? Woodchips updraft gasifier and 1500 KW gas engines operating at 32% efficiency in CHP configuration, Babcock & Wilcox Volund R&D Center. Todres, H. A., A. Mishulovich, and J. Ahmed. 1992. Cement kiln dust management: Permeability. Skokie, Illinois: Portland Cement Association. Serial Number 1907. Trezza, M. A., and A. N. Scian. 2000. Burning wastes as an industrial resource: Their effect on portland cement clinker. Cement and Concrete Research 30, no. 1:137- 144. Walters, L. J. Jr., M. S. May III, D. E. Johnson, R. S. Macmann, and W.A. Woodward. 1999. Time-variability of NO x emissions from portland cement kilns. Environmental Science & Technology 33, no. 5:700-704. Weisweiler, W., and W. Kr?mar. 1989. Arsenic and antimony balances of a cement kiln plant with grate preheater Zement-Kalk-Gips, no. 3:133. Wilen, C., A. Moilanen, and E. Kurkula. 1996. Biomass feedstock analyses VTT Publications 282.( Phyllis database) Wurst, F. and T. Prey. 2002. Alternative Fuels in the Cement Industry. PMT- Zyclontechnik GmbH. Krems: Austria. 278 Young, G. L. 2002. NO x formation in rotary kilns producing cement clinker: Applicable NO x control techniques and cost effectiveness of these control techniques. (paper presented at Cement Industry Technical Conference, 2002). IEEE-IAS/PCA. APPENDIX A: TEST PROCEDURE Table A.1: Analyzing the Chemical Composition of the Raw Materials Item # Material Analyzed Test Sampling Frequency Specimen Preparation Method Sampling Period Tested by Routine? 1 Raw Material One Standard Cement Plant Parameters (Table A.8) 1 1 / burn Discrete During Each Burn Cement Plant Yes 2 Raw Material Two 3 Raw Material Three 3 4 Raw Material Four 5 Raw Material Five 6 Raw Material One Standard External Lab Parameters (Table A.10) 1 / burn Discrete During Each Burn External Lab No 7 Raw Material Two 8 Raw Material Three 3 9 Raw Material Four 10 Raw Material Five 11 Kiln Feed (Raw Material Seven) Standard Cement Plant Parameters (Table A.8) 2 2 / day Discrete Standard Sampling Period Cement Plant Yes 12 Kiln Feed (Raw Material Seven) Standard External Lab Parameters (Table A.10) 2 / day 3-Day Composites Standard Sampling Period External Lab No 13 Raw Material Six Standard Cement Plant Parameters (Table A.8) 1 1 / burn Discrete During Each Grinding Period Cement Plant Yes 14 Raw Material Six Standard External Lab Parameters (Table A.10) 1 / burn 3-Day Composites During Each Grinding Period External Lab No 279 Notes: 1 Na 2 O eq is not collected 2 Moisture is not collected 3 Moisture and LOI is not collected Table A.2.a: Analyzing the Chemical Composition of Fuels Item # Material Analyzed Test Sampling Frequency Specimen Preparation Method Sampling Period Tested by Routine? 1 Pulverized Coal Proximate Analysis (Table A.9) 2 / day 3-Day Composites Standard Sampling Period Cement Plant Yes 2 Pulverized Coal Ultimate Analysis (Table A.9) Cement Plant Yes 3 Pulverized Coal Standard Cement Plant Parameters (Table A.8) 1 Cement Plant Yes 4 Pulverized Coal Combustion Analysis (Table A.9) Cement Plant Yes 5 Pulverized Coal Proximate Analysis (Table A.9) 2 / day 3-Day Composites Standard Sampling Period External Lab No 6 Pulverized Coal Ultimate Analysis (Table A.9) External Lab No 7 Pulverized Coal Standard External Lab Parameters (Table A.10) 2 External Lab No 8 Pulverized Coal Combustion Analysis (Table A.9) External Lab No 280 Notes: 1 Moisture, LOI, and Na 2 O eq is not collected 2 Moisture is not collected Table A.2.b: Analyzing the Chemical Composition of Fuels Item # Material Analyzed Test Sampling Frequency Specimen Preparation Method Sampling Period Tested by Routine? 1 Tires Proximate Analysis (Table A.9) 1 / burn One Composite Sample Prepared from 8 Discrete Radial Section Samples Removed from Random Tires During Each Burn 2 External Lab No 2 Tires Ultimate Analysis (Table A.9) External Lab No 3 Tires Standard External Lab Parameters (Table A.10) 1 External Lab No 4 Tires Combustion Analysis (Table A.9) External Lab No 5 Plastics Proximate Analysis. (Table A.9) 8 / day Discrete (Every Fourth Sample Analyzed in Duplicate) During Burn CTP External Lab No 6 Plastics Ultimate Analysis (Table A.9) External Lab No 7 Plastics Standard External Lab Parameters (Table A.10) 1 External Lab No 8 Plastics Combustion Analysis (Table A.9) External Lab No 281 Notes: 1 To be determined for both the fuel and the fuel?s ash after combustion 2 Tires are not collected during the coal only burn period Table A.2.c: Analyzing the Chemical Composition of Fuels Item # Material Analyzed Test Sampling Frequency Specimen Preparation Method Sampling Period Tested by Routine? 9 Broiler Litter Proximate Analysis (Table A.9) 8 / day Discrete (Every Fourth Sample Analyzed in Duplicate) During Burn CTB External Lab No 10 Broiler Litter Ultimate Analysis (Table A.9) External Lab No 11 Broiler Litter Standard External Lab Parameters (Table A.10) 1 External Lab No 12 Broiler Litter Combustion Analysis (Table A.9) External Lab No 13 Woodchips Proximate Analysis (Table A.9) 8 / day Discrete (Every Fourth Sample Analyzed in Duplicate) During Burn CTW External Lab No 14 Woodchips Ultimate Analysis (Table A.9) External Lab No 16 Woodchips Standard External Lab Parameters (Table A.10) 1 External Lab No 17 Woodchips Combustion Analysis (Table A.9) External Lab No 282 Notes: 1 To be determined for both the fuel and the fuel?s ash after combustion Table A.2.d: Analyzing the Chemical Composition of Fuels Item # Material Analyzed Test Sampling Frequency Specimen Preparation Method Sampling Period Tested by Routine? 18 Switchgrass Proximate Analysis (Table A.9) 8 / day Discrete (Every Fourth Sample Analyzed in Duplicate) During Burn CTS External Lab No 19 Switchgrass Ultimate Analysis (Table A.9) External Lab No 20 Switchgrass Standard External Lab Parameters (Table A.10) 1 External Lab No 21 Switchgrasss Combustion Analysis (Table A.9) External Lab No 283 Table A.3: Analyzing the Chemical Composition of Cement Kiln Dust (CKD) Item # Test Sampling Frequency Specimen Preparation Method Sample Period Tested by Routine? 1 Standard Cement Plant Parameters (Table A.8) 1 2 / day Discrete Standard Sampling Period Cement Plant Yes 2 Standard External Lab Parameters (Table A.10) 2 / day Discrete Standard Sampling Period External Lab No Notes: 1 Na 2 O eq , Moisture, and LOI are not collected Table A.2: Analyzing the Chemical Composition of Clinker Item # Test Specification Sampling Frequency Specimen Preparation Method Sampling Period Tested by Routine? 1 Chemical Composition: Standard Cement Plant Parameters (Table A.8) 1 XRF 12 / day Discrete Standard Sampling Period Cement Plant Yes 2 Additional Chemical Composition: Free CaO ASTM C 114 12 / day Discrete Cement Plant Yes 3 Clinker Phase Composition: C 3 S, C 2 S, C 3 A, C 4 AF ASTM C 150 N/A N/A N/A Cement Plant Yes 4 Clinker Phase Composition: C 3 S, C 2 S, C 3 A, C 4 AF Rietveld Analysis 12 / day 1-Day Composites Standard Sampling Period Cement Plant Specialty Lab No 5 Trace Element Content of Clinker: Standard External Lab Parameters (Table A.10) XRF External Lab No 284 Notes: 1 Moisture and LOI are not collected Table A.3: Analyzing the Chemical Composition of Cement Item # Test Specification Sampling Frequency Specimen Preparation Method Sampling Period Tested by Routine? 1 Chemical Composition: Standard Cement Plant Parameters (Table A.8) 1 XRF 8 / day Discrete Standard Sampling Period Cement Plant Yes 2 Additional Chemical Composition: Free CaO Blaine Specific Surface Area ASTM C 114 ASTM C 204 8 / day Discrete Cement Plant Yes 3 Clinker Phase Composition: C 3 S, C 2 S, C 3 A, C 4 AF ASTM C 150 N/A N/A Cement Plant Yes 4 Clinker Phase Composition: C 3 S, C 2 S, C 3 A, C 4 AF Rietveld Analysis 8 / day 1-Day Composites Cement Plant Specialty Lab No 5 Chemical Composition: Standard Cement Plant Parameters (Table A.8) 2 XRF 8 / day 1-Day Composites Cement Plant Yes 6 Trace Element Content of Cement: Standard External Lab Parameters (Table A.10) XRF 8 / day 1-Day Composites External Lab No 7 Additional Chemical Analysis: Total organic carbon (TOC) TOC Analyzer 8 / day 1-Day Composites External Lab No 285 Notes: 1 Moisture is not collected. 2 Moisture is not collected. FCaO is collected Table A.4: Analyzing the Physical Properties of Cement Item # Test Specification Sampling Frequenc y Specimen Preparation Method Sampling Period Tested by Routine? 1 Standard Physical Properties: Air content of mortar (%) Blaine specific surface area (m 2 /kg) ASTM C 185 ASTM C 204 8 / day 1-Day Composites Standard Sampling Period ) Cement Plant Yes 2 Standard Physical Properties: Normal Consistency (%) Autoclave expansion (%) Compressive strength (MPa): 1, 3, 7, 28 days Cube Flow (%) Gillmore Test: Initial and Final Set Times Vicat Test: Initial and Final Set Times ASTM C 187 ASTM C 151 ASTM C 109 ASTM C 230 ASTM C 266 ASTM C 191 8 / day 1-Day Composites 1 Standard Sampling Period Cement Plant, and Auburn University Yes 4 Additional Physical Properties: Particle Size Distribution Heat of hydration (kJ/kg): 7 and 28 days Laser Diffraction ASTM C 186 8 / day 1-Day Composites Standard Sampling Period Cement Plant Specialty Lab No 5 Additional Physical Properties: Drying Shrinkage of Mortar Prisms (%): 4, 11, 18, and 25 days ASTM C 596 8 / day 3-Day Composites Standard Sampling Period Auburn University No 286 Notes: 1 Auburn University conducts these tests on one three-day composite sample during each burn period Table A.5: Analyzing the Properties of Concrete to be Conducted by Auburn University and the Cement Plant Item # Test Specification Material Type Concrete Age (days) Sampling Frequency Sample Method 1 Fresh Properties: Total Air Content Slump Setting Time Unit Weight ASTM C 231 ASTM C 143 ASTM C 403 ASTM C 138 Concrete Concrete Mortar Concrete Fresh State Fresh State Early-age Fresh State 8 / day Single Composite Over Entire Burn Phase 2 Physical Properties: Compressive strength Splitting Tensile Strength 1 Drying Shrinkage Development Heat of Hydration Under Semi- Adiabatic Conditions 1 ASTM C 39 ASTM C 496 ASTM C 157 RILEM 119-TCE Concrete Concrete Concrete Concrete 1, 3, 7, 28, 91 1, 3, 7, 28, 91 4 to 448 0.1 to 7 3 Durability: Permeability (RCPT) ASTM C 1202 Concrete 91 Notes: 287 1 Test conducted by the cement plant Two standard concrete mixtures developed to evaluate the response of the cement: (A) Cement only, w/c = 0.44 (For AEA) (B) Cement only, w/c = 0.37 (For AEA and Type F Admixtures) Table A.6: Analyzing Emissions Item # Material Analyzed Test Spec. Sampling Frequency Specimen Preparation Method Data Collection Period Tested by Routine? 1 Main Stack Emissions CO NO x SO 2 VOC CEMS Continuous Real - Time Standard Emissions Sampling Frequency Cement Plant Yes 288 Table A.7: ASTM Methods Method Number Method Title C39 Standard Test Method for Compressive Strength of Cylindrical Concrete Specimens C109 Standard Test Method for Compressive Strength of Hydraulic Cement Mortars (Using 2-in. or [50-mm] Cube Specimens) C151 Standard Test Method for Autoclave Expansion of Hydraulic Cement C157 Standard Test Method for Length Change of Hardened Hydraulic-Cement, Mortar, and Concrete C185 Standard Test Method for Air Content of Hydraulic Cement Mortar C186 Standard Test Method for Heat of Hydration of Hydraulic Cement C191 Standard Test Method for Time of Setting of Hydraulic Cement by Vicat Needle C204 Standard Test Method for Fineness of Hydraulic Cement by Air Permeability Apparatus C230 Standard Specification for Flow Table for Use in Tests of Hydraulic Cement C231 Standard Test Method for Air Content of Freshly Mixed Concrete by the Pressure Method C266 Standard Test Method for Time of Setting of Hydraulic-Cement Paste by Gillmore Needles C403 Standard Test Method for Time of Setting of Concrete Mixtures by Penetration Resistance C496 Standard Test Method for Splitting Tensile Strength of Cylindrical Concrete Specimens C596 Standard Test Method for Drying Shrinkage of Mortar Containing Hydraulic Cement C1202 Standard Test Method for Electrical Indication of Concrete's Ability to Resist Chloride Ion Penetration 289 290 Table A.8: Standard Cement Plant Parameters Parameter Analysis Technique Al 2 O 3 ASTM C 114 and XRF CaO Fe 2 O 3 K 2 O MgO Na 2 O Na 2 O eq SiO 2 SO 3 Loss On Ignition ASTM C 114 Moisture Table A.9: Fuel Test Parameters Table A.10: Standard External Lab Parameters Test Parameter Proximate Analysis Volatile Matter, Fixed Carbon, Percent Ash, Percent Moisture Ultimate Analysis Carbon, Hydrogen, Oxygen, Sulfur, Nitrogen Combustion Analysis Energy Content Parameter Analysis Technique Al 2 O 3 ASTM C 114 and XRF CaO Fe 2 O 3 K 2 O MgO Na 2 O P 2 O 5 SiO 2 SO 3 TiO 2 As Ba Cd Cl Co Cr Cu Hg Mn Mo Ni Pb Sb Se Sr V Zn Loss On Ignition ASTM C 114 Moisture Table A.11: Abbreviations Abbreviation Definition % NC % Normal Consistency AEA Air entraining agent ASTM American Society for Testing and Materials C 2 S Dicalcium silicate C 3 A Tricalcium aluminate C 3 S Tricalcium silicate C 4 AF Tetracalcium aluminoferrite CEMS Continuous emissions monitoring system CKD Cement kiln dust LOI Loss on ignition RCPT Rapid chloride permeability test T Alkalis Total alkalis TOC Total organic carbon VOC Volatile organic compounds XRF X-ray fluorescence 291 335 APPENDIX B.3 RAW DATA FOR CTP BURN B.3.1. GENERAL COMMENTS ? The raw data from the CTP burn are presented in this appendix. ? Coal, scrap tires, and waste plastics are the fuels used in the burn ? The burn period lasted from 7 AM on April 3, 2007 to 7 AM April 6, 2007. B.3.2. NOTATION CPR ? Cement Plant Results ELR ? External Lab Results AUR ? Auburn University Results C. V. ? Coefficient of Variation B.3.3. CHEMICAL COMPOSITION OF RAW MATERIALS 336 Property (wt. %) Raw Material On Material Five Raw Material Six Al 2 O 3 23.22 0.39 2.98 7.60 1.14 2.62 CaO 4.27 52.85 41.59 38.10 1.66 32.57 Fe 2 O 3 14.41 0.00 1.30 14.50 1.63 0.25 K 2 O 2.15 0.07 0.26 0.05 0.28 0.25 MgO 2.21 0.97 3.29 12.90 0.19 3.15 Na 2 O 0.42 0.03 0.10 NR NR 0.20 SiO 2 43.03 2.04 13.77 24.60 95.90 13.56 SO 3 0.13 0.10 0.15 0.41 0.21 34.95 Moisture 34.60 3.00 NR 6.50 3.40 10.40 LOI 7.10 43.20 NR 0.10 0.40 11.40 Notes: NC - Not Collected NR - Not Reported Table B.3.1: CPR - Chemical Composition of Raw Materials e Raw Material Two Raw Material Three Raw Material Four Raw Table B.3.2: ELR - Chemical Composition of Raw Materials 337 ND - Not Detected Property Raw Material One Raw Material Two Raw Material Three Raw Material Four Raw Material Five Raw Material Six Al 2 O 3 (wt. %) 26.87 0.87 8.09 4.27 1.00 2.71 CaO (wt. %) 3.20 91.85 43.79 29.01 0.41 38.80 Fe 2 O 3 (wt. %) 12.35 0.47 3.56 34.03 0.59 0.50 K 2 O (wt. %) 2.69 0.14 0.69 0.20 0.17 0.26 MgO (wt. %) 1.52 3.04 1.86 12.16 0.18 2.78 Na 2 O (wt. %) 0.60 0.47 0.11 0.13 0.04 0.16 P 2 O 5 (wt. %) 0.63 0.01 0.04 0.47 0.00 0.03 SiO 2 (wt. %) 50.21 2.86 41.12 15.27 97.37 13.21 SO 3 (wt. %) 0.09 0.20 0.12 0.30 0.00 41.23 TiO 2 (wt. %) 1.37 0.00 0.43 0.25 0.20 0.10 Moisture (wt. %) 22.26 2.93 6.51 6.01 2.29 4.06 LOI (wt. %) 11.99 42.91 27.56 ND 0.35 18.06 As (ppm) 299 6 23 4 4 < 2 Ba (ppm) 2000 2000 3000 2000 2000 3000 Cd (ppm) ND ND ND ND ND ND Cl (ppm) 25 29 34 100 13 30 Co (ppm) 64 12 15 4 5 7 Cr (ppm) 203 16 54 3249 9 32 Cu (ppm) 219 18 46 61 33 < 10 Hg (ppm) ND ND ND ND ND ND Mn (ppm) 1000 3000 12000 38700 2000 12000 Mo (ppm) 40 12 13 90 23 23 Ni (ppm) 122 14 16 75 < 5 5 Pb (ppm) 195 4 27 21 9 23 Sb (ppm) ND ND ND ND ND ND Se (ppm) ND ND ND ND ND ND Sr (ppm) 1800 400 400 200 100 800 V (ppm) 325 17 74 604 20 18 Zn (ppm) 363 26 52 198 2 8 Notes: B.3.4. CHEMICAL COMPOSITION OF KILN FEED Table B.3.3: CPR - Chemical Composition of Kiln Feed 338 4:52 AM 1:54 PM 1:32 AM 1:40 PM 1:40 AM 1:46 PM 1:43 AM Al 2 O 3 2.97 2.95 3.03 3.13 3.04 2.96 3.05 3.02 2.1 0.386 CaO 43.53 43.48 43.52 43.6 43.85 44.11 44.11 43.74 0.6 2 0.078 Fe 2 O 3 1.96 1.84 1.77 1.98 1.96 1.91 1.9 1.90 4.0 0.356 K 2 O 0.29 0.28 0.29 0.29 0.29 0.28 0.29 0.29 1.7 2 <0.005 MgO 2.06 2.11 2.01 2.18 2.1 2.03 2.03 2.07 2.9 0.440 Na 2 O 0.05 0.04 0.05 0.05 0.03 0.05 0.04 0.04 17.8 2 0.021 Na 2 O eq 0.24 0.22 0.24 0.24 0.22 0.23 0.23 0.23 3.9 2 0.091 SiO 2 13.83 13.88 13.83 13.74 13.47 13.52 13.41 13.67 1.4 0.156 SO 3 0.11 0.11 0.08 0.11 0.14 0.14 0.13 0.12 18.3 0.223 LOI 34.9 34.9 35 34.4 34.4 34.8 34.7 34.73 0.7 0.183 Notes: NC - Not Collected 1 Based on Anderson-Darling Normality Test NA - Not Applicable 2 Data not normally distributed C. V. (%) Normality P-Value 1 Property (wt. %) 4/3/2007 Average 4/4/2007 4/5/2007 Table B.3.4: ELR - Chemical Composition of Kiln Feed 339 NR - Not Reported Property 3-Day Composite Al 2 O 3 (wt. %) 4.91 CaO (wt. %) 65.27 Fe 2 O 3 (wt. %) 3.01 K 2 O (wt. %) 0.50 MgO (wt. %) 3.35 Na 2 O (wt. %) 0.02 P 2 O 5 (wt. %) 0.07 SiO 2 (wt. %) 21.87 SO 3 (wt. %) 0.34 TiO 2 (wt. %) 0.24 Moisture (wt. %) 0.10 LOI (wt. %) 34.67 As (ppm) 18 Ba (ppm) 400 Cd (ppm) NR Cl (ppm) 63 Co (ppm) 14 Cr (ppm) 86 Cu (ppm) 41 Hg (ppm) NR Mn (ppm) 1700 Mo (ppm) 16 Ni (ppm) 12 Pb (ppm) < 4 Sb (ppm) NR Se (ppm) NR Sr (ppm) 500 V (ppm) 73 Zn (ppm) 37 Notes: B.3.5. CHEMICAL COMPOSITION OF FUELS Table B.3.5: CPR - Chemical Composition of Coal 340 Notes: 1 Value is Reported as BTU/lb Test Parameter Value (wt. %) Ash 23.43 Fixed Carbon 48.43 Volatile Matter 28.14 Carbon 64.41 Hydrogen 4.01 Nitrogen 1.31 Oxygen 3.05 Sulfur 3.79 Al 2 O 3 15.43 CaO 3.23 Fe 2 O 3 36.24 K 2 O 1.94 MgO 1.04 Na 2 O 0.36 SiO 2 36.17 SO 3 4.40 11255Heat Value 1 Proximat e Analysis Ul timate An alysis St a ndar d Par a m e t e r s Table B.3.6: ELR - Proximate, Ultimate, and Combustion of Coal Test Parameter Value (wt. %) Ash 24.54 Fixed Carbon 47.68 Volatile Matter 27.78 Carbon 64.68 Hydrogen 3.93 Nitrogen 1.08 Oxygen 4.11 Sulfur 1.66 11369 Notes: 1 Value is Reported as BTU/lb Proximat e Analysis Ulti mate Analysis Heat Value 1 341 Table B.3.7: ELR - Standard Parameters of Coal 342 ND - Not Detected Property 3-Day Composite Al 2 O 3 (wt. %) 21.04 CaO (wt. %) 8.25 Fe 2 O 3 (wt. %) 15.16 K 2 O (wt. %) 2.49 MgO (wt. %) 1.25 Na 2 O (wt. %) 0.36 P 2 O 5 (wt. %) 0.23 SiO 2 (wt. %) 43.44 SO 3 (wt. %) 6.50 TiO 2 (wt. %) 0.96 As (ppm) 316 Ba (ppm) 1300 Cd (ppm) 5 Cl (ppm) 134 Co (ppm) 44 Cr (ppm) 117 Cu (ppm) 103 Hg (ppm) 0.022 Mn (ppm) 1500 Mo (ppm) 39 Ni (ppm) 92 Pb (ppm) 45 Sb (ppm) NR Se (ppm) 1 Sr (ppm) 500 V (ppm) 214 Zn (ppm) 197 Notes: Table B.3.8: ELR - Proximate, Ultimate, and Combustion Analysis of Tires Test Parameter Value (wt. %) Ash 14.56 Fixed Carbon 26.38 Moisture 1 0.07 Volatile Matter 59.06 Carbon 75.94 Hydrogen 6.52 Nitrogen 0.52 Oxygen 0.46 Sulfur 2.00 14687 Notes: 1 As Received 2 Value is Reported as BTU/lb Ul ti mate Analysis Heat Value 2 P r oximate Analysis 343 Table B.3.9: ELR - Standard Parameters of Tires 344 NR - Not Reported Property 3-Day Composite Al 2 O 3 (wt. %) 1.15 CaO (wt. %) 1.68 Fe 2 O 3 (wt. %) 84.72 K 2 O (wt. %) 0.17 MgO (wt. %) 0.33 Na 2 O (wt. %) 0.19 P 2 O 5 (wt. %) 0.12 SiO 2 (wt. %) 4.91 SO 3 (wt. %) 0.51 TiO 2 (wt. %) 0.56 As (ppm) 5 Ba (ppm) 300 Cd (ppm) 3 Cl (ppm) NR Co (ppm) 536 Cr (ppm) 178 Cu (ppm) 900 Hg (ppm) <0.001 Mn (ppm) 5200 Mo (ppm) 23 Ni (ppm) 239 Pb (ppm) 13 Sb (ppm) NR Se (ppm) <1 Sr (ppm) 100 V (ppm) 50 Zn (ppm) 48400 Notes: Table B.3.10: ELR - Proximate, Ultimate, and Combustion Analysis of Plastics Test Parameter Value (wt. %) Ash 8.75 Fixed Carbon 2.95 Moisture 1 0.32 Volatile Matter 88.30 Carbon 65.25 Hydrogen 8.21 Nitrogen 1.27 Oxygen 17.46 Sulfur 0.22 12754 Notes: 1 As Received 2 Value is Reported as BTU/lb Ul ti mate Analysis Heat Value 2 P r oximate Analysis 345 Table B.3.11: ELR - Standard Parameters of Plastics 346 NR - Not Reported Property 3-Day Composite Al 2 O 3 (wt. %) 0.48 CaO (wt. %) 92.00 Fe 2 O 3 (wt. %) 0.54 K 2 O (wt. %) 0.13 MgO (wt. %) 1.75 Na 2 O (wt. %) 0.17 P 2 O 5 (wt. %) 0.14 SiO 2 (wt. %) 2.12 SO 3 (wt. %) 0.41 TiO 2 (wt. %) 1.77 As (ppm) 62 Ba (ppm) 4093 Cd (ppm) 7 Cl (ppm) 54 Co (ppm) 142 Cr (ppm) 356 Cu (ppm) 369 Hg (ppm) <0.001 Mn (ppm) 283 Mo (ppm) 6 Ni (ppm) 50 Pb (ppm) 628 Sb (ppm) NR Se (ppm) NR Sr (ppm) 593 V (ppm) 66 Zn (ppm) 283 Notes: ND - Not Detected 347 Table B.3.12: AUR - Density of Plastics Sample # Density (kg/m 3 ) 1 95.1 2 101.3 3 112.7 4 94.5 5 91.1 6 87.7 7 81.1 8 96.0 9 87.2 10 68.3 11 69.1 12 94.4 13 94.7 14 91.7 15 74.0 16 79.7 17 77.6 18 71.2 19 83.1 20 72.6 21 74.5 22 80.3 23 73.4 24 72.5 Average 84.3 B.3.6. CHEMICAL COMPOSITION OF CEMENT KILN DUST (CKD) Table B.3.13: CPR - Chemical Composition of Cement Kiln Dust 4/5/2007 8:24 AM 7:38 PM 7:56 AM 7:39 PM 9:32 AM 1:47 AM 6:15 AM Al 2 O 3 4.03 4.21 4.08 3.04 3.11 3.49 3.62 3.65 CaO 43.36 45.18 47.41 51 51.41 48.59 46.49 47.63 Fe 2 O 3 1.93 1.93 1.76 1.55 1.56 1.68 1.75 1.74 K 2 O 0.4 0.4 0.37 0.34 0.42 0.39 0.37 0.38 MgO 1.19 1.96 2.25 1.8 2.48 1.67 1.31 1.81 Na 2 O 0.03 0.07 0.07 0.05 0.06 0.05 0.03 0.05 SiO 2 12.4 13.43 14.15 9.67 9.34 10.61 11.37 11.57 SO 3 0.36 0.57 0.64 0.8 2.43 0.88 0.24 0.85 4/3/2007 4/6/2007 AverageProperty (wt. %) 4/4/2007 348 Table B.3.14: ELR - Chemical Composition of Cement Kiln Dust 349 ND - Not Detected 8:24 AM 7:38 PM 7:56 AM 7:39 PM 9:32 AM 1:47 AM Al 2 O 3 (wt. %) 6.33 5.82 4.86 3.96 4.63 5.09 5.12 CaO (wt. %) 67.34 68.92 72.99 76.21 74.05 72.57 72.01 Fe 2 O 3 (wt. %) 2.88 2.95 2.47 2.23 2.41 2.51 2.58 K 2 O (wt. %) 0.42 0.57 0.49 0.41 0.45 0.46 0.47 MgO (wt. %) 1.99 2.42 2.73 3.16 2.66 2.30 2.54 Na 2 O (wt. %) 0.11 0.08 0.08 0.06 0.06 0.09 0.08 P 2 O 5 (wt. %) 0.11 0.08 0.06 0.04 0.04 0.06 0.07 SiO 2 (wt. %) 19.66 17.53 14.52 12.34 14.27 15.92 15.71 SO 3 (wt. %) 0.62 1.10 1.43 1.26 1.05 0.61 1.01 TiO 2 (wt. %) 0.36 0.30 0.22 0.18 0.22 0.23 0.25 Moisture (wt. %) 0.11 0.14 0.13 0.12 0.16 0.16 0.14 LOI (wt. %) 35.44 34.49 32.21 29.67 32.62 35.09 33.25 As (ppm) 32 31 23 33 27 30 29 Ba (ppm) 400 500 300 300 300 200 333 Cd (ppm) NR NR NR NR NR NR NA Cl (ppm) 80 124 213 137 115 115 131 Co (ppm) 13 14 18 8 13 12 13 Cr (ppm) 62 77 44 37 50 54 54 Cu (ppm) 85 38 54 43 21 41 47 Hg (ppm) NR NR NR NR NR NR NA Mn (ppm) 900 1200 800 700 800 900 883 Mo (ppm) 13 27 15 12 21 9 16 Ni (ppm) 15 25 10 10 16 10 14 Pb (ppm) 29 25 33 15 < 4 6 22 Sb (ppm) NR NR NR NR NR NR NA Se (ppm) NR NR NR NR NR NR NA Sr (ppm) 600 600 500 500 500 500 533 V (ppm) 82 75 61 44 57 67 64 Zn (ppm) 54 47 31 28 32 37 38 Notes: NA - Not Applicable Property 4/3/2007 4/4/2007 4/5/2007 Average B.3.7. CHEMICAL COMPOSITION OF CLINKER Table B.3.15: CPR - Chemical Composition of Clinker for 4/3/07 and 4/4/07 7:50 AM 9:30 AM 11:50 AM 1:51 PM 4:47 PM 5:30 PM 7:37 PM 9:35 PM 11:35 PM 1:34 AM 3:35 AM 6:09 AM 7:56 AM 10:03 AM 11:41 AM 1:40 PM 3:56 PM 5:57 PM 7:39 PM 9:57 PM 11:37 PM Al 2 O 3 5.08 5.24 5.15 5.22 5.32 5.10 5.13 5.07 5.12 5.16 5.21 5.16 5.18 5.21 5.19 5.22 5.24 5.14 5.13 4.70 5.39 CaO 64.39 64.22 64.44 64.47 64.20 64.69 64.38 64.07 64.44 64.28 64.08 64.21 64.07 64.36 64.41 64.50 64.51 64.57 64.70 63.26 64.40 Fe 2 O 3 3.50 3.53 3.38 3.40 3.42 3.24 3.27 3.31 3.28 3.30 3.28 3.24 3.33 3.34 3.48 3.55 3.67 3.73 3.67 3.24 3.92 K 2 O 0.43 0.45 0.48 0.45 0.47 0.45 0.50 0.46 0.41 0.44 0.47 0.47 0.45 0.47 0.43 0.44 0.51 0.47 0.45 0.46 0.47 MgO 3.27 3.24 3.24 3.25 3.23 3.24 3.19 3.14 3.20 3.19 3.18 3.19 3.21 3.30 3.34 3.38 3.46 3.43 3.42 2.98 3.42 Na 2 O 0.07 0.07 0.08 0.07 0.07 0.07 0.08 0.07 0.06 0.07 0.07 0.07 0.07 0.07 0.06 0.07 0.07 0.07 0.07 0.07 0.07 Na 2 O eq 0.35 0.37 0.39 0.37 0.38 0.37 0.41 0.37 0.33 0.36 0.38 0.38 0.36 0.38 0.35 0.36 0.41 0.38 0.37 0.37 0.38 SiO 2 21.57 21.43 21.48 21.57 21.45 21.51 21.47 21.30 21.42 21.39 21.37 21.27 21.32 21.41 21.48 21.56 21.51 21.52 21.51 20.22 21.37 SO 3 0.93 0.86 0.98 0.79 0.92 0.58 1.04 1.66 0.49 0.60 0.97 0.88 0.83 0.88 0.69 0.70 1.02 0.94 0.82 0.84 1.03 F CaO 0.33 0.58 1.05 0.75 2.24 1.74 1.68 1.57 0.97 1.10 1.52 1.22 0.86 1.10 0.88 0.58 0.72 0.55 1.10 1.46 0.97 C 3 A 7.50 7.90 7.90 8.10 8.30 8.00 8.10 7.80 8.00 8.10 8.30 8.20 8.10 8.20 7.90 7.80 7.70 7.30 7.40 7.00 7.70 C 4 AF 10.70 10.70 10.30 10.40 10.40 9.90 9.90 10.10 10.00 10.00 10.00 9.90 10.10 10.10 10.60 10.80 11.20 11.40 11.20 9.90 11.90 C 3 S 59.10 58.40 59.70 58.60 57.70 61.00 59.80 60.20 60.40 59.70 58.70 60.40 59.20 59.50 59.20 58.60 58.70 59.50 60.30 67.70 57.90 C 2 S 17.30 17.40 16.60 17.70 18.00 15.70 16.50 15.70 15.90 16.30 17.00 15.40 16.40 16.50 16.90 17.60 17.40 16.80 16.20 6.90 17.50 Property (wt. %) 4/3/2007 4/4/2007 Table B.3.16: CPR - Chemical Composition of Clinker for 4/5/07 and 4/6/07 350 3:43 AM 5:41 AM 7:26 AM 8:03 AM 9:51 AM 11:52 AM 1:46 PM 3:46 PM 5:55 PM 7:37 PM 10:32 PM 11:47 PM 1:42 AM 4:19 AM 5:37 AM Al 2 O 3 5.10 5.14 5.17 5.10 5.19 5.08 5.14 5.19 5.11 5.12 5.03 5.13 5.15 5.22 5.16 5.15 2.0 <0.005 CaO 64.79 64.80 64.77 64.78 64.83 64.88 64.99 64.88 64.98 64.91 65.05 64.97 64.89 64.95 64.88 64.56 0.6 0.039 Fe 2 O 3 3.67 3.70 3.90 3.80 3.76 3.81 3.63 3.70 3.72 3.74 3.70 3.81 3.73 3.80 3.83 3.57 6.1 <0.005 K 2 O 0.47 0.50 0.45 0.47 0.49 0.45 0.48 0.48 0.47 0.47 0.48 0.45 0.49 0.49 0.47 0.47 4.6 0.077 MgO 3.36 3.36 3.38 3.32 3.32 3.28 3.27 3.27 3.22 3.20 3.19 3.16 3.12 3.12 3.09 3.25 3.3 0.589 Na 2 O 0.07 0.08 0.07 0.08 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.07 5.8 <0.005 Na 2 O eq 0.39 0.40 0.36 0.38 0.39 0.37 0.39 0.39 0.38 0.38 0.38 0.37 0.39 0.40 0.37 0.38 4.4 0.053 SiO 2 21.35 21.19 21.38 21.41 21.12 21.36 21.24 21.22 21.06 21.22 21.22 21.21 21.07 20.98 21.02 21.31 1.2 <0.005 SO 3 1.01 1.07 0.75 0.95 0.98 0.90 0.93 1.09 0.94 0.94 0.97 0.87 1.04 1.11 1.06 0.92 21.1 <0.005 F CaO 1.82 1.96 0.97 0.97 1.88 0.64 1.88 1.44 2.24 1.68 1.27 0.55 1.68 1.52 1.19 1.24 41.0 0.374 C 3 A 7.30 7.40 7.10 7.10 7.40 7.00 7.50 7.50 7.20 7.30 7.10 7.20 7.30 7.40 7.20 7.62 5.4 0.021 C 4 AF 11.20 11.30 11.90 11.60 11.40 11.60 11.10 11.30 11.30 11.40 11.30 11.60 11.40 11.60 11.60 10.86 6.2 <0.005 C 3 S 62.00 62.90 60.90 61.30 63.10 62.20 63.40 62.70 64.80 63.20 64.50 63.40 64.10 64.50 64.20 61.15 3.9 0.033 C 2 S 14.50 13.30 15.40 15.10 12.90 14.30 13.00 13.50 11.50 13.10 12.20 13.00 12.10 11.50 11.80 14.97 16.4 0.007 Notes: 1 Based on Anderson-Darling Normality Test 2 Data not normally distributed Normality P-Value 1 AverageProperty (wt. %) C. V. (%) 4/5/2007 4/6/2007 Table B.3.17: ELR - Chemical Composition of Clinker Comp. 1 Comp. 2 Comp. 1 Comp. 2 Comp. 1 Comp. 2 Al 2 O 3 (wt. %) 4.87 5.01 5.13 5.03 4.84 4.90 4.96 CaO (wt. %) 64.78 64.73 64.16 64.63 65.03 64.93 64.71 Fe 2 O 3 (wt. %) 3.21 3.23 3.26 3.24 3.51 3.51 3.33 K 2 O (wt. %) 0.43 0.39 0.45 0.38 0.43 0.45 0.42 MgO (wt. %) 3.37 3.40 3.46 3.44 3.37 3.38 3.40 Na 2 O (wt. %) 0.19 0.10 0.09 0.07 0.09 0.07 0.10 P 2 O 5 (wt. %) 0.08 0.07 0.07 0.07 0.07 0.08 0.07 SiO 2 (wt. %) 21.46 21.71 21.90 21.76 21.08 21.14 21.51 SO 3 (wt. %) 1.11 0.87 0.97 0.87 1.05 1.02 0.98 TiO 2 (wt. %) 0.27 0.27 0.27 0.27 0.24 0.24 0.26 Moisture (wt. %) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 LOI (wt. %) 0.12 0.12 0.16 0.16 0.10 0.12 0.13 As (ppm) 34 40 39 36 30 34 36 Ba (ppm) 400 300 400 400 400 300 367 Cd (ppm) NR NR NR NR NR NR NA Cl (ppm) 129 140 273 177 188 154 177 Co (ppm) 14 13 10 11 12 13 12 Cr (ppm) 79 71 90 103 96 100 90 Cu (ppm) 22 34 27 32 29 21 28 Hg (ppm) NR NR NR NR NR NR NA Mn (ppm) 1500 1500 1600 1600 1900 2000 1683 Mo (ppm) 23 6 27 14281619 Ni (ppm) 18 10 21 8 26 9 15 Pb (ppm) 4619< 414112 Sb (ppm) NR NR NR NR NR NR NA Se (ppm) NR NR NR NR NR NR NA Sr (ppm) 500 500 500 500 500 500 500 V (ppm) 63 63 62 67 74 67 66 Zn (ppm) 64 60 70 75 66 72 68 Notes: NA - Not Applicable ND - Not Detected AverageProperty 4/3/2007 4/4/2007 4/5/2007 351 B.3.8. CHEMICAL COMPOSITION OF CEMENT Table B.3.18: CPR - Chemical Composition of Cement 352 7:07 AM 10:12 AM 11:34 AM 1:09 PM 2:39 PM 4:01 PM 6:43 PM 9:54 PM 1:13 AM 4:12 AM 11:53 AM Al 2 O 3 4.7 4.68 4.99 4.92 4.87 4.88 4.88 4.93 4.95 4.72 4.83 4.85 2.2 0.164 CaO 63.26 63.21 62.8 62.85 62.96 63.11 63.13 62.6 62.59 61.38 62.83 62.79 0.8 0.009 Fe 2 O 3 3.28 3.29 3.21 3.29 3.29 3.28 3.28 3.14 3.02 2.96 3.33 3.22 3.8 <0.005 K 2 O 0.44 0.45 0.43 0.44 0.43 0.45 0.42 0.43 0.45 0.45 0.45 0.44 2.5 0.021 MgO 3.2 3.19 3.26 3.23 3.2 3.24 3.24 3.28 3.28 3.07 3.19 3.22 1.8 0.095 Na 2 O 0.08 0.08 0.09 0.09 0.09 0.08 0.09 0.09 0.09 0.09 0.07 0.09 8.0 <0.005 Na 2 O eq 0.37 0.38 0.37 0.38 0.37 0.38 0.37 0.37 0.39 0.39 0.37 0.38 2.1 <0.005 SiO 2 20.54 20.55 20.82 20.66 20.57 20.51 20.56 20.65 20.84 20.06 20.8 20.60 1.0 0.049 SO 3 2.7 2.75 2.6 2.6 2.46 2.84 2.46 2.44 2.58 3.26 2.8 2.68 8.8 0.126 F CaO 1.44 1.44 NR 0.86 NR 1.38 1.46 1.1 1.41 1.79 1.63 1.39 19.6 0.183 LOI 1.27 1.29 0.97 1.26 NR 1.18 0.81 1.57 1.47 1.41 1.27 1.25 18.0 0.347 C 3 A 6.9 6.9 7.8 7.5 7.4 7.4 7.4 7.8 8 7.5 7.2 7.44 4.7 0.413 C 4 AF 10 10 9.8 10 10 10 10 9.6 9.2 9 10.1 9.79 3.8 <0.005 C 3 S 57.5 57.1 51.9 53.7 55.5 55.5 56.2 53.3 51.5 52.2 52.5 54.26 4.0 0.330 C 2 S 15.5 15.8 20.5 18.7 17.1 17 16.5 19 20.9 18.2 20 18.11 10.4 0.732 Blaine SSA (m 2 /kg) 366 357 332 408 345 395 357 365 379 379 372 369 5.9 0.927 Notes: 1 Based on Anderson-Darling Normality Test 2 Data not norm NC - Not Collected Property (wt. %) Average Normality P-Value 1 C. V. (%) 0074/9/2007 4/10/2 Table B.3.19: ELR - Chemical Composition of Cement 353 NR - Not Reported Property 4/9/2007 4/9/2007 4/10/2007 Average Al 2 O 3 (wt. %) 4.86 4.86 5.07 4.93 CaO (wt. %) 63.24 63.54 62.76 63.18 Fe 2 O 3 (wt. %) 2.94 3.24 3.15 3.11 K 2 O (wt. %) 0.43 0.40 0.39 0.41 MgO (wt. %) 3.40 3.46 3.56 3.47 Na 2 O (wt. %) 0.11 0.07 0.20 0.13 P 2 O 5 (wt. %) 0.07 0.06 0.06 0.06 SiO 2 (wt. %) 21.60 21.17 21.77 21.51 SO 3 (wt. %) 2.88 2.71 2.55 2.71 TiO 2 (wt. %) 0.26 0.26 0.26 0.26 Moisture (wt. %) 0.22 0.68 0.26 0.39 LOI (wt. %) 1.02 0.80 0.92 0.91 C 3 S (wt. %) -- -- -- 48.40 C 2 S (wt. %) -- -- -- 25.17 C 3 A (wt. %) -- -- -- 7.80 C 4 AF (wt. %) -- -- -- 9.46 TOC (wt. %) 0.08 0.03 0.04 0.05 As (ppm) 25 29 27 27 Ba (ppm) 300 300 300 300 Cd (ppm) NR NR NR NA Cl (ppm) 53 54 63 57 Co (ppm) 13 15 11 13 Cr (ppm) 78 104 95 92 Cu (ppm) 14 17 12 14 Hg (ppm) NR NR NR NA Mn (ppm) 1400 1800 1600 1600 Mo (ppm) < 1132 Ni (ppm) 10 14 12 12 Pb (ppm) 8 423027 Sb (ppm) NR NR NR NA Se (ppm) NR NR NR NA Sr (ppm) 500 500 500 500 V (ppm) 64 69 74 69 Zn (ppm) 65 67 55 62 Notes: NA - Not Applicable B.3.9. PHYSICAL PROPERTIES OF CEMENT Table B.3.20: CPR - Physical Properties of Cement 354 Vicat Fi 225 Notes: % Ex Property 4/9/2007 4/10/2007 Average Air in Mortar (%) 6.4 6.8 6.6 Blaine Specific Surface Area (m 2 /kg) 375 372 374 Autoclave Expansion (% Exp.) 0.18 0.19 0.18 Cube Flow (%) 119.0 126.0 122.5 Comp Str 1day (MPa) 13.1 14.0 13.6 Comp Str 3day (MPa) 21.5 22.8 22.2 Comp Str 7day (MPa) 30.7 30.6 30.7 Comp Str 28day (MPa) 42.6 42.9 42.8 Normal Consistency (%) 26.0 25.8 25.9 Gillmore Initial Set (Min) 105 90 98 Gillmore Final Set (Min) 255 270 263 Vicat Initial Set (Min) 65 58 62 nal Set (Min) 240 210 p. - % Expansion Table B.3.21: AUR - Physical Properties of Cement Property Composite Autoclave Expansion (% Exp.) 0.04 Cube Flow (%) 111 Comp Str 1day (MPa) 11.5 Comp Str 3day (MPa) 17.1 Comp Str 7day (MPa) 24.8 Comp Str 28day (MPa) 38.8 Normal Consistency (%) 26.2 Gillmore Initial Set (Min) 72 Gillmore Final Set (Min) 105 Vicat Initial Set (Min) 66 Vicat Final Set (Min) 115 Drying Shrinkage @ 7 days (% LC) -0.045 Drying Shrinkage @ 14 days (% LC) -0.069 Drying Shrinkage @ 21 days (% LC) -0.081 Drying Shrinkage @ 28 days (% LC) -0.089 Notes: % LC - Percent Length Change % Exp. - Percent Expansion B.3.10. PROPERTIES OF CONCRETE Table B.3.22: Concrete Properties CPR Mix w/c=0.44 Mix w/c=0.37 Mix w/c=0.44 Total Air Content (%) 4.0 5.0 CIP Slump (mm) 90.0 150 CIP Unit Weight (kg/m 3 ) 2464 2413 CIP Setting Time (Min) Initial Set Final Set 216 266 239 290 CIP CIP Compressive Strength (MPa) 1 day 3 days 7 days 28 days 91 days 14.0 23.1 28.5 39.0 CIP 22.3 33.1 38.0 51.0 CIP CIP CIP CIP CIP CIP Splitting Tensile Strength (MPa) 1 day 3 days 7 days 28 days 91 days 1.7 2.3 2.8 3.5 CIP 2.7 3.4 3.5 4.0 CIP NC NC NC NC NC Drying Shrinkage Development (% Length Change) 7 days 28 days 448 days -0.011 -0.029 CIP -0.018 -0.036 CIP NC NC NC Rapid Chloride Ion Penetration Test Electrical Conductance (Coulombs) 91 days 365 days CIP CIP CIP CIP CIP CIP Notes: CIP - Collection in Progress NC - Not Collected Property AUR AUR - Auburn University Result CPR - Cement Plant Result 355 B.3.11. EMISSIONS Table B.3.23: CPR - Emissions 356 4/5/2007 3:00 1.00E-03 3.10E-07 1.84E-05 5.36E-04 4/5/2007 4:00 1.23E-03 5.41E-07 2.24E-05 5.40E-04 4/5/2007 5:00 1.17E-03 3.85E-07 1.93E-05 5.65E-04 4/5/2007 6:00 1.11E-03 1.11E-07 1.64E-05 4.45E-04 Time NO x (tons/ton clinker) SO 2 (tons/ton clinker) VOC (tons/ton clinker) CO (tons/ton clinker) 4/3/2007 7:00 6.67E-04 4.81E-06 2.10E-05 3.69E-04 4/3/2007 8:00 7.83E-04 1.82E-06 2.11E-05 4.77E-04 4/3/2007 9:00 9.95E-04 5.92E-08 3.36E-05 6.71E-04 4/3/2007 10:00 1.06E-03 1.12E-07 3.80E-05 7.22E-04 4/3/2007 11:00 NC NC NC 5.71E-04 4/3/2007 12:00 NC NC NC 7.71E-04 4/3/2007 13:00 9.31E-04 NC 3.64E-05 7.09E-04 4/3/2007 14:00 1.10E-03 6.02E-08 4.43E-05 7.55E-04 4/3/2007 15:00 8.74E-04 4.60E-08 3.62E-05 6.31E-04 4/3/2007 16:00 1.11E-03 7.33E-08 4.73E-05 7.37E-04 4/3/2007 17:00 9.45E-04 5.31E-08 3.36E-05 5.75E-04 4/3/2007 18:00 9.60E-04 6.79E-08 3.09E-05 5.79E-04 4/3/2007 19:00 9.85E-04 NC 3.48E-05 6.75E-04 4/3/2007 20:00 1.16E-03 2.12E-08 3.62E-05 8.22E-04 4/3/2007 21:00 1.14E-03 NC 3.29E-05 7.44E-04 4/3/2007 22:00 9.86E-04 3.22E-07 2.57E-05 6.56E-04 4/3/2007 23:00 1.06E-03 2.37E-07 2.61E-05 7.54E-04 4/4/2007 0:00 9.55E-04 2.70E-07 2.35E-05 6.86E-04 4/4/2007 1:00 9.85E-04 3.15E-07 2.81E-05 7.92E-04 4/4/2007 2:00 1.21E-03 3.74E-07 2.79E-05 7.00E-04 4/4/2007 3:00 9.93E-04 3.11E-07 2.16E-05 6.69E-04 4/4/2007 4:00 1.00E-03 2.95E-07 2.42E-05 6.87E-04 4/4/2007 5:00 1.10E-03 4.36E-07 2.60E-05 6.54E-04 4/4/2007 6:00 6.20E-04 4.43E-07 1.26E-05 3.12E-04 4/4/2007 7:00 1.12E-03 9.63E-09 2.40E-05 7.65E-04 4/4/2007 8:00 1.02E-03 2.82E-08 2.67E-05 8.14E-04 4/4/2007 9:00 1.00E-03 1.58E-07 2.71E-05 6.37E-04 4/4/2007 10:00 1.00E-03 1.57E-07 2.70E-05 6.43E-04 4/4/2007 11:00 1.00E-03 1.14E-07 2.80E-05 5.58E-04 4/4/2007 12:00 1.04E-03 1.15E-07 2.78E-05 5.47E-04 4/4/2007 13:00 9.97E-04 8.75E-08 2.83E-05 5.45E-04 4/4/2007 14:00 9.78E-04 1.01E-07 3.05E-05 5.74E-04 4/4/2007 15:00 9.61E-04 1.08E-07 3.08E-05 5.88E-04 4/4/2007 16:00 1.10E-03 9.19E-08 3.31E-05 5.96E-04 4/4/2007 17:00 9.93E-04 1.07E-07 2.76E-05 5.42E-04 4/4/2007 18:00 9.82E-04 1.56E-07 2.45E-05 5.39E-04 4/4/2007 19:00 1.01E-03 1.28E-07 2.66E-05 6.14E-04 4/4/2007 20:00 9.22E-04 1.30E-07 2.33E-05 5.82E-04 4/4/2007 21:00 1.10E-03 1.43E-07 2.43E-05 6.17E-04 4/4/2007 22:00 9.83E-04 2.97E-07 2.10E-05 5.58E-04 4/4/2007 23:00 1.09E-03 2.44E-07 2.29E-05 5.48E-04 4/5/2007 0:00 9.28E-04 9.20E-08 1.99E-05 3.83E-04 4/5/2007 1:00 9.39E-04 1.20E-07 1.92E-05 4.90E-04 4/5/2007 2:00 1.09E-03 6.11E-07 2.10E-05 6.14E-04 357 Table B.3.24: CPR - Emissions Time NO x (tons/ton clinker) SO 2 (tons/ton clinker) VOC (tons/ton clinker) CO (tons/ton clinker) 4/5/2007 7:00 1.06E-03 1.16E-07 1.55E-05 4.21E-04 4/5/2007 8:00 9.97E-04 1.07E-07 1.97E-05 4.04E-04 4/5/2007 9:00 9.59E-04 1.30E-07 1.94E-05 3.93E-04 4/5/2007 10:00 1.04E-03 9.41E-08 2.14E-05 4.14E-04 4/5/2007 11:00 1.01E-03 2.02E-07 2.23E-05 4.48E-04 4/5/2007 12:00 1.09E-03 1.80E-07 2.30E-05 4.47E-04 4/5/2007 13:00 1.04E-03 1.23E-07 2.29E-05 3.64E-04 4/5/2007 14:00 1.03E-03 2.64E-07 2.39E-05 3.92E-04 4/5/2007 15:00 1.15E-03 1.83E-07 2.66E-05 4.26E-04 4/5/2007 16:00 1.15E-03 3.77E-07 2.77E-05 4.23E-04 4/5/2007 17:00 1.36E-03 1.51E-06 2.80E-05 5.86E-04 4/5/2007 18:00 1.09E-03 3.24E-07 2.38E-05 3.88E-04 4/5/2007 19:00 9.63E-04 NC 4.04E-05 6.48E-04 4/5/2007 20:00 1.12E-03 1.34E-06 2.55E-05 4.98E-04 4/5/2007 21:00 1.02E-03 5.49E-07 2.33E-05 4.11E-04 4/5/2007 22:00 1.04E-03 5.29E-07 2.27E-05 3.98E-04 4/5/2007 23:00 1.08E-03 5.36E-07 2.49E-05 4.39E-04 4/6/2007 0:00 1.11E-03 1.02E-06 2.67E-05 4.98E-04 4/6/2007 1:00 1.26E-03 1.59E-06 3.08E-05 6.39E-04 4/6/2007 2:00 1.15E-03 6.08E-07 2.56E-05 5.89E-04 4/6/2007 3:00 1.22E-03 6.04E-07 2.61E-05 5.51E-04 4/6/2007 4:00 1.26E-03 9.08E-07 2.86E-05 5.65E-04 4/6/2007 5:00 1.11E-03 6.93E-07 2.44E-05 4.85E-04 4/6/2007 6:00 1.07E-03 5.09E-07 2.35E-05 4.57E-04 Average 1.04E-03 4.08E-07 2.64E-05 5.67E-04 C. V. (%) 11.4 163.7 24.0 22.0 Normality P-Value 1 0.035 <0.005 0.023 0.375 Notes: 1 Based on Anderson Darling Normality Test NC - Not Collected 292 APPENDIX B.1 RAW DATA FOR C BURN B.1.1. GENERAL COMMENTS ? The raw data from the C burn are presented in this appendix. ? Coal is the only fuel used in this burn. ? The burn lasted from 7 AM on April 17, 2006 to 7 AM on April 21, 2006. B.1.2. NOTATION CPR ? Cement Plant Results ELR ? External Lab Results AUR ? Auburn University Results C. V. ? Coefficient of Variation B.1.3. CHEMICAL COMPOSITION OF RAW MATERIALS Table B.1.1: CPR - Chemical Composition of Raw Materials Property (wt. %) Raw Material One Raw Material Two Raw Material Three Raw Material Four Raw Material Five Raw Material Six Al 2 O 3 25.80 0.33 2.68 4.22 1.79 0.87 CaO 3.95 54.00 41.54 28.90 0.87 36.80 Fe 2 O 3 10.20 0.14 NR 34.70 1.72 0.45 K 2 O 2.57 0.07 0.18 0.19 0.32 0.11 MgO 1.21 1.15 3.50 8.80 0.08 1.05 Na 2 O 0.38 0.00 0.01 0.00 0.03 0.00 SiO 2 43.70 0.96 14.00 15.40 93.70 3.98 SO 3 0.66 0.18 0.12 1.27 0.38 44.40 Moisture 9.07 5.80 NC 8.00 7.70 12.30 LOI 9.07 43.18 NC 2.99 0.48 12.24 Notes: NR - Not Reported NC - Not Collected 293 Table B.1.2: ELR - Chemical Composition of Raw Materials Property Raw Material One Raw Material Two Raw Material Three Raw Material Four Raw Material Five Raw Material Six Al 2 O 3 (wt. %) 24.76 0.19 3.23 3.64 1.47 1.22 CaO (wt. %) 2.95 50.49 43.00 5.57 0.19 33.31 Fe 2 O 3 (wt. %) 9.96 0.13 1.89 52.83 0.91 0.74 K 2 O (wt. %) 2.25 0.06 0.34 0.79 0.43 0.13 MgO (wt. %) 1.26 0.77 1.17 1.66 0.30 1.50 Na 2 O (wt. %) 0.53 0.00 0.00 0.20 0.00 0.03 P 2 O 5 (wt. %) 0.63 0.01 0.03 0.56 0.01 0.03 SiO 2 (wt. %) 43.44 0.51 15.92 13.51 95.59 5.93 SO 3 (wt. %) 0.30 0.12 0.29 0.69 0.25 38.60 TiO 2 (wt. %) 1.15 0.01 0.23 0.16 0.43 0.05 Moisture (wt. %) 17.71 2.54 4.53 12.49 4.31 2.09 LOI (wt. %) 12.77 47.72 33.93 20.39 0.45 18.44 As (ppm) 173 ND 7 6 ND ND Ba (ppm) 1867 68 316 308 131 73 Cd (ppm) ND ND ND 6 ND ND Cl (ppm) 23 24 42 114 43 7 Co (ppm) 43 ND 26 38 ND ND Cr (ppm) 139 ND 62 285 ND ND Cu (ppm) 269 ND 21 545 23 36 Hg (ppm) 0.07 0.01 0.04 0.01 0.01 0.09 Mn (ppm) 280 24 801 7919 153 340 Mo (ppm) ND ND ND 18 ND ND Ni (ppm) 112 ND ND 192 ND ND Pb (ppm) 63 12 17 450 40 8 Sb (ppm) 20 32 82 ND ND ND Se (ppm) 31 1 2ND1 Sr (ppm) 1432 172 240 127 50 573 V (ppm) 303 ND 49 97 ND ND Zn (ppm) 84 ND 27 6464 80 ND Notes: ND - Not Detected 294 B.1.4. CHEMICAL COMPOSITION OF KILN FEED Table B.1.3: CPR - Chemical Composition of Kiln Feed 4/21/2006 8:21 AM 2:30 PM 1:49 AM 8:41 AM 2:22 PM 8:27 PM 2:23 AM 8:08 AM 3:32 PM 2:17 AM Al 2 O 3 3.13 3.00 3.10 3.10 3.15 3.25 3.18 3.11 3.00 3.08 3.11 2.4 0.561 CaO 43.90 43.70 43.63 44.25 43.93 44.10 44.00 44.11 43.77 44.11 43.95 0.5 0.642 Fe 2 O 3 2.03 2.00 2.21 1.93 1.98 1.96 2.06 2.08 2.08 2.05 2.04 3.9 0.526 K 2 O 0.35 0.33 0.35 0.33 0.33 0.34 0.33 0.33 0.32 0.33 0.33 2.9 2 0.005 MgO 1.98 2.00 1.95 1.90 1.94 1.89 1.91 1.92 1.88 1.85 1.92 2.4 0.954 Na 2 O 0.06 0.05 0.05 0.05 0.04 0.05 0.04 0.05 0.04 0.04 0.05 14.4 2 0.008 Na 2 O eq 0.29 0.27 0.28 0.27 0.26 0.27 0.26 0.27 0.25 0.26 0.27 4.2 0.241 SiO 2 13.77 13.80 13.93 13.44 13.70 13.53 13.73 13.62 13.66 13.52 13.67 1.1 0.960 SO 3 0.26 0.22 0.29 0.32 0.31 0.35 0.31 0.31 0.29 0.27 0.29 12.4 0.502 LOI 36.61 36.47 36.37 36.80 36.60 36.67 36.62 36.71 36.41 36.64 36.59 0.4 0.430 Notes: NC - Not Collected 1 Based on Anderson-Darling Normality Test NA - Not Applicable 2 Data not normally distributed Average C. V. (%) Normality P-Value 1 4/18/2006 4/19/2006 4/20/2006 Property (wt. %) 295 Table B.1.4: ELR - Chemical Composition of Kiln Feed Property 3-Day Composite Al 2 O 3 (wt. %) 3.05 CaO (wt. %) 44.18 Fe 2 O 3 (wt. %) 2.15 K 2 O (wt. %) 0.33 MgO (wt. %) 1.90 Na 2 O (wt. %) 0.01 P 2 O 5 (wt. %) 0.05 SiO 2 (wt. %) 13.38 SO 3 (wt. %) 0.35 TiO 2 (wt. %) 0.17 Moisture (wt. %) 0.06 LOI (wt. %) 34.44 As (ppm) 3 Ba (ppm) 192 Cd (ppm) ND Cl (ppm) 111 Co (ppm) ND Cr (ppm) 51 Cu (ppm) 43 Hg (ppm) 0.02 Mn (ppm) 664 Mo (ppm) ND Ni (ppm) ND Pb (ppm) 24 Sb (ppm) 33 Se (ppm) 1 Sr (ppm) 261 V (ppm) 39 Zn (ppm) 113 Notes: ND - Not Detected 296 B.1.5. CHEMICAL COMPOSITION OF FUELS Table B.1.5: CPR - Chemical Composition of Coal Test Parameter Value (wt. %) Ash 18.9 Fixed Carbon 50.17 Volatile Matter 30.93 Carbon 69.06 Hydrogen 4.25 Nitrogen 1.51 Oxygen 5.22 Sulfur 1.06 Al 2 O 3 24.67 CaO 13.32 Fe 2 O 3 5.83 K 2 O 1.97 MgO 1.18 Na 2 O 0.39 SiO 2 42.89 SO 3 8.36 12102 Notes: 1 Value is Reported as BTU/lb Ultimate Analysis Standard Parameters Heat Value 1 Proximat e Analysi s 297 Table B.1.6: ELR - Proximate, Ultimate, and Combustion Analysis of Coal Test Parameter Value (wt. %) Ash 22.45 Fixed Carbon 49.58 Volatile Matter 27.97 Carbon 67.61 Hydrogen 3.61 Nitrogen 1.1 Oxygen 3.95 Sulfur 1.28 11698 Notes: 1 Value is Reported as BTU/lb Pr oximate A n alysis Ultimat e Analysis Heat Value 1 298 299 Table B.1.7: ELR - Standard Parameters of Coal Property 3-Day Composite Al 2 O 3 (wt. %) 25.08 CaO (wt. %) 7.53 Fe 2 O 3 (wt. %) 7.61 K 2 O (wt. %) 2.58 MgO (wt. %) 1.35 Na 2 O (wt. %) 0.22 P 2 O 5 (wt. %) 0.18 SiO 2 (wt. %) 47.39 SO 3 (wt. %) 6.95 TiO 2 (wt. %) 1.12 As (ppm) 325 Ba (ppm) 1274 Cd (ppm) ND Cl (ppm) - Co (ppm) ND Cr (ppm) 109 Cu (ppm) 150 Hg (ppm) - Mn (ppm) 221 Mo (ppm) ND Ni (ppm) 81 Pb (ppm) 42 Sb (ppm) ND Se (ppm) ND Sr (ppm) 487 V (ppm) 226 Zn (ppm) 68 Notes: ND - Not Detected B.1.6. CHEMICAL COMPOSITION OF CEMENT KILN DUST (CKD) Table B.1.8: CPR - Chemical Composition of CKD 8:00 AM 7:00 PM 7:00 AM 7:00 PM 7:00 AM 7:00 PM Al 2 O 3 3.64 3.42 4.04 3.08 3.61 4.37 3.69 CaO 49.46 47.2 44.87 52.22 46.85 44.68 47.55 Fe 2 O 3 1.73 1.81 1.92 1.48 1.89 2.08 1.82 K 2 O 0.71 0.45 0.46 0.39 0.39 0.49 0.48 MgO 2.29 1.59 1.22 1.85 1.47 1.53 1.66 Na 2 O 0.08 0.07 0.07 0.06 0.06 0.08 0.07 SiO 2 10.06 11 12.42 9.58 12.83 14.2 11.68 SO 3 2.74 1.21 0.42 1.48 0.34 0.59 1.13 4/19/20064/18/2006 4/20/2006 Property (wt. %) Average 300 Table B.1.9: ELR - Chemical Composition of CKD 301 0 1 1 8:00 AM 7:00 PM 7:00 AM 7:00 PM 7:00 AM 7:00 PM Al 2 O 3 (wt. %) 3.64 3.83 4.02 4.11 3.44 3.56 3.77 CaO (wt. %) 52.71 58.08 47.08 51.87 54.76 73.46 56.33 Fe 2 O 3 (wt. %) 1.97 2.03 1.96 2.27 1.93 1.88 2.01 K 2 O (wt. %) 0.43 0.45 0.44 0.39 0.40 0.46 0.43 MgO (wt. %) 1.77 2.34 1.28 1.67 1.73 2.58 1.90 Na 2 O (wt. %) 0.00 0.02 0.02 0.02 0.00 0.00 0.01 P 2 O 5 (wt. %) 0.05 0.06 0.08 0.07 0.05 0.05 0.06 SiO 2 (wt. %) 10.64 10.02 11.87 13.94 11.37 10.10 11.32 SO 3 (wt. %) 1.54 2.59 0.53 0.77 0.85 2.32 1.43 TiO 2 (wt. %) 0.21 0.23 0.22 0.25 0.19 0.21 0.22 Moisture (wt. %) 0.06 0.03 0.15 0.09 0.02 0.05 0.07 LOI (wt. %) 27.04 20.36 32.48 24.64 25.28 5.45 22.54 As (ppm) 426ND3ND3.7 Ba (ppm) 279 345 257 239 236 314 278.39 Cd (ppm) ND ND ND ND ND ND NA Cl (ppm) 286 863 124 1067 233 324 482.83 Co (ppm) 14 12 ND 15 12 22 15.00 Cr (ppm) 45 33 31 38 25 27 32.95 Cu (ppm) 38 66 53 45 49 46 49.35 Hg (ppm) 0.02 ND 0.02 0.01 ND 0.01 0.02 Mn (ppm) 290 243 300 421 365 272 315.07 Mo (ppm) ND ND ND ND ND ND NA Ni (ppm) ND 11 ND ND ND ND 11.00 Pb (ppm) 7 271036142820.4 Sb (ppm) 57 52 58 47 44 72 55.10 Se (ppm) 221ND12.3 Sr (ppm) 300 336 301 295 298 394 320.66 V (ppm) 48 59 55 62 48 57 54.85 Zn (ppm) 104 76 74 122 95 78 91.47 Notes: NA - Not Applicable ND - Not Detected Property 4/18/2006 4/19/2006 4/20/2006 Average B.1.7. CHEMICAL COMPOSITION OF CLINKER Table B.1.10: CPR - Chemical Composition of Clinker for 4/18/06 8:25 AM 10:18 AM 12:02 PM 2:33 PM 4:21 PM 5:52 PM 7:51 PM 10:12 PM Al 2 O 3 5.36 5.17 5.27 5.23 5.34 5.23 5.39 5.38 CaO 64.83 64.76 64.83 64.86 64.64 64.74 64.66 64.64 Fe 2 O 3 3.53 3.42 3.53 3.42 3.61 3.74 3.75 3.80 K 2 O 0.59 0.62 0.55 0.57 0.57 0.58 0.56 0.55 MgO 2.98 3.00 2.94 3.03 3.04 2.99 3.04 3.03 Na 2 O 0.08 0.07 0.08 0.07 0.08 0.08 0.07 0.07 Na 2 O eq 0.47 0.48 0.44 0.45 0.46 0.46 0.44 0.43 SiO 2 21.47 21.60 21.70 21.60 21.53 21.53 21.62 21.65 SO 3 0.92 0.82 0.59 0.65 0.88 0.78 0.73 0.69 F CaO 0.64 0.54 0.29 0.59 0.78 1.22 0.64 0.59 C 3 A 8.20 7.90 8.00 8.10 8.00 7.50 7.90 7.80 C 4 AF 10.70 10.40 10.70 10.40 11.00 11.40 11.40 11.60 C 3 S 59.70 59.90 58.60 59.90 58.50 59.40 57.30 57.00 C 2 S 16.50 16.80 18.00 16.80 17.60 16.90 18.70 19.00 Property (wt. %) 4/18/2006 302 Table B.1.11: CPR - Chemical Composition of Clinker for 4/19/06 12:03 AM 1:49 AM 3:42 AM 5:44 AM 8:40 AM 10:24 AM 11:41 AM 12:31 PM 2:22 PM 4:11 PM 5:39 PM 8:27 PM 10:04 PM 11:49 PM Al 2 O 3 5.37 5.29 5.28 5.28 5.50 5.32 5.47 5.38 5.41 5.47 5.48 5.38 5.50 5.46 CaO 64.49 64.61 64.66 64.81 64.80 65.25 65.04 65.14 64.95 64.86 65.11 65.18 65.00 64.98 Fe 2 O 3 3.87 3.91 3.75 3.66 3.62 3.19 3.20 3.12 3.23 3.15 3.14 3.12 3.20 3.27 K 2 O 0.57 0.55 0.57 0.56 0.54 0.55 0.56 0.55 0.56 0.60 0.54 0.50 0.53 0.55 MgO 2.99 3.00 2.93 2.94 2.94 2.91 2.94 2.97 2.95 2.94 2.96 2.84 2.87 2.88 Na 2 O 0.08 0.07 0.08 0.08 0.07 0.07 0.07 0.08 0.07 0.07 0.07 0.07 0.07 0.08 Na 2 O eq 0.46 0.43 0.46 0.45 0.43 0.43 0.44 0.44 0.44 0.46 0.43 0.40 0.42 0.44 SiO 2 21.62 21.67 21.53 21.43 21.29 21.05 21.22 21.21 21.27 21.29 21.37 21.41 21.37 21.31 SO 3 0.71 0.73 0.78 0.80 0.81 0.86 1.02 0.85 0.95 0.97 0.88 0.82 0.85 0.88 F CaO 0.83 0.73 0.78 0.73 0.93 1.91 1.81 2.06 1.22 1.47 1.03 0.88 1.08 1.13 C 3 A 7.70 7.40 7.60 7.80 8.40 8.70 9.10 9.00 8.90 9.20 9.20 9.00 9.20 8.90 C 4 AF 11.80 11.90 11.40 11.10 11.00 9.70 9.70 9.50 9.80 9.60 9.60 9.50 9.70 10.00 C 3 S 56.60 57.20 58.80 60.30 59.90 65.40 62.20 63.40 61.80 61.00 61.30 62.00 60.70 61.20 C 2 S 19.30 19.00 17.40 16.00 15.90 11.00 13.90 13.00 14.40 15.00 15.00 14.60 15.50 14.90 Property (wt. %) 4/19/2006 303 304 2:21 AM 3:53 AM 5:49 AM 8:07 AM 10:11 AM 11:50 AM 2:25 PM 4:00 PM 5:40 PM 7:54 PM 9:53 PM 11:47 PM 2:16 AM 3:59 AM 5:40 AM Al 2 O 3 5.61 5.35 5.35 5.40 5.30 5.45 5.42 5.22 5.12 4.98 4.94 4.90 5.05 5.11 5.06 5.30 3.2 2 0.033 CaO 64.83 64.99 64.90 64.89 64.96 65.19 65.27 65.24 65.25 65.23 65.39 65.29 65.23 65.21 65.16 64.97 0.4 0.116 Fe 2 O 3 3.41 3.28 3.47 3.45 3.48 3.38 3.41 3.32 3.26 3.23 3.25 3.22 3.30 3.30 3.22 3.41 6.6 2 0.012 K 2 O 0.57 0.56 0.57 0.57 0.55 0.58 0.57 0.54 0.54 0.56 0.51 0.56 0.56 0.57 0.60 0.56 4.1 2 0.022 MgO 2.87 2.84 2.88 2.93 3.04 2.93 2.96 2.92 2.88 2.88 2.77 2.88 2.80 2.87 2.89 2.93 2.3 0.453 Na 2 O 0.07 0.08 0.08 0.08 0.08 0.07 0.08 0.07 0.08 0.08 0.07 0.07 0.07 0.07 0.07 0.07 6.8 2 <0.005 Na 2 O e Table B.1.12: CPR - Chemical Composition of Clinker for 4/20/06 and 4/21/06 q 0.45 0.45 0.46 0.46 0.44 0.45 0.46 0.43 0.44 0.45 0.41 0.44 0.44 0.45 0.46 0.44 3.7 2 0.022 SiO 2 21.31 21.47 21.31 21.26 21.32 21.07 21.05 21.21 21.02 21.29 21.50 21.47 21.47 21.34 21.25 21.38 0.9 0.391 SO 3 0.89 0.93 0.95 0.95 0.83 0.95 0.84 0.92 0.95 0.95 0.85 0.93 0.75 0.74 1.02 0.85 12.1 0.323 F CaO 1.27 0.64 1.32 1.13 1.22 1.47 0.98 1.32 1.52 1.52 1.47 1.42 1.08 1.08 1.42 1.10 37.1 0.605 C 3 A 9.10 8.60 8.30 8.50 8.20 8.70 8.60 8.20 8.10 7.70 7.60 7.50 7.80 8.00 8.00 8.28 6.8 2 0.043 C 4 AF 10.40 10.00 10.60 10.50 10.60 10.30 10.40 10.10 9.90 9.80 9.90 9.80 10.00 10.00 9.80 10.38 6.7 2 0.009 C 3 S 59.40 60.80 61.30 61.40 61.80 63.80 64.40 64.60 66.80 65.70 65.00 65.10 63.70 64.20 65.20 61.49 4.4 0.362 C 2 S 16.30 15.70 14.80 14.60 14.50 12.30 11.70 12.10 9.90 11.50 12.60 12.40 13.50 12.70 11.80 14.91 16.6 0.742 Notes: 1 Based on Anderson-Darling Normality Test 2 Data not normally distributed C. V. (%) Normality P-Value 1 Property (wt. %) Average 4/20/2006 4/21/2006 Table 13: ELR - Chemical Composition of Clinker 305 5 0 Comp. 1Comp. 2Comp. 1Comp. 2Comp. 1Comp. 2 Al 2 O 3 (wt. %) 5.52 5.37 5.27 5.18 5.29 4.98 5.27 CaO (wt. %) 64.01 64.57 65.68 65.62 65.08 65.94 65.15 Fe 2 O 3 (wt. %) 3.55 3.51 3.27 3.16 3.26 3.29 3.34 K 2 O (wt. %) 0.64 0.60 0.58 0.59 0.58 0.61 0.60 MgO (wt. %) 2.87 2.89 2.89 2.89 2.85 2.89 2.88 Na 2 O (wt. %) 0.05 0.02 0.00 0.01 0.00 0.01 0.01 P 2 O 5 (wt. %) 0.09 0.09 0.08 0.08 0.08 0.08 0.08 SiO 2 (wt. %) 21.95 21.64 20.84 20.68 21.53 20.77 21.24 SO 3 (wt. %) 0.89 0.85 1.01 1.19 0.91 0.95 0.97 TiO 2 (wt. %) 0.32 0.31 0.29 0.33 0.28 0.29 0.30 Moisture (wt. %) 0.00 0.00 0.02 0.04 0.01 0.00 0.01 LOI (wt. %) 0.09 0.14 0.09 0.27 0.14 0.19 0.15 As (ppm) 10899798.6 Ba (ppm) 382 397 365 403 335 313 365.75 Cd (ppm) ND ND ND ND ND ND NA Cl (ppm) 265 182 158 315 238 274 238.67 Co (ppm) 15 ND 12 24 12 13 15.19 Cr (ppm) 78 69 63 73 66 84 72.34 Cu (ppm) 50 75 68 69 51 77 65.00 Hg (ppm) 0.03 ND 0.02 ND 0.01 0.01 0.02 Mn (ppm) 985 976 916 924 965 985 958.50 Mo (ppm) 11 ND ND 16 9 ND 12.00 Ni (ppm) 137 13 14 ND 10 ND 43.36 Pb (ppm) 46 34 70 30 11 26 36.15 Sb (ppm) 47 49 34 57 79 78 57.16 Se (ppm) 1111111. Sr (ppm) 429 401 397 390 394 403 402.31 V (ppm) 68 68 56 70 56 67 64.03 Zn (ppm) 163 146 109 113 147 130 134.69 Notes: NA - Not Applicable ND - Not Detected Property Average 4/18/2006 4/19/2006 4/20/2006 B.1.8. CHEMICAL COMPOSITION OF CEMENT Table B.1.14: CPR - Chemical Composition of Cement for 4/18/06 and 4/19/06 7:12 AM 10:25 AM 1:17 PM 3:11 PM 4:21 PM 11:31 AM 1:24 PM 4:18 PM 7:02 PM 10:00 PM Al 2 O 3 4.64 4.68 4.92 4.93 4.96 5.17 5.16 5.16 5.08 4.93 CaO 64.03 63.81 63.11 63.13 63.15 62.93 62.98 63.26 63.47 63.52 Fe 2 O 3 2.88 2.97 3.17 3.2 3.24 3.26 3.25 3.3 3.09 3.07 K 2 O 0.52 0.52 0.51 0.51 0.51 0.52 0.51 0.51 0.52 0.53 MgO 3.16 3.01 2.89 2.88 2.92 2.9 2.91 2.87 2.84 2.93 Na 2 O 0.11 0.1 0.09 0.09 0.1 0.09 0.09 0.09 0.1 0.1 Na 2 O eq 0.45 0.44 0.43 0.43 0.44 0.43 0.43 0.43 0.44 0.45 SiO 2 20.64 20.72 20.66 20.65 20.75 20.58 20.64 20.69 20.47 20.68 SO 3 2.55 2.72 3.06 2.71 2.65 2.62 2.76 2.57 2.47 2.5 F CaO 0.98 0.98 0.59 NC 0.54 0.69 0.98 1.17 1.08 0.98 LOI 0.99 1.03 1.03 NC 0.79 0.94 1.23 0.97 0.63 0.89 C 3 A 7.4 7.4 7.7 7.7 7.7 8.2 8.2 8.1 8.2 7.9 C 4 AF 8.8 9 9.6 9.7 9.9 9.9 9.9 10 9.4 9.3 C 3 S 61.2 58.8 53.6 54.6 53.9 52.9 52.3 53.6 57.2 56.8 C 2 S 13 15 18.8 18 18.9 19.1 19.7 18.9 15.5 16.5 Blaine SSA (m 2 /kg) 387 387 400 402 372 391 379 370 366 368 Notes: NC - Not Collected Property (wt. %) 4/18/2006 4/19/2006 306 307 1:07 AM 3:52 AM 5:27 AM 7:04 AM 10:16 AM 12:52 PM 4:00 PM 6:57 PM 9:53 PM 1:28 AM 4:00 AM Al 2 O 3 4.93 5 5.08 5.02 5.02 5.1 5.06 5.03 4.93 4.88 4.93 4.98 2.8 2 0.065 CaO 63.65 63.55 63.6 63.29 63.4 63.31 63.46 63.88 64.03 63.76 63.97 63.49 0.5 0.843 Fe 2 O 3 3.09 3.05 3.16 3.06 3.11 3.07 3.04 3.07 3.07 3.06 3.09 3.11 3.2 2 0.056 K 2 O 0.52 0.53 0.52 0.52 0.52 0.51 0.55 0.53 0.53 0.53 0.53 0.52 1.9 2 <0.005 MgO 2.87 2.86 2.88 2.81 2.8 2.82 2.79 2.85 2.81 2.8 2.85 2.88 2.9 2 <0.005 Na 2 O 0.09 0.09 0.09 0.1 0.1 0.09 0.08 0.09 0.08 0.1 0.09 0.09 7.8 2 <0.005 Na 2 O e Table B.1.15: CPR - Chemical Composition of Cement for 4/20/06 and 4/21/06 q 0.43 0.44 0.43 0.44 0.44 0.43 0.44 0.44 0.43 0.45 0.44 0.44 1.6 2 <0.005 SiO 2 20.6 20.5 20.58 20.41 20.49 20.58 20.54 20.53 20.4 20.39 20.44 20.57 0.5 0.646 SO 3 2.45 2.42 2.41 2.71 2.75 2.73 2.72 2.4 2.66 2.71 2.44 2.62 6.2 2 0.075 F CaO 1.13 0.98 NC 0.98 0.59 0.64 1.13 1.03 1.08 1.08 1.27 0.94 23.3 2 <0.005 LOI 1.05 1.12 NC 0.96 0.9 1.02 1.1 1.16 1.39 1.3 1.25 1.04 17.4 0.859 C 3 A 7.8 8.1 8.1 8.1 8 8.3 8.3 8.1 7.9 7.8 7.8 7.94 3.3 0.118 C 4 AF 9.4 9.3 9.6 9.3 9.5 9.3 9.3 9.3 9.3 9.3 9.4 9.45 3.2 2 0.016 C 3 S 58 58 57 56.7 56.4 54.9 56.1 59 60.5 59.7 60.6 56.75 4.7 0.738 C 2 S 15.3 15 16 15.7 16.2 17.6 16.5 14.4 12.8 13.4 12.9 16.15 13.5 0.380 Blaine SSA (m 2 /kg) 368 370 NC 373 366 368 372 379 372 370 381 377.05 2.9 2 <0.005 Notes: 1 Based on Anderson-Darling Normality Test 2 Data not normally distributed NC - Not Collected Property (wt. %) Average Normality P-Value 1 C. V. (%) 4/20/2006 4/21/2006 Table B.1.16: ELR - Chemical Composition of Cement Property 4/18/2006 4/19/2006 4/20/2006 Average Al 2 O 3 (wt. %) 5.12 5.04 4.99 5.05 CaO (wt. %) 63.64 64.02 64.34 64.00 Fe 2 O 3 (wt. %) 3.26 3.21 3.13 3.20 K 2 O (wt. %) 0.45 0.53 0.49 0.49 MgO (wt. %) 2.92 2.88 2.87 2.89 Na 2 O (wt. %) 0.05 0.00 0.00 0.02 P 2 O 5 (wt. %) 0.08 0.08 0.08 0.08 SiO 2 (wt. %) 20.56 20.62 20.42 20.53 SO 3 (wt. %) 2.96 2.65 2.73 2.78 TiO 2 (wt. %) 0.27 0.27 0.26 0.27 Moisture (wt. %) 0.23 0.28 0.35 0.29 LOI (wt. %) 0.68 0.71 0.69 0.69 C 3 S (wt. %) -- -- -- 58.07 C 2 S (wt. %) -- -- -- 15.06 C 3 A (wt. %) -- -- -- 7.96 C 4 AF (wt. %) -- -- -- 9.74 TOC (wt. %) < 0.1 <0.1 <0.1 NA As (ppm) 9698.00 Ba (ppm) 324 316 323 321.10 Cd (ppm) ND ND ND NA Cl (ppm) 59 76 105 80.00 Co (ppm) ND 13 16 14.50 Cr (ppm) 85 81 81 82.36 Cu (ppm) 56 75 61 64.02 Hg (ppm) 0.01 0.01 0.02 0.01 Mn (ppm) 982 955 938 958.30 Mo (ppm) ND 9 ND 9.00 Ni (ppm) ND ND ND NA Pb (ppm) 28 29 43 33.34 Sb (ppm) 35 59 59 51.01 Se (ppm) 1211.33 Sr (ppm) 418 401 410 409.79 V (ppm) 73 61 52 62.02 Zn (ppm) 131 125 122 126.04 Notes: NA - Not Applicable ND - Not Detected 308 B.1.9. PHYSICAL PROPERTIES OF CEMENT Table B.1.17: CPR - Physical Properties of Cement Air in Mortar (%) 6.5 6.4 7.3 6.73 Blaine Specific Surface Area (m 2 /kg) 368.0 361.0 368.0 365.67 Autoclave Expansion (% Exp.) 0.1 0.1 0.1 0.06 Cube Flow (%) 124.0 127.0 126.0 125.67 Comp Str 1day (MPa) 13.5 15.6 16.9 15.33 Comp Str 3day (MPa) 22.3 24.3 26.2 24.27 Comp Str 7day (MPa) 31.7 30.7 33.4 31.93 Comp Str 28day (MPa) 45.8 41.6 40.7 42.70 Normal Consistency (%) 25.7 25.8 25.2 25.57 Gillmore Initial Set (Min) 120.0 105.0 90.0 105.00 Gillmore Final Set (Min) 270.0 315.0 240.0 275.00 Vicat Initial Set (Min) 95.0 79.0 65.0 79.67 Vicat Final Set (Min) 198.0 179.0 163.0 180.00 Notes: % Exp. - % Expansion 4/18/2006 4/19/2006 4/20/2006Property Average 309 Table B.1.18: AUR - Physical Properties of Cement Property Composite Autoclave Expansion (% Exp.) 0.05 Cube Flow (%) 91.4 Comp Str 1day (MPa) 9.3 Comp Str 3day (MPa) 17.2 Comp Str 7day (MPa) 25.8 Comp Str 28day (MPa) 35.1 Normal Consistency (%) 25.4 Gillmore Initial Set (Min) 150 Gillmore Final Set (Min) 238 Vicat Initial Set (Min) 106 Vicat Final Set (Min) 236 Drying Shrinkage @ 7 days (% LC) -0.042 Drying Shrinkage @ 14 days (% LC) -0.068 Drying Shrinkage @ 21 days (% LC) -0.079 Drying Shrinkage @ 28 days (% LC) -0.087 Notes: % LC - Percent Length Change % Exp. - Percent Expansion 310 311 B.1.10. PROPERTIES OF CONCRETE Table B.1.19: Concrete Properties CPR Mix w/c=0.44 Mix w/c=0.37 Mix w/c=0.44 Total Air Content (%) 4.0 6.0 3.6 Slump (mm) 100 150 30 Unit Weight (kg/m 3 ) 2394 2374 2450 Initial Set (Min.) 211 318 218 Final Set (Min.) 298 405 322.0 Compressive Strength (MPa) 1 day 12.3 20.8 15.8 3 days 22.7 31.9 23.3 7 days 25.2 37.7 33.3 28 days 35.0 44.3 43.3 91 days 41.6 51.5 48.2 Splitting Tensile Strength (MPa) 1 day 1.7 2.5 NC 3 days 2.4 3.3 NC 7 days 2.6 3.7 NC 28 days 3.2 4.1 NC 91 days 3.7 4.3 NC Drying Shrinkage Development (% Length Change) 1 4 days 0.009 0.013 NC 7 days 0.018 0.019 NC 14 days 0.028 0.032 NC 28 days 0.029 0.037 NC 56 days 0.038 0.043 NC 112 days 0.045 0.051 NC 224 days 0.049 0.053 NC 448 days 0.050 0.054 NC Permeability @ 91 days (Coulombs) 2650 2650 2660 Property AUR Notes: CIP - Collection in Progress NC - Not Collected 1 Percentage decrease in length B.1.11. EMISSIONS Table B.1.20: CPR - Emissions Time NO x (tons/ton clinker) SO 2 (tons/ton clinker) VOC (tons/ton clinker) CO (tons/ton clinker) 4/18/2006 7:00 9.45E-04 4.38E-06 4.47E-05 9.28E-04 4/18/2006 8:00 8.07E-04 5.05E-06 5.50E-05 1.10E-03 4/18/2006 9:00 7.84E-04 8.88E-07 4.50E-05 9.76E-04 4/18/2006 10:00 8.16E-04 1.88E-07 5.09E-05 8.54E-04 4/18/2006 11:00 7.97E-04 1.31E-07 5.03E-05 8.59E-04 4/18/2006 12:00 8.04E-04 7.85E-08 4.21E-05 8.35E-04 4/18/2006 13:00 8.25E-04 1.36E-07 3.96E-05 8.17E-04 4/18/2006 14:00 8.43E-04 9.76E-08 3.65E-05 7.85E-04 4/18/2006 15:00 8.74E-04 2.57E-08 3.37E-05 8.45E-04 4/18/2006 16:00 8.26E-04 2.05E-08 3.07E-05 8.09E-04 4/18/2006 17:00 9.19E-04 1.08E-07 2.75E-05 7.84E-04 4/18/2006 18:00 9.27E-04 1.18E-07 2.51E-05 8.22E-04 4/18/2006 19:00 8.49E-04 4.63E-08 2.10E-05 8.54E-04 4/18/2006 20:00 8.45E-04 2.58E-08 2.04E-05 8.05E-04 4/18/2006 21:00 8.90E-04 1.64E-07 2.74E-05 7.66E-04 4/18/2006 22:00 8.61E-04 1.08E-07 3.46E-05 8.10E-04 4/18/2006 23:00 8.30E-04 6.69E-08 2.18E-05 7.21E-04 4/19/2006 0:00 8.09E-04 1.79E-07 1.15E-05 7.14E-04 4/19/2006 1:00 8.27E-04 1.80E-07 1.11E-05 7.51E-04 4/19/2006 2:00 8.17E-04 1.23E-07 9.59E-06 7.60E-04 4/19/2006 3:00 8.15E-04 9.82E-08 9.42E-06 7.49E-04 4/19/2006 4:00 7.71E-04 9.74E-08 1.03E-05 7.82E-04 4/19/2006 5:00 8.04E-04 1.70E-07 1.56E-05 8.29E-04 4/19/2006 6:00 8.52E-04 2.11E-07 9.91E-06 7.53E-04 4/19/2006 7:00 7.93E-04 2.21E-07 6.12E-06 7.17E-04 4/19/2006 8:00 7.48E-04 8.24E-08 3.09E-06 7.08E-04 4/19/2006 9:00 7.75E-04 5.65E-08 5.01E-06 7.07E-04 4/19/2006 10:00 8.37E-04 2.82E-06 2.24E-05 6.94E-04 4/19/2006 11:00 7.87E-04 1.30E-07 2.85E-05 7.11E-04 4/19/2006 12:00 7.97E-04 1.23E-07 3.96E-05 7.60E-04 4/19/2006 13:00 8.42E-04 1.42E-07 3.85E-05 7.87E-04 4/19/2006 14:00 8.08E-04 3.53E-08 3.61E-05 7.94E-04 4/19/2006 15:00 7.64E-04 1.16E-08 3.60E-05 7.43E-04 4/19/2006 16:00 7.83E-04 1.34E-07 3.53E-05 7.27E-04 4/19/2006 17:00 7.93E-04 1.18E-07 3.22E-05 7.42E-04 4/19/2006 18:00 8.23E-04 1.24E-07 3.46E-05 7.52E-04 4/19/2006 19:00 7.41E-04 8.24E-08 2.47E-05 7.69E-04 4/19/2006 20:00 7.40E-04 1.34E-07 1.52E-05 8.08E-04 4/19/2006 21:00 8.85E-04 2.18E-06 1.37E-05 7.32E-04 4/19/2006 22:00 8.17E-04 3.63E-07 1.36E-05 7.23E-04 4/19/2006 23:00 7.93E-04 5.41E-07 1.04E-05 7.84E-04 4/20/2006 0:00 7.64E-04 1.09E-06 9.02E-06 7.18E-04 4/20/2006 1:00 9.12E-04 2.28E-07 1.57E-05 7.06E-04 4/20/2006 2:00 9.54E-04 3.74E-07 1.44E-05 7.38E-04 4/20/2006 3:00 8.92E-04 2.35E-07 1.26E-05 6.80E-04 4/20/2006 4:00 9.21E-04 3.86E-07 1.43E-05 6.89E-04 4/20/2006 5:00 7.90E-04 1.83E-07 1.07E-05 7.27E-04 4/20/2006 6:00 8.04E-04 9.03E-08 1.74E-05 7.20E-04 312 313 Table B.1.21: CPR - Emission (Continued) Time NO x (tons/ton clinker) SO 2 (tons/ton clinker) VOC (tons/ton clinker) CO (tons/ton clinker) 4/20/2006 7:00 9.55E-04 2.34E-07 2.40E-05 6.88E-04 4/20/2006 8:00 NC NC 3.48E-05 7.60E-04 4/20/2006 9:00 NC NC 3.93E-05 7.58E-04 4/20/2006 10:00 NC NC 3.87E-05 7.11E-04 4/20/2006 11:00 8.10E-04 NC 4.84E-05 9.65E-04 4/20/2006 12:00 8.40E-04 1.14E-08 2.99E-05 9.15E-04 4/20/2006 13:00 8.44E-04 2.10E-07 4.37E-05 8.30E-04 4/20/2006 14:00 8.81E-04 1.66E-07 4.07E-05 8.42E-04 4/20/2006 15:00 8.85E-04 1.48E-07 1.69E-05 8.40E-04 4/20/2006 16:00 7.68E-04 6.14E-08 1.39E-06 8.86E-04 4/20/2006 17:00 7.64E-04 4.29E-08 NC 8.80E-04 4/20/2006 18:00 8.35E-04 1.84E-07 2.66E-06 8.86E-04 4/20/2006 19:00 8.42E-04 1.96E-07 3.57E-06 7.99E-04 4/20/2006 20:00 7.86E-04 3.59E-07 3.46E-06 7.34E-04 4/20/2006 21:00 6.23E-04 4.59E-07 NC 6.75E-04 4/20/2006 22:00 6.54E-04 2.10E-07 NC 5.96E-04 4/20/2006 23:00 8.01E-04 1.99E-07 2.82E-06 6.28E-04 4/21/2006 0:00 6.70E-04 7.38E-08 NC 6.62E-04 4/21/2006 1:00 7.76E-04 2.28E-07 5.32E-06 6.91E-04 4/21/2006 2:00 6.70E-04 9.68E-08 NC 6.87E-04 4/21/2006 3:00 6.85E-04 3.80E-07 NC 6.78E-04 4/21/2006 4:00 8.83E-04 4.79E-07 5.78E-06 6.95E-04 4/21/2006 5:00 9.00E-04 3.57E-07 5.57E-06 7.05E-04 4/21/2006 6:00 8.69E-04 5.20E-07 5.32E-06 7.53E-04 Average 8.18E-04 4.00E-07 2.31E-05 7.72E-04 C. V. (%) 8.3 218.9 64.5 11.0 Normality P-Value 1 0.064 <0.006 <0.005 0.007 Notes: 1 Based on Anderson Darling Normality Test NC - Not Collected 314 APPENDIX B.2 RAW DATA FOR CT1 BURN B.2.1. GENERAL COMMENTS ? The raw data from the CT1 burn are presented in this appendix. ? Coal and scrap tires are the fuels used in the burn. ? The burn lasted from 7 AM on July 11, 2006 to 7 AM on July 14, 2006. B.2.2. NOTATION CPR ? Cement Plant Results ELR ? External Lab Results AUR ? Auburn University Results C. V. ? Coefficient of Variation B.2.3. CHEMICAL COMPOSITION OF RAW MATERIALS Table B.2.1: CPR - Chemical Composition of Raw Materials Property (wt. %) Raw Material One Raw Material Two Raw Material Three Raw Material Four Raw Material Five Raw Material Six Al 2 O 3 22.80 0.30 3.16 6.28 0.76 1.87 CaO 4.38 54.10 40.94 35.10 2.16 29.10 Fe 2 O 3 9.27 0.17 1.43 25.00 1.45 0.00 K 2 O 2.08 0.01 0.17 0.00 0.16 0.19 MgO 1.09 0.95 3.48 10.40 0.19 1.40 Na 2 O 0.40 NR 0.07 NR NR 0.00 SiO 2 44.90 0.85 14.35 16.50 92.20 8.14 SO 3 1.21 1.05 0.14 0.60 1.12 41.67 Moisture 19.81 1.80 NC 4.46 4.30 8.70 LOI 11.63 42.47 NC 1.84 1.56 17.63 Notes: NR - Not Reported NC - Not Collected 315 Table B.2.2: ELR - Chemical Composition of Raw Materials Property Raw Material One Raw Material Two Raw Material Three Raw Material Four Raw Material Five Raw Material Six Al 2 O 3 (wt. %) 24.07 0.07 5.32 3.90 1.92 0.76 CaO (wt. %) 2.74 54.92 36.02 31.68 0.37 30.90 Fe 2 O 3 (wt. %) 10.97 0.15 2.75 40.25 1.17 0.25 K 2 O (wt. %) 2.25 0.06 0.40 0.03 0.25 0.16 MgO (wt. %) 1.07 0.82 1.18 11.95 0.19 0.62 Na 2 O (wt. %) 0.55 0.03 0.08 0.03 0.07 0.06 P 2 O 5 (wt. %) 0.56 0.00 0.06 0.61 0.03 0.01 SiO 2 (wt. %) 43.09 0.49 22.11 12.37 94.77 4.58 SO 3 (wt. %) 0.15 0.15 0.25 0.20 0.01 41.90 TiO 2 (wt. %) 1.10 0.00 1.04 0.26 0.28 0.02 Moisture (wt. %) 23.67 0.02 0.34 0.31 4.20 0.80 LOI (wt. %) 13.44 43.32 30.78 ND 0.93 20.74 As (ppm) 137 ND 18 ND 7 ND Ba (ppm) 1510 88 293 ND ND ND Cd (ppm) ND ND ND 3 ND ND Cl (ppm) 125 265 158 238 59 105 Co (ppm) 45 ND ND ND ND ND Cr (ppm) 135 ND 40 2672 ND ND Cu (ppm) 200 ND ND 22 30 ND Hg (ppm) 0.01 0.03 0.03 0.05 0.01 0.09 Mn (ppm) 302 18 96 19571 78 82 Mo (ppm) ND ND ND 72 ND ND Ni (ppm) 114 ND 21 11 22 9 Pb (ppm) 67 12 47 13 8 21 Sb (ppm) ND 80 30 36 ND ND Se (ppm) 3NDND 2 1ND Sr (ppm) 1373 225 259 169 122 566 V (ppm) 271 ND 103 687 ND ND Zn (ppm) 150 24 90 134 13 ND Notes: ND - Not Detected 316 B.2.4. CHEMICAL COMPOSITION OF KILN FEED Table B.2.3: CPR - Chemical Composition of Kiln Feed 7/14/2006 8:30 AM 2:11 PM 8:36 PM 2:31 AM 8:27 AM 2:38 PM 8:31 PM 2:34 AM 8:09 AM 2:52 PM 8:09 PM 2:13 AM Al 2 O 3 3.29 3.17 3.09 3.29 3.18 3.27 3.27 3.2 3.27 3.3 3.34 3.09 3.23 2.6 2 0.092 CaO 43.2 43.34 42.81 43.33 42.43 42.7 43.44 43.42 42.94 43.34 42.74 42.9 43.05 0.8 0.166 Fe 2 O 3 1.9 1.94 1.98 1.99 2.04 2.07 1.97 2 2.06 2.03 2.11 2.1 2.02 3.2 0.965 K 2 O 0.28 0.27 0.28 0.28 0.28 0.31 0.31 0.3 0.31 0.31 0.31 0.3 0.30 5.3 2 <0.005 MgO 2.77 2.77 2.54 2.71 2.61 2.31 2.34 2.4 2.43 2.43 2.4 2.42 2.51 6.6 2 0.064 Na 2 O 0.11 0.1 0.13 0.1 0.14 0.12 0.09 0.1 0.1 0.09 0.09 0.07 0.10 18.6 0.238 Na 2 O eq 0.29 0.28 0.31 0.28 0.32 0.32 0.29 0.3 0.3 0.29 0.29 0.27 0.30 5.3 0.336 SiO 2 14.47 14.24 13.78 14.37 14.35 14.18 14.45 14.39 14.54 14.52 14.73 14.57 14.38 1.7 0.181 SO 3 0.28 0.29 0.23 0.35 0.29 0.31 0.3 0.24 0.27 0.31 0.31 0.34 0.29 12.1 0.611 LOI 34.71 35.26 35.88 34.22 35.22 34.81 35.3 35.22 34.78 35.11 35.07 35.07 35.05 1.2 0.249 Notes: NC - Not Collected 1 Based on Anderson-Darling Normality Test NA - Not Applicable 2 Data not normally distributed 7/11/2006 7/12/2006 7/13/2006 Average C. V. (%) Normality P-Value 1 Property (wt. %) 317 Table 2.4: ELR - Chemical Composition of Kiln Feed Property 3-Day Composite Al 2 O 3 (wt. %) 2.75 CaO (wt. %) 40.23 Fe 2 O 3 (wt. %) 1.92 K 2 O (wt. %) 0.29 MgO (wt. %) 2.08 Na 2 O (wt. %) 0.03 P 2 O 5 (wt. %) 0.04 SiO 2 (wt. %) 17.00 SO 3 (wt. %) 0.24 TiO 2 (wt. %) 0.21 Moisture (wt. %) 0.19 LOI (wt. %) 35.19 As (ppm) 13 Ba (ppm) 257 Cd (ppm) ND Cl (ppm) 76 Co (ppm) 21 Cr (ppm) 60 Cu (ppm) ND Hg (ppm) 0.10 Mn (ppm) 317 Mo (ppm) ND Ni (ppm) 15 Pb (ppm) 9 Sb (ppm) 88 Se (ppm) ND Sr (ppm) 229 V (ppm) 48 Zn (ppm) 106 Notes: ND - Not Detected 318 B.2.5. CHEMICAL COMPOSITION OF FUELS Table B.2.4: CPR - Chemical Composition of Coal Test Parameter Value (wt. %) Ash 17.82 Fixed Carbon 52.05 Volatile Matter 30.13 Carbon 71.17 Hydrogen 4.34 Nitrogen 1.45 Oxygen 3.69 Sulfur 1.53 Al 2 O 3 23.45 CaO 12.74 Fe 2 O 3 6.24 K 2 O 2.16 MgO 1.49 Na 2 O 0.31 SiO 2 46.21 SO 3 7.41 12506 Notes: 1 Value is Reported as BTU/lb Ul ti mate An alysis St andar d Par a m e t e r s Heat Value 1 P r oximate Analysis 319 Table B.2.5: ELR - Proximate, Ultimate, and Combustion Analysis of Coal Test Parameter Value (wt. %) Ash 16.74 Fixed Carbon 54.81 Volatile Matter 28.45 Carbon 73.09 Hydrogen 4.66 Nitrogen 1.22 Oxygen 3.14 Sulfur 1.15 12624 Notes: 1 Value is Reported as BTU/lb Proximat e Analysis Ulti mate Analysis Heat Value 1 320 Table B.2.6: ELR - Standard Parameters of Coal Property 3-Day Composite Al 2 O 3 (wt. %) 25.54 CaO (wt. %) 7.97 Fe 2 O 3 (wt. %) 7.35 K 2 O (wt. %) 2.67 MgO (wt. %) 1.34 Na 2 O (wt. %) 0.43 P 2 O 5 (wt. %) 0.20 SiO 2 (wt. %) 46.01 SO 3 (wt. %) 7.33 TiO 2 (wt. %) 1.15 As (ppm) 80 Ba (ppm) 1083 Cd (ppm) ND Cl (ppm) 182 Co (ppm) 30 Cr (ppm) 127 Cu (ppm) 116 Hg (ppm) ND Mn (ppm) 355 Mo (ppm) 9 Ni (ppm) 100 Pb (ppm) 48 Sb (ppm) ND Se (ppm) 8 Sr (ppm) 591 V (ppm) 225 Zn (ppm) 133 Notes: ND - Not Detected 321 Table B.2.7: ELR - Proximate, Ultimate, and Combustion Analysis of Tires Test Parameter Value (wt. %) Ash 13.72 Fixed Carbon 24.6 Moisture 1 0.14 Volatile Matter 61.68 Carbon 72.34 Hydrogen 7.05 Nitrogen 0.36 Oxygen 4.98 Sulfur 1.54 14467 Notes: 1 As Received 2 Value is Reported as BTU/lb Ul ti mate An alysis Heat Value 2 P r oximate Analysis 322 323 Table B.2.8: ELR - Standard Parameters for Tires Property 3-Day Composite Al 2 O 3 (wt. %) 1.18 CaO (wt. %) 2.36 Fe 2 O 3 (wt. %) 68.64 K 2 O (wt. %) 0.33 MgO (wt. %) 0.35 Na 2 O (wt. %) 0.31 P 2 O 5 (wt. %) 0.21 SiO 2 (wt. %) 16.87 SO 3 (wt. %) 2.64 TiO 2 (wt. %) 0.20 As (ppm) NR Ba (ppm) 300 Cd (ppm) 6 Cl (ppm) 405 Co (ppm) 616 Cr (ppm) 118 Cu (ppm) 1398 Hg (ppm) 0.4 Mn (ppm) 4100 Mo (ppm) 28 Ni (ppm) 367 Pb (ppm) 11 Sb (ppm) NR Se (ppm) < 1 Sr (ppm) 200 V (ppm) 37 Zn (ppm) 54000 Notes: ND - Not Detected NR - Not Reported B.2.6. CHEMICAL COMPOSITION OF CEMENT KILN DUST (CKD) Table 2.109: CPR - Chemical Composition of Cement Kiln Dust (CKD) 7/11/2006 7/14/2006 7:15 AM 5:26 AM 8:28 AM 1:28 AM 2:53 PM 11:04 PM 6:51 AM Al 2 O 3 4.05 4.03 3.83 3.93 4.18 3.99 3.97 4.00 CaO 43.92 45.13 47.91 44.65 43.33 43.86 44.03 44.69 Fe 2 O 3 2.04 1.99 1.81 2.02 2.12 2.07 2.05 2.01 K 2 O 0.38 0.45 0.5 0.4 0.42 0.4 0.39 0.42 MgO 1.66 1.97 2.18 1.36 1.51 1.4 1.5 1.65 Na 2 O 0.08 0.1 0.1 0.07 0.08 0.09 0.08 0.09 SiO 2 12.54 12.23 10.37 11.96 12.55 12.32 12.35 12.05 SO 3 0.45 1.57 3.14 0.3 0.64 0.24 0.31 0.95 7/12/2006 7/13/2006 AverageProperty (wt. %) 324 Table 2.11: ELR - Chemical Composition of Cement Kiln Dust 7/11/2006 7:15 AM 5:26 AM 8:28 AM 1:28 AM 2:53 PM 11:04 PM Al 2 O 3 (wt. %) 4.08 3.63 3.65 3.53 3.79 3.62 3.72 CaO (wt. %) 43.41 45.38 57.84 44.60 45.03 44.41 46.78 Fe 2 O 3 (wt. %) 2.04 2.09 2.11 2.03 2.21 2.11 2.10 K 2 O (wt. %) 0.38 1.21 0.60 0.39 0.43 0.40 0.57 MgO (wt. %) 1.61 1.47 2.27 1.26 1.35 1.23 1.53 Na 2 O (wt. %) 0.06 0.00 0.00 0.06 0.00 0.00 0.02 P 2 O 5 (wt. %) 0.06 0.04 0.03 0.05 0.06 0.05 0.05 SiO 2 (wt. %) 12.13 10.85 9.16 11.21 11.61 11.52 11.08 SO 3 (wt. %) 0.28 1.55 4.43 0.29 0.72 0.28 1.26 TiO 2 (wt. %) 0.24 0.21 0.17 0.24 0.22 0.22 0.22 Moisture (wt. %) 0.23 0.23 0.04 0.28 0.25 0.29 0.22 LOI (wt. %) 35.71 32.90 19.70 36.34 34.53 36.10 32.55 As (ppm) 7 1825162 2018 Ba (ppm) 443 294 246 295 278 298 309 Cd (ppm) ND ND ND ND ND ND NA Cl (ppm) 23 24 42 114 43 111 60 Co (ppm) 18 13 ND 20 13 19 17 Cr (ppm) 44 36 63 42 43 42 45 Cu (ppm) 14 ND 18 14 13 ND 15 Hg (ppm) <0.01 0.02 <0.01 <0.01 <0.01 <0.01 <0.01 Mn (ppm) 222 188 125 153 160 162 168 Mo (ppm) ND ND ND ND ND ND NA Ni (ppm) 15 17 17 14 15 11 15 Pb (ppm) 19 22 ND 25 15 11 18 Sb (ppm) 30 73 76 45 74 50 58 Se (ppm) ND 2 4 ND 2 2 2 Sr (ppm) 310 281 341 276 283 270 293 V (ppm) 58 48 43 52 44 54 50 Zn (ppm) 110 93 61 108 120 114 101 Notes: NA - Not Applicable ND - Not Detected 7/12/2006 7/13/2006 AverageProperty 325 B.2.7. CHEMICAL COMPOSITION OF CLINKER Table B.2.12.a: CPR - Chemical Composition of Clinker for 7/11/06 and 7/12/06 8:30 AM 9:51 AM 11:50 AM 2:11 PM 4:00 PM 5:56 PM 8:25 PM 10:26 PM 12:09 AM 2:30 AM 4:32 AM 6:05 AM 8:27 AM 10:27 AM 11:41 AM 2:12 PM 3:48 PM 6:09 PM 8:31 PM Al 2 O 3 5.22 5.12 5.14 4.91 4.97 5.06 5.06 5.00 5.20 5.06 4.95 4.95 5.06 4.88 4.98 5.08 5.28 5.28 5.13 CaO 64.43 64.44 64.29 64.53 64.53 64.35 64.33 64.55 64.51 64.56 64.38 64.53 64.39 64.26 64.39 64.63 64.57 64.58 64.71 Fe 2 O 3 3.15 3.18 3.08 3.16 3.09 3.11 3.19 3.23 3.20 3.27 3.28 3.37 3.38 3.45 3.53 3.37 3.43 3.31 3.16 K 2 O 0.48 0.46 0.50 0.47 0.47 0.47 0.45 0.46 0.52 0.48 0.50 0.46 0.47 0.51 0.48 0.47 0.50 0.51 0.49 MgO 3.59 3.66 3.75 3.83 3.62 3.70 3.56 3.69 3.61 3.75 3.77 3.73 3.60 3.71 3.75 3.45 3.27 3.22 3.22 Na 2 O 0.11 0.11 0.10 0.10 0.10 0.12 0.12 0.10 0.11 0.11 0.11 0.10 0.10 0.11 0.10 0.10 0.09 0.10 0.10 Na 2 O eq 0.43 0.41 0.43 0.41 0.41 0.43 0.42 0.40 0.45 0.43 0.44 0.40 0.41 0.45 0.42 0.41 0.42 0.44 0.42 SiO 2 20.98 21.03 21.07 21.03 20.94 20.92 20.74 21.13 21.06 21.10 21.05 21.24 21.14 21.15 21.28 21.18 21.20 21.15 21.37 SO 3 0.69 0.65 0.70 0.80 0.65 0.67 0.66 0.62 0.78 0.71 0.86 0.63 0.70 0.79 0.73 0.68 0.64 0.89 0.71 F CaO 1.09 0.76 1.04 0.93 0.93 1.42 1.74 1.74 1.74 1.64 1.80 0.65 0.60 1.04 0.87 1.47 1.04 1.14 0.82 C 3 A 8.50 8.20 8.40 7.70 7.90 8.10 8.00 7.80 8.40 7.90 7.60 7.40 7.70 7.10 7.20 7.80 8.20 8.40 8.20 C 4 AF 9.60 9.70 9.40 9.60 9.40 9.50 9.70 9.80 9.70 10.00 10.00 10.30 10.30 10.50 10.70 10.30 10.40 10.10 9.60 C 3 S 63.27 63.56 62.66 65.37 65.75 64.54 65.71 63.99 63.05 63.79 64.17 63.20 62.64 63.15 61.90 63.19 61.37 61.96 62.04 C 2 S 12.42 12.34 13.14 10.98 10.43 11.29 9.89 12.31 12.81 12.37 11.94 13.21 13.35 13.00 14.31 13.05 14.48 13.89 14.46 7/12/2006 Property (wt. %) 7/11/2006 326 Table B.2.12.b: CPR - Chemical Composition of Clinker for 7/13/06 and 7/14/06 1:05 AM 2:34 AM 4:08 AM 5:44 AM 8:09 AM 10:18 AM 12:04 PM 2:52 PM 4:06 PM 5:54 PM 8:09 PM 10:08 PM 12:21 AM 2:12 AM 4:01 AM 5:44 AM Al 2 O 3 4.96 5.09 5.12 5.03 5.07 5.16 5.17 5.09 5.07 5.14 5.17 5.10 5.20 5.04 5.07 4.99 5.08 2.0 0.840 CaO 64.65 64.68 64.50 64.48 64.51 64.56 64.58 64.49 64.54 64.45 64.47 64.41 64.35 64.45 64.36 64.48 64.48 0.2 0.908 Fe 2 O 3 3.26 3.29 3.34 3.39 3.39 3.44 3.43 3.46 3.64 3.55 3.59 3.56 3.49 3.54 3.57 3.55 3.36 4.7 0.289 K 2 O 0.50 0.49 0.51 0.45 0.48 0.50 0.50 0.48 0.48 0.45 0.46 0.49 0.50 0.47 0.49 0.49 0.48 3.8 0.118 MgO 3.35 3.22 3.32 3.45 3.35 3.32 3.33 3.39 3.33 3.37 3.36 3.38 3.31 3.42 3.36 3.44 3.49 5.4 2 <0.005 Na 2 O 0.11 0.09 0.10 0.12 0.10 0.10 0.10 0.09 0.08 0.09 0.10 0.10 0.10 0.08 0.11 0.09 0.10 9.6 2 <0.005 Na 2 O eq 0.44 0.41 0.44 0.42 0.42 0.43 0.43 0.41 0.40 0.39 0.40 0.42 0.43 0.39 0.43 0.41 0.42 3.7 2 0.069 SiO 2 21.27 21.22 21.32 21.35 21.30 21.29 21.32 21.41 21.31 21.30 21.51 21.54 21.40 21.57 21.46 21.50 21.22 0.9 0.869 SO 3 0.60 0.61 0.64 0.54 0.66 0.72 0.67 0.61 0.65 0.57 0.58 0.73 0.55 0.59 0.64 0.61 0.67 12.1 0.117 F CaO 2.13 0.87 1.14 0.71 1.14 0.87 0.71 1.09 1.36 0.71 0.93 0.60 0.55 0.60 0.71 0.60 1.06 38.8 2 <0.005 C 3 A 7.60 7.90 7.90 7.60 7.70 7.90 7.90 7.60 7.30 7.60 7.60 7.50 7.90 7.40 7.40 7.20 7.79 4.9 0.416 C 4 AF 9.90 10.00 10.20 10.30 10.30 10.50 10.40 10.50 11.10 10.80 10.90 10.80 10.60 10.80 10.90 10.80 10.21 4.7 0.206 C 3 S 63.56 63.14 61.38 61.60 61.83 61.44 61.24 60.68 61.52 60.89 59.12 59.16 59.40 59.52 59.75 60.50 62.29 2.8 0.544 C 2 S 13.04 13.20 14.82 14.74 14.42 14.69 14.93 15.61 14.68 15.13 17.07 17.13 16.54 16.94 16.45 16.00 13.86 13.2 0.602 Notes: 1 Based on Anderson-Darling Normality Test 2 Data not normally distributed Property (wt. %) Average C. V. (%) Normality P-Value 1 7/13/2006 7/14/2006 Table B.2.13: ELR - Chemical Composition of Clinker Property 4/18/2006 4/19/2006 4/20/2006 Average Al 2 O 3 (wt. %) 4.91 5.27 4.93 5.04 CaO (wt. %) 64.72 63.53 64.57 64.27 Fe 2 O 3 (wt. %) 3.15 3.35 3.29 3.26 K 2 O (wt. %) 0.48 0.57 0.49 0.51 MgO (wt. %) 3.85 3.47 3.28 3.53 Na 2 O (wt. %) 0.00 0.09 0.06 0.05 P 2 O 5 (wt. %) 0.06 0.07 0.08 0.07 SiO 2 (wt. %) 21.36 22.20 22.07 21.88 SO 3 (wt. %) 0.67 0.82 0.62 0.71 TiO 2 (wt. %) 0.25 0.27 0.28 0.27 Moisture (wt. %) 0.04 0.01 0.04 0.03 LOI (wt. %) 0.47 0.36 0.33 0.39 As (ppm) 19 23 22 21 Ba (ppm) 186 200 224 203 Cd (ppm) ND ND 3 3 Cl (ppm) 286 863 124 424 Co (ppm) ND ND ND NA Cr (ppm) 75 81 78 78 Cu (ppm) 19 29 29 26 Hg (ppm) 0.03 0.04 0.02 0.03 Mn (ppm) 619 513 450 527 Mo (ppm) ND ND ND NA Ni (ppm) 15 23 16 18 Pb (ppm) 30 ND 38 34 Sb (ppm) 60 53 35 49 Se (ppm) ND ND 2 2 Sr (ppm) 389 403 398 397 V (ppm) 60 66 69 65 Zn (ppm) 168 190 204 187 Notes: NA - Not Applicable ND - Not Detected 327 B.2.8. CHEMICAL COMPOSITION OF CEMENT Table B.2.14.a: CPR - Chemical Composition of Cement for 7/11/06 and 7/12/06 328 7:15 AM 9:51 AM 1:17 PM 4:01 PM 6:54 PM 9:58 PM 1:13 AM 2:45 AM 4:25 AM 7:19 AM 10:27 AM 11:25 AM 1:11 PM 3:47 PM 7:40 PM 10:15 PM Al 2 O 3 4.4 4.61 4.66 4.55 4.6 4.56 4.67 4.71 4.67 4.61 4.48 4.67 4.77 4.78 4.67 4.66 CaO 62.86 62.81 61.92 62.56 61.72 62.62 62.77 62.91 63.16 62.48 63.01 62.53 62.46 62.64 62.43 62.99 Fe 2 O 3 3 3 2.89 2.86 2.88 2.91 2.93 2.96 2.97 2.98 3.04 3.1 3.11 3.07 2.95 2.93 K 2 O 0.44 0.45 0.42 0.43 0.42 0.43 0.44 0.42 0.42 0.46 0.44 0.45 0.44 0.46 0.44 0.46 MgO 3.12 3.32 3.54 3.49 3.52 3.49 3.56 3.55 3.47 3.24 3.35 3.55 3.49 3.17 3.12 3.05 Na 2 O 0.11 0.1 0.17 0.13 0.14 0.12 0.13 0.12 0.11 0.11 0.11 0.13 0.12 0.12 0.13 0.11 Na 2 O eq 0.4 0.4 0.45 0.41 0.42 0.4 0.42 0.4 0.39 0.41 0.4 0.43 0.41 0.42 0.42 0.41 SiO 2 19.95 20.36 19.74 19.59 19.47 19.58 19.89 19.94 19.84 19.97 19.46 20.07 20.16 19.85 19.66 19.91 SO 3 2.74 2.44 2.37 2.32 2.78 2.95 2.87 2.26 2.55 2.69 2.23 2.55 2.53 2.63 2.76 2.8 F CaO 1.14 1.2 1.04 0.93 0.93 1.31 1.36 NR 1.09 1.2 0.87 NR 0.93 1.2 1.25 1.04 LOI 1.41 1.48 1.1 1.2 0.92 1.09 1.12 NR 0.97 1.4 0.92 NR 1.4 0.98 1.14 1.31 C 3 A 6.6 7.1 7.5 7.2 7.3 7.2 7.4 7.5 7.4 7.2 6.7 7.1 7.4 7.5 7.4 7.4 C 4 AF 9.1 9.1 8.8 8.7 8.8 8.9 8.9 9 9 9.1 9.3 9.4 9.5 9.3 9 8.9 C 3 S 62.6 58.7 59.8 64.5 60.3 62.9 60.6 62.2 63.4 59.7 67.8 58.9 57.3 60.1 61.3 61.6 C 2 S 10 14.1 11.4 7.5 10.3 8.7 11.3 10.2 9 12.2 4.6 13.1 14.5 11.5 10.1 10.6 Blaine SSA (m 2 /kg) 379 391 391 389 402 398 389 NR 389 402 389 NR 377 381 381 388 Notes: NR - Not Reported Property (wt. %) 7/12/20067/11/2006 Table B.2.14.b: CPR - Chemical Composition of Cement for 7/13/06 and 7/14/06 1:33 AM 4:01 AM 7:02 AM 10:15 AM 3:18 PM 4:01 PM 6:56 PM 9:52 PM 12:58 AM 3:35 AM 6:50 AM 9:47 AM Al 2 O 3 4.7 4.61 4.65 4.62 4.73 4.64 4.87 4.83 4.74 4.69 4.71 4.62 4.66 2.1 0.331 CaO 63.03 62.96 62.87 62.56 62.47 62.59 62.87 62.45 61.74 61.47 62.57 62.29 62.56 0.7 2 0.008 Fe 2 O 3 3 3 3.04 3.04 3.08 3.1 3.14 3.14 3.13 3.13 3.17 3.14 3.02 3.0 0.297 K 2 O 0.45 0.45 0.44 0.46 0.45 0.46 0.46 0.46 0.47 0.45 0.47 0.45 0.45 3.4 2 0.023 MgO 3.1 3.08 3.12 3.08 3.16 3.09 3.24 3.22 3.18 3.17 3.17 3.13 3.28 5.5 2 <0.005 Na 2 O 0.12 0.12 0.11 0.12 0.12 0.1 0.11 0.12 0.1 0.11 0.11 0.11 0.12 12.0 2 <0.005 Na 2 O eq 0.42 0.42 0.4 0.42 0.42 0.4 0.41 0.42 0.41 0.41 0.42 0.41 0.41 2.9 2 <0.005 SiO 2 20.06 19.93 20.06 19.76 20.19 19.95 20.44 20.4 20.17 20.22 20.43 20.08 19.97 1.4 0.810 SO 3 2.5 2.53 2.7 2.84 2.62 2.81 2.49 2.64 2.72 2.72 2.71 3 2.63 7.5 0.751 F CaO 0.71 1.04 0.98 1.14 0.76 1.09 0.82 0.6 0.71 0.55 0.87 1.04 0.99 21.5 0.751 LOI 1.3 1.28 1.14 1.21 1.35 1.17 1.29 1.26 1.38 1.4 1.26 1.34 1.22 13.1 0.270 C 3 A 7.4 7.1 7.2 7.1 7.3 7.1 7.6 7.5 7.3 7.1 7.1 6.9 7.24 3.3 2 0.030 C 4 AF 9.1 9.1 9.3 9.3 9.4 9.4 9.6 9.6 9.5 9.5 9.6 9.6 9.21 3.0 0.109 C 3 S 61.1 62.4 60.2 61 57.2 59.6 56.3 54.7 54 52.8 55.5 56.9 59.76 5.6 0.623 C 2 S 11.4 10.1 12.1 10.6 14.7 12.3 16.1 17.2 17.1 18.1 16.7 14.7 12.15 26.2 0.281 Blaine SSA (m 2 /kg) 377 377 364 366 363 372 379 368 370 365 379 374 381 3.0 0.376 Notes: 1 Based on Anderson-Darling Normality Test 2 Data not normally distributed 7/13/2006 7/14/2006 Property (wt. %) Average Normality P-Value 1 C. V. (%) 329 Table B.2.15: ELR - Chemical Composition of Cement Property 7/11/2006 7/12/2006 7/13/2006 Average Al 2 O 3 (wt. %) 4.85 4.76 4.85 4.82 CaO (wt. %) 62.88 63.34 62.95 63.06 Fe 2 O 3 (wt. %) 2.96 3.07 3.18 3.07 K 2 O (wt. %) 0.47 0.47 0.49 0.48 MgO (wt. %) 3.61 3.32 3.22 3.39 Na 2 O (wt. %) 0.09 0.08 0.06 0.08 P 2 O 5 (wt. %) 0.05 0.07 0.06 0.06 SiO 2 (wt. %) 20.99 20.89 21.29 21.06 SO 3 (wt. %) 2.96 2.82 2.94 2.91 TiO 2 (wt. %) 0.25 0.24 0.25 0.25 Moisture (wt. %) 0.39 0.47 0.58 0.48 LOI (wt. %) 0.89 0.94 0.71 0.85 C 3 S (wt. %) 51.21 54.70 48.97 51.63 C 2 S (wt. %) 21.55 18.63 24.10 21.42 C 3 A (wt. %) 7.85 7.42 7.46 7.58 C 4 AF (wt. %) 8.99 9.34 9.68 9.34 TOC (wt. %) <0.1 <0.1 <0.1 <0.1 As (ppm) 19 17 19 18 Ba (ppm) 71 171 171 138 Cd (ppm) 3NDND3 Cl (ppm) 1067 233 324 541 Co (ppm) ND ND ND NA Cr (ppm) 82 80 76 80 Cu (ppm) 22 43 29 31 Hg (ppm) 0.02 0.02 0.02 0.02 Mn (ppm) 596 467 441 502 Mo (ppm) ND ND ND NA Ni (ppm) 22 20 16 19 Pb (ppm) 7 446137 Sb (ppm) 72 64 53 63 Se (ppm) 1ND2 2 Sr (ppm) 404 403 399 402 V (ppm) 39 57 62 53 Zn (ppm) 152 193 203 183 Notes: NA - Not Applicable ND - Not Detected 330 B.2.9. PHYSICAL PROPERTIES OF CEMENT Table B.2.16: CPR - Physical Properties of Cement Property 7/11/2006 7/12/2006 7/13/2006 Average Air in Mortar (%) 5.1 5.8 6.5 5.8 Blaine Specific Surface Area (m 2 /kg) 385 391 368 381 Autoclave Expansion (% Exp.) 0.10 0.12 0.08 0.10 Cube Flow (%) 119.0 123.0 128.0 123.3 Comp Str 1day (MPa) 16.7 14.9 14.5 15.4 Comp Str 3day (MPa) 26.5 24.6 24.0 25.0 Comp Str 7day (MPa) 33.5 32.6 31.6 32.6 Comp Str 28day (MPa) 45.9 43.7 42.4 44.0 Normal Consistency (%) 25.7 25.8 25.7 25.7 Gillmore Initial Set (Min) 120 105 120 115 Gillmore Final Set (Min) 225 255 320 267 Vicat Initial Set (Min) 80 61 78 73 Vicat Final Set (Min) 210 240 255 235 Notes: % Exp. - % Expansion Table B.2.17: AUR - Physical Properties of Cement Property Composite Autoclave Expansion (% Exp.) 0.03 Cube Flow (%) 98 Comp Str 1day (MPa) 11 Comp Str 3day (MPa) 23.1 Comp Str 7day (MPa) 29.8 Comp Str 28day (MPa) 39.5 Normal Consistency (%) 26.2 Gillmore Initial Set (Min) 72 Gillmore Final Set (Min) 145 Vicat Initial Set (Min) 69 Vicat Final Set (Min) 137 Drying Shrinkage @ 7 days (% LC) -0.051 Drying Shrinkage @ 14 days (% LC) -0.072 Drying Shrinkage @ 21 days (% LC) -0.083 Drying Shrinkage @ 28 days (% LC) -0.094 Notes: % LC - Percent Length Change % Exp. - Percent Expansion 331 332 448 days 0.049 0.047 NC Permeability @ 91 days (Coulombs) 2930 2550 2660 Notes: CIP - Collection in Progress NC - Not Collected 1 Percentage decrease in length B.2.10. PROPERTIES OF CONCRETE Table B.2.18: Concrete Properties CPR Mix w/c=0.44 Mix w/c=0.37 Mix w/c=0.44 Total Air Content (%) 4.25 4.0 3.2 Slump (mm) 90 160 30 Unit Weight (kg/m 3 ) 2439 2427 2448 Initial Set (Min.) 218 239 247 Final Set (Min.) 273 290 NC Compressive Strength (MPa) 1 day 13.9 25.9 15.1 3 days 20.7 36.1 21.9 7 days 28.4 40.0 32.8 28 days 37.1 49.7 42.2 91 days 41.4 59.1 49.6 Splitting Tensile Strength (MPa) 1 day 2.0 3.0 NC 3 days 2.3 3.7 NC 7 days 2.8 3.9 NC 28 days 3.3 4.3 NC 91 days 4.0 4.9 NC Drying Shrinkage Development (% Length Change) 1 4 days 0.018 0.011 NC 7 days 0.027 0.020 NC 14 days 0.034 0.025 NC 28 days 0.035 0.030 NC 56 days 0.036 0.039 NC 112 days 0.044 0.040 NC 224 days 0.047 0.045 NC Property AUR B.2.11. EMISSIONS Table B.2.19: CPR - Emissions Time NO x (tons/ton clinker) SO 2 (tons/ton clinker) VOC (tons/ton clinker) CO (tons/ton clinker) 7/11/2006 7:00 1.45E-03 1.03E-05 2.35E-05 6.20E-04 7/11/2006 8:00 1.36E-03 8.88E-06 2.82E-05 5.83E-04 7/11/2006 9:00 1.32E-03 9.61E-06 3.72E-05 5.93E-04 7/11/2006 10:00 9.53E-04 8.59E-06 2.18E-05 3.67E-04 7/11/2006 11:00 8.24E-04 1.30E-05 1.21E-05 3.39E-04 7/11/2006 12:00 1.07E-03 8.63E-06 3.14E-05 4.71E-04 7/11/2006 13:00 1.22E-03 7.61E-06 3.31E-05 4.48E-04 7/11/2006 14:00 1.22E-03 9.65E-06 3.86E-05 4.71E-04 7/11/2006 15:00 1.29E-03 8.22E-06 3.93E-05 4.99E-04 7/11/2006 16:00 1.27E-03 9.87E-06 4.12E-05 4.99E-04 7/11/2006 17:00 1.33E-03 1.14E-05 4.12E-05 5.54E-04 7/11/2006 18:00 1.37E-03 1.02E-05 4.50E-05 5.62E-04 7/11/2006 19:00 1.42E-03 1.16E-05 4.43E-05 5.82E-04 7/11/2006 20:00 1.40E-03 9.13E-06 4.89E-05 5.46E-04 7/11/2006 21:00 1.27E-03 4.88E-06 5.86E-05 5.63E-04 7/11/2006 22:00 1.31E-03 7.59E-06 7.40E-05 5.44E-04 7/11/2006 23:00 1.37E-03 1.01E-05 7.55E-05 5.18E-04 7/12/2006 0:00 1.46E-03 1.27E-05 4.23E-05 5.29E-04 7/12/2006 1:00 1.30E-03 8.17E-06 3.49E-05 5.86E-04 7/12/2006 2:00 1.27E-03 1.37E-05 3.30E-05 6.33E-04 7/12/2006 3:00 1.23E-03 1.19E-05 3.00E-05 5.93E-04 7/12/2006 4:00 1.34E-03 1.39E-05 3.10E-05 6.00E-04 7/12/2006 5:00 1.33E-03 2.03E-05 2.22E-05 6.83E-04 7/12/2006 6:00 1.25E-03 1.26E-05 2.93E-05 6.98E-04 7/12/2006 7:00 1.33E-03 1.59E-05 2.05E-05 6.47E-04 7/12/2006 8:00 1.19E-03 1.75E-05 1.53E-05 5.99E-04 7/12/2006 9:00 1.19E-03 1.68E-05 1.64E-05 5.55E-04 7/12/2006 10:00 1.15E-03 1.90E-05 1.96E-05 5.11E-04 7/12/2006 11:00 1.19E-03 2.02E-05 2.34E-05 5.59E-04 7/12/2006 12:00 1.24E-03 1.07E-05 2.55E-05 5.71E-04 7/12/2006 13:00 1.10E-03 8.74E-06 3.22E-05 5.84E-04 7/12/2006 14:00 1.09E-03 5.53E-06 4.72E-05 5.97E-04 7/12/2006 15:00 1.12E-03 5.55E-06 4.32E-05 5.90E-04 7/12/2006 16:00 1.21E-03 4.89E-06 4.27E-05 5.69E-04 7/12/2006 17:00 1.17E-03 5.52E-06 4.15E-05 5.42E-04 7/12/2006 18:00 1.14E-03 5.73E-06 4.10E-05 5.53E-04 7/12/2006 19:00 1.13E-03 5.61E-06 3.90E-05 5.91E-04 7/12/2006 20:00 1.18E-03 5.22E-06 3.67E-05 5.73E-04 7/12/2006 21:00 1.18E-03 5.05E-06 3.57E-05 5.44E-04 7/12/2006 22:00 1.15E-03 6.43E-06 2.88E-05 4.73E-04 7/12/2006 23:00 1.15E-03 6.90E-06 2.83E-05 4.95E-04 7/13/2006 0:00 1.17E-03 7.77E-06 2.76E-05 5.78E-04 7/13/2006 1:00 1.20E-03 6.61E-06 2.65E-05 5.39E-04 7/13/2006 2:00 1.21E-03 6.57E-06 2.63E-05 5.47E-04 7/13/2006 3:00 1.20E-03 5.74E-06 2.62E-05 5.43E-04 7/13/2006 4:00 1.14E-03 6.52E-06 2.57E-05 5.74E-04 7/13/2006 5:00 1.22E-03 5.75E-06 2.43E-05 5.14E-04 7/13/2006 6:00 1.25E-03 1.00E-05 2.10E-05 4.75E-04 333 334 Table B.2.20: CPR - Emissions Time NO x (tons/ton clinker) SO 2 (tons/ton clinker) VOC (tons/ton clinker) CO (tons/ton clinker) 7/13/2006 7:00 1.23E-03 5.89E-05 1.15E-05 5.63E-04 7/13/2006 8:00 1.08E-03 3.68E-06 2.67E-05 5.87E-04 7/13/2006 9:00 1.10E-03 3.40E-06 3.20E-05 5.18E-04 7/13/2006 10:00 1.19E-03 2.13E-05 3.35E-05 6.10E-04 7/13/2006 11:00 1.23E-03 1.14E-04 2.62E-05 6.37E-04 7/13/2006 12:00 1.15E-03 7.42E-05 3.57E-05 5.66E-04 7/13/2006 13:00 1.15E-03 3.13E-06 4.87E-05 5.60E-04 7/13/2006 14:00 1.20E-03 3.24E-06 4.91E-05 5.02E-04 7/13/2006 15:00 1.20E-03 3.59E-06 4.50E-05 5.09E-04 7/13/2006 16:00 1.12E-03 3.17E-06 4.64E-05 5.13E-04 7/13/2006 17:00 1.10E-03 2.75E-06 4.61E-05 5.12E-04 7/13/2006 18:00 1.10E-03 3.66E-06 4.52E-05 5.02E-04 7/13/2006 19:00 1.14E-03 3.61E-06 4.47E-05 4.81E-04 7/13/2006 20:00 1.13E-03 2.68E-06 4.69E-05 4.84E-04 7/13/2006 21:00 1.11E-03 3.34E-06 5.42E-05 4.66E-04 7/13/2006 22:00 1.12E-03 3.65E-06 3.08E-05 4.64E-04 7/13/2006 23:00 1.12E-03 3.82E-06 2.77E-05 4.91E-04 7/14/2006 0:00 1.15E-03 3.62E-06 2.98E-05 5.30E-04 7/14/2006 1:00 1.12E-03 3.86E-06 2.73E-05 4.83E-04 7/14/2006 2:00 1.21E-03 4.57E-06 2.64E-05 5.07E-04 7/14/2006 3:00 1.20E-03 4.90E-06 2.62E-05 4.79E-04 7/14/2006 4:00 1.21E-03 4.51E-06 2.47E-05 4.74E-04 7/14/2006 5:00 1.22E-03 4.58E-06 2.47E-05 4.61E-04 7/14/2006 6:00 1.21E-03 3.95E-06 2.51E-05 4.69E-04 Average 1.20E-03 1.12E-05 3.42E-05 5.39E-04 C. V. (%) 8.8 145.6 35.8 11.7 Normality P-Value 1 0.017 <0.005 0.008 0.22 Notes: 1 Based on Anderson Darling Normality Test NC - Not Collected 358 APPENDIX B.4 RAW DATA FOR CT2 BURN B.4.1. GENERAL COMMENTS ? The raw data from the CT2 burn are presented in this appendix. ? Coal and scrap tires are the fuels used in the burn. ? The burn lasted from 9 AM on May 16, 2007 to 9 AM on May 19, 2007. ? Cement and concrete results not collected for the burn. B.4.2. NOTATION CPR ? Cement Plant Results ELR ? External Lab Results AUR ? Auburn University Results C. V. ? Coefficient of Variation 359 B.4.3. Property (wt. %) Raw Material O Material Five Raw Material Six Al 2 O 3 23.90 0.69 NR 10.60 1.54 0.74 CaO 3.02 53.00 NR 31.70 5.02 43.20 Fe 2 O 3 2.14 NR NR 16.80 NR 0.49 K 2 O 2.34 0.08 NR 0.10 0.19 0.09 MgO 0.97 1.20 NR 12.80 0.92 0.51 Na 2 O 0.30 NR NR NR NR NR SiO 2 57.70 1.83 NR 23.80 87.70 3.41 SO 3 0.93 0.16 NR 0.92 3.95 47.60 Moisture 30.10 3.10 NR NR 4.90 25.00 LOI 6.90 43.00 NR NR 0.43 3.90 Notes: NR - Not Reported CHEMICAL COMPOSITION OF RAW MATERIALS Table B.4.1: CPR - Chemical Composition of Raw Materials ne Raw Material Two Raw Material Three Raw Material Four Raw Table B.4.2: ELR - Chemical Composition of Raw Materials Property Raw Material One Raw Material Two Raw Material Three Raw Material Four Raw Material Five Raw Material Six Al 2 O 3 (wt. %) 26.84 1.86 3.19 4.50 1.37 0.55 CaO (wt. %) 2.82 90.04 71.72 34.88 4.08 43.11 Fe 2 O 3 (wt. %) 12.35 1.02 2.25 30.69 3.45 0.35 K 2 O (wt. %) 2.81 0.30 0.51 0.03 0.12 0.15 MgO (wt. %) 1.46 1.77 2.43 12.82 1.56 0.53 Na 2 O (wt. %) 0.49 0.06 0.04 0.05 0.02 0.06 P 2 O 5 (wt. %) 0.57 0.05 0.01 0.48 0.04 0.00 SiO 2 (wt. %) 50.61 4.53 19.36 11.57 88.40 4.39 SO 3 (wt. %) 0.17 0.20 0.14 0.30 0.04 50.73 TiO 2 (wt. %) 1.39 0.06 0.24 0.24 0.18 0.02 Moisture (wt. %) 21.56 2.26 0.77 2.42 3.41 19.36 LOI (wt. %) 7.35 40.66 34.34 0.55 0.41 7.34 As (ppm) 163 3 5 10 5 2 Ba (ppm) 2300 500 253 290 200 200 Cd (ppm) ND ND ND ND ND ND Cl (ppm) 76 39 30 30 42 16 Co (ppm) 67 15 14 11 5 2 Cr (ppm) 159 18 29 2078 220 ND Cu (ppm) 184 5 15 12 ND ND Hg (ppm) ND ND ND ND ND ND Mn (ppm) 500 200 253 43970 6900 200 Mo (ppm) 18 ND ND 114 ND ND Ni (ppm) 121 ND ND 35 ND ND Pb (ppm) 79 ND ND ND 5 7 Sb (ppm) NR NR NR NR NR NR Se (ppm) ND ND ND ND 4 ND Sr (ppm) 2000 600 400 300 100 800 V (ppm) 326 26 35 680 170 11 Zn (ppm) 157 8 8 82 0 ND Notes: ND - Not Detected 360 361 B.4.4. CHEMICAL COMPOSITION OF KILN FEED Table B.4.3: CPR - Chemical Composition of Kiln Feed 5/16/2007 1:49 PM 1:36 AM 2:13 PM 2:04 AM 1:55 PM 2:02 AM 11:00 AM 2:15 AM 2:10 PM Al 2 O 3 3.05 2.98 3.12 3.16 3.04 3.04 2.98 3.13 3.09 3.07 2.1 CaO 43.74 43.94 43.62 43.71 43.70 43.69 43.64 43.80 43.58 43.71 0.2 Fe 2 O 3 1.97 1.95 2.06 1.95 1.99 1.97 2.06 2.00 2.14 2.01 3.2 K 2 O 0.30 0.32 0.34 0.35 0.34 0.34 0.33 0.30 0.29 0.32 6.7 MgO 2.11 2.04 2.06 1.93 2.00 2.05 2.23 2.18 2.17 2.09 4.6 Na 2 O 0.03 0.04 0.03 0.04 0.03 0.04 0.03 0.03 0.03 0.03 15.0 Na 2 O eq 0.23 0.25 0.25 0.27 0.25 0.26 0.25 0.23 0.22 0.25 6.5 SiO 2 13.42 13.02 13.33 13.03 12.99 13.30 13.46 13.06 12.97 13.18 1.5 SO 3 0.22 0.19 0.16 0.15 0.15 0.16 0.18 0.17 0.18 0.17 12.9 LOI NR NR NR NR NR NR NR NR NR NR NA Notes: NR - Not Reported NA - Not Applicable 5/20/2007 C. V. (%)Property (wt. %) Average 5/17/2007 5/18/2007 5/19/2007 Table B.4.4: ELR - Chemical Composition of Kiln Feed Property 3-Day Composite Al 2 O 3 (wt. %) 4.09 CaO (wt. %) 64.08 Fe 2 O 3 (wt. %) 3.11 K 2 O (wt. %) 0.46 MgO (wt. %) 3.18 Na 2 O (wt. %) 0.08 P 2 O 5 (wt. %) 0.05 SiO 2 (wt. %) 24.18 SO 3 (wt. %) 0.26 TiO 2 (wt. %) 0.26 Moisture (wt. %) 0.31 LOI (wt. %) 33.30 As (ppm) 23 Ba (ppm) 200 Cd (ppm) ND Cl (ppm) 97 Co (ppm) 14 Cr (ppm) 96 Cu (ppm) 28 Hg (ppm) ND Mn (ppm) 1800 Mo (ppm) ND Ni (ppm) 5 Pb (ppm) ND Sb (ppm) NR Se (ppm) 3 Sr (ppm) 500 V (ppm) 61 Zn (ppm) 21 Notes: NR - Not Reported ND - Not Detected 362 B.4.5. CHEMICAL COMPOSITION OF FUELS Table B.4.5: CPR - Chemical Composition of Coal Test Parameter Value (wt. %) Ash 16.17 Fixed Carbon 54.88 Volatile Matter 28.95 Carbon 72.63 Hydrogen 4.38 Nitrogen 1.39 Oxygen 3.56 Sulfur 2.72 Al 2 O 3 21.60 CaO 7.83 Fe 2 O 3 15.74 K 2 O 2.05 MgO 1.03 Na 2 O 0.15 SiO 2 43.35 SO 3 6.80 12864 Notes: 1 Value is Reported as BTU/lb Heat Value 1 Proximate Analysis Ul ti mate An alysis S t an d a rd Parameters 363 Table B.4.6: ELR - Proximate, Ultimate, and Combustion Analysis of Coal Test Parameter Value (wt. %) Ash 14.51 Fixed Carbon 30.19 Volatile Matter 55.3 Carbon 72.24 Hydrogen 3.71 Nitrogen 0.5 Oxygen 7.49 Sulfur 1.55 12864 Notes: 1 Value is Reported as BTU/lb Proximate Analysis Ul ti mate An aly s is Heat Value 1 364 Table B.4.7: ELR - Standard Parameters of Coal Property 3-Day Composite Al 2 O 3 (wt. %) 22.86 CaO (wt. %) 5.63 Fe 2 O 3 (wt. %) 18.66 K 2 O (wt. %) 1.78 MgO (wt. %) 1.01 Na 2 O (wt. %) 0.25 P 2 O 5 (wt. %) 0.35 SiO 2 (wt. %) 42.36 SO 3 (wt. %) 5.54 TiO 2 (wt. %) 1.02 As (ppm) 200 Ba (ppm) 1500 Cd (ppm) ND Cl (ppm) 94 Co (ppm) 61 Cr (ppm) 107 Cu (ppm) 116 Hg (ppm) 0.130 Mn (ppm) 2900 Mo (ppm) 37 Ni (ppm) 107 Pb (ppm) 39 Sb (ppm) NR Se (ppm) 7 Sr (ppm) 900 V (ppm) 210 Zn (ppm) 179 Notes: NR - Not Reported ND - Not Detected 365 Table B.4.8: ELR - Proximate, Ultimate, and Combustion Analysis of Tires Test Parameter Value (wt. %) Ash 14.54 Fixed Carbon 46.91 Moisture 1 0.09 Volatile Matter 38.46 Carbon 77.85 Hydrogen 5.57 Nitrogen 0.07 Oxygen 0.65 Sulfur 1.31 15456 Ul ti mate Analysis Heat Value 2 Proximate Analysis Notes: 1 As Received 2 Value is Reported as BTU/lb 366 367 Table B.4.9: ELR - Standard Parameters for Tires Property 3-Day Composite Al 2 O 3 (wt. %) 0.78 CaO (wt. %) 3.82 Fe 2 O 3 (wt. %) 57.42 K 2 O (wt. %) 0.29 MgO (wt. %) 0.04 Na 2 O (wt. %) 0.47 P 2 O 5 (wt. %) 0.22 SiO 2 (wt. %) 25.12 SO 3 (wt. %) 0.85 TiO 2 (wt. %) 0.40 As (ppm) ND Ba (ppm) 1135 Cd (ppm) ND Cl (ppm) 1174 Co (ppm) 852 Cr (ppm) 94 Cu (ppm) 546 Hg (ppm) 0.2 Mn (ppm) 3600 Mo (ppm) 31 Ni (ppm) 91 Pb (ppm) 17 Sb (ppm) NR Se (ppm) ND Sr (ppm) 0 V (ppm) 50 Zn (ppm) 0 ND - Not Detected Notes: NR - Not Reported 368 B.4.6. CHEMICAL COMPOSITION OF CEMENT KILN DUST (CKD) Table B.4.10: CPR - Chemical Composition of Cement Kiln Dust (CKD) 8:34 AM 3:08 PM 7:54 PM 2:13 PM 11:07 PM 8:06 AM 7:59 PM Al 2 O 3 3.61 4.02 3.82 4.08 3.63 3.6 3.24 3.71 CaO 45.48 43.96 44.77 44.31 45.18 45.08 46.66 45.06 Fe 2 O 3 1.87 2.12 2.02 2.04 1.97 1.86 1.81 1.96 K 2 O 0.43 0.46 0.44 0.48 0.43 0.44 0.41 0.44 MgO 1.28 1.32 1.28 1.28 1.33 1.27 1.32 1.30 Na 2 O 0.04 0.04 0.04 0.04 0.03 0.03 0.03 0.04 SiO 2 11.85 12.32 12.08 12.62 11.86 12.15 11.06 11.99 SO 3 0.15 0.15 0.16 0.27 0.17 0.13 0.16 0.17 5/18/2007 AverageProperty (wt. %) 5/16/2007 5/17/2007 Table B.4.11: ELR - Chemical Composition of Cement Kiln Dust 121212 Al 2 O 3 (wt. %) 5.71 5.40 5.52 5.23 5.20 5.69 5.46 CaO (wt. %) 69.01 70.00 69.40 70.34 70.23 70.47 69.91 Fe 2 O 3 (wt. %) 3.23 2.98 3.10 3.04 2.86 2.69 2.99 K 2 O (wt. %) 0.69 0.66 0.69 0.64 0.64 0.60 0.65 MgO (wt. %) 2.20 2.24 2.08 2.18 2.06 2.18 2.16 Na 2 O (wt. %) 0.08 0.07 0.07 0.07 0.06 0.06 0.07 P 2 O 5 (wt. %) 0.08 0.06 0.07 0.07 0.05 0.05 0.06 SiO 2 (wt. %) 18.13 17.69 18.12 17.66 18.15 17.47 17.87 SO 3 (wt. %) 0.31 0.39 0.40 0.27 0.25 0.31 0.32 TiO 2 (wt. %) 0.35 0.33 0.36 0.33 0.34 0.31 0.34 Moisture (wt. %) 0.28 0.26 0.20 0.29 0.33 0.34 0.28 LOI (wt. %) 35.41 35.04 34.81 35.92 36.07 36.36 35.60 As (ppm) 34 33 27 27 26 19 28 Ba (ppm) 481 489 390 363 503 483 452 Cd (ppm) ND ND ND ND ND ND ND Cl (ppm) 180 155 561 135 118 83 205 Co (ppm) 10 10 14 15 9 18 13 Cr (ppm) 82 48 60 56 52 48 57 Cu (ppm) 26 13 22 ND 35 8 21 Hg (ppm) 0.49 0.39 1.31 0.25 0.26 0.04 0 Mn (ppm) 842 733 781 848 377 604 697 Mo (ppm) ND 1 4 5 ND ND 3 Ni (ppm) 11910129 10 Pb (ppm) 23 ND 7 5 ND 21 14 Sb (ppm) NR NR NR NR NR NR NA Se (ppm) ND ND ND ND ND ND ND Sr (ppm) 481 489 521 484 503 483 493 V (ppm) 77 83 73 74 67 63 73 Zn (ppm) 34 26 26 28 30 24 28 Average Notes: ND - Not Detected NR - Not Reported NA - Not Applicable Property 5/16/2007 5/17/2007 5/18/2007 369 370 B.4.7. CHEMICAL COMPOSITION OF CLINKER Table B.4.12.a: CPR - Chemical Composition of Clinker for 5/16/2007 7:47 AM 9:40 AM 12:06 PM 1:48 PM 4:05 PM 5:45 PM 7:55 PM 10:05 PM 11:27 PM Al 2 O 3 5.00 4.99 5.01 5.08 5.04 5.04 5.10 5.04 5.05 CaO 64.67 64.72 64.80 64.72 64.71 64.53 64.75 64.82 64.78 Fe 2 O 3 3.36 3.35 3.36 3.37 3.31 3.41 3.41 3.38 3.36 K 2 O 0.45 0.44 0.45 0.45 0.47 0.55 0.47 0.45 0.50 MgO 3.53 3.54 3.53 3.50 3.53 3.51 3.48 3.50 3.52 Na 2 O 0.06 0.06 0.06 0.06 0.06 0.06 0.07 0.06 0.06 Na 2 O eq 0.35 0.35 0.35 0.35 0.37 0.43 0.38 0.36 0.39 SiO 2 21.80 21.77 21.62 21.77 21.68 21.66 21.64 21.67 21.63 SO 3 0.71 0.68 0.58 0.69 0.72 0.88 0.71 0.62 0.65 F CaO 0.64 0.91 1.50 0.81 0.48 1.40 1.07 1.02 0.59 C 3 A 7.60 7.50 7.60 7.80 7.70 7.60 7.70 7.60 7.70 C 4 AF 10.20 10.20 10.20 10.30 10.10 10.40 10.40 10.30 10.20 C 3 S 59.30 59.70 61.00 59.10 60.10 59.40 60.00 60.40 60.60 C 2 S 17.80 17.40 15.90 17.80 16.80 17.30 16.80 16.50 16.30 5/16/2007 Property (wt. %) Table B.4.12.b: CPR - Chemical Composition of Clinker for 5/17/2007 371 1:46 AM 4:02 AM 5:49 AM 8:04 AM 10:25 AM 11:40 AM 2:07 PM 3:58 PM 6:05 PM 8:08 PM 10:05 PM 11:51 PM Al 2 O 3 4.94 5.00 4.84 5.24 5.20 5.12 5.17 5.17 5.09 5.16 5.12 5.17 CaO 64.84 64.74 62.78 64.59 64.59 65.03 64.91 64.75 64.83 64.84 64.90 64.79 Fe 2 O 3 3.21 3.41 3.45 3.74 3.63 3.38 3.54 3.47 3.45 3.48 3.40 3.39 K 2 O 0.52 0.52 0.56 0.49 0.52 0.47 0.54 0.51 0.50 0.52 0.51 0.55 MgO 3.41 3.44 3.00 3.40 3.41 3.37 3.39 3.37 3.35 3.31 3.31 3.34 Na 2 O 0.06 0.06 0.07 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 Na 2 O eq 0.40 0.40 0.44 0.39 0.41 0.36 0.41 0.39 0.39 0.41 0.39 0.42 SiO 2 21.70 21.60 20.45 21.50 21.54 21.44 21.40 21.48 21.59 21.57 21.54 21.52 SO 3 0.78 0.78 0.98 0.75 0.77 0.52 0.64 0.64 0.64 0.66 0.59 0.75 F CaO 0.38 0.38 0.54 0.81 0.97 1.34 1.45 1.24 0.21 0.59 0.59 0.59 C 3 A 7.70 7.50 7.00 7.60 7.60 7.80 7.70 7.80 7.70 7.80 7.80 8.00 C 4 AF 9.80 10.40 10.50 11.40 11.00 10.30 10.80 10.60 10.50 10.60 10.30 10.30 C 3 S 61.30 60.90 62.70 59.00 59.10 62.50 61.80 60.60 60.70 60.40 61.20 60.60 C 2 S 16.00 16.00 11.30 17.10 17.10 14.30 14.70 15.80 16.10 16.30 15.60 15.90 Property (wt. %) 5/17/2007 Table B.4.12.c: CPR - Chemical Composition of Clinker for 5/18/2007 2:04 AM 3:55 AM 5:34 AM 8:02 AM 10:02 AM 11:38 AM 1:49 PM 4:05 PM 6:45 PM 7:56 PM 10:34 PM Al 2 O 3 5.15 4.94 5.33 5.39 5.39 5.25 5.33 5.37 5.37 5.21 5.20 CaO 64.84 63.44 64.56 64.49 64.49 64.86 64.54 64.42 64.34 64.64 64.58 Fe 2 O 3 3.36 3.18 3.51 3.60 3.62 3.37 3.63 3.76 3.81 3.56 3.56 K 2 O 0.52 0.59 0.55 0.56 0.56 0.52 0.56 0.55 0.56 0.54 0.53 MgO 3.29 2.90 3.29 3.30 3.27 3.23 3.30 3.32 3.36 3.33 3.36 Na 2 O 0.06 0.06 0.06 0.06 0.07 0.06 0.06 0.06 0.06 0.06 0.07 Na 2 O eq 0.40 0.45 0.43 0.43 0.43 0.40 0.42 0.42 0.43 0.42 0.41 SiO 2 21.60 20.77 21.61 21.59 21.59 21.53 21.56 21.58 21.58 21.61 21.69 SO 3 0.67 0.64 0.79 0.82 0.83 0.60 0.70 0.81 0.79 0.79 0.72 F CaO 0.32 0.64 0.32 0.70 0.75 0.81 0.54 0.54 0.91 0.86 0.86 C 3 A 8.00 7.70 8.20 8.20 8.20 8.20 8.00 7.90 7.80 7.80 7.80 C 4 AF 10.20 9.70 10.70 11.00 11.00 10.20 11.00 11.40 11.60 10.80 10.80 C 3 S 60.40 62.70 57.70 57.10 57.10 60.30 57.90 56.80 56.40 58.90 58.00 C 2 S 16.30 12.30 18.40 18.80 18.90 16.20 18.20 19.00 19.30 17.50 18.40 Property (wt. %) 5/18/2007 372 Table B.4.12.d: CPR - Chemical Composition of Clinker for 5/19/2007 12:01 AM 1:57 AM 4:21 AM 5:33 AM 7:49 AM Al 2 O 3 5.17 5.29 5.21 5.18 5.09 5.08 2.1 <0.005 CaO 64.51 64.52 64.51 64.52 64.40 64.62 0.8 0.039 Fe 2 O 3 3.51 3.56 3.46 3.50 3.66 3.41 3.4 <0.005 K 2 O 0.54 0.53 0.54 0.55 0.55 0.50 8.2 0.077 MgO 3.40 3.40 3.40 3.46 3.45 3.38 4.7 0.589 Na 2 O 0.06 0.06 0.06 0.06 0.07 0.06 4.6 <0.005 Na 2 O eq 0.42 0.41 0.41 0.42 0.43 0.39 7.6 0.053 SiO 2 21.69 21.70 21.75 21.73 21.80 21.52 1.4 <0.005 SO 3 0.85 0.66 0.73 0.60 0.81 0.70 14.2 <0.005 F CaO 1.13 0.81 0.64 1.34 0.81 0.78 49.6 0.374 C 3 A 7.70 8.00 8.00 7.80 7.30 7.70 2.9 0.021 C 4 AF 10.70 10.80 10.50 10.70 11.10 10.39 3.4 <0.005 C 3 S 58.00 57.10 57.40 57.60 57.10 60.47 2.0 0.033 C 2 S 18.40 19.10 19.10 18.80 19.40 16.08 10.1 0.007 AverageProperty (wt. %) 5/19/2007 Notes: 1 Based on Anderson-Darling Normality Test C. V. (%) Normality P-Value 1 373 Table B.4.13: ELR - Chemical Composition of Clinker 1 2 1 212 Al 2 O 3 (wt. %) 4.89 4.93 4.86 4.88 4.99 5.08 4.94 CaO (wt. %) 64.42 64.44 65.08 65.04 64.94 64.76 64.78 Fe 2 O 3 (wt. %) 3.23 3.34 3.12 3.25 3.19 3.32 3.24 K 2 O (wt. %) 0.52 0.53 0.54 0.54 0.54 0.56 0.54 MgO (wt. %) 3.58 3.61 3.46 3.50 3.36 3.38 3.48 Na 2 O (wt. %) 0.07 0.05 0.07 0.06 0.06 0.07 0.06 P 2 O 5 (wt. %) 0.06 0.06 0.05 0.06 0.06 0.06 0.06 SiO 2 (wt. %) 21.83 21.57 21.53 21.48 21.68 21.54 21.60 SO 3 (wt. %) 0.87 0.93 0.75 0.68 0.65 0.73 0.77 TiO 2 (wt. %) 0.25 0.26 0.27 0.27 0.28 0.27 0.27 Moisture (wt. %) 0.05 0.03 0.02 0.02 0.03 0.02 0.03 LOI (wt. %) 0.17 0.32 0.26 0.22 0.18 0.20 0.22 As (ppm) 18 24 16 19 26 24 21 Ba (ppm) 391 393 396 393 395 393 393 Cd (ppm) ND ND ND ND ND ND ND Cl (ppm) 103 119 205 161 155 123 144 Co (ppm) 7912714110 Cr (ppm) 92 89 88 94 80 75 86 Cu (ppm) 27 ND 18 11 20 11 14 Hg (ppm) ND ND ND ND ND ND ND Mn (ppm) 1953 1963 1683 1770 1483 1472 1721 Mo (ppm) 10 1 7 3 ND 3 4 Ni (ppm) 6 8 6 111015 9 Pb (ppm) 24 ND 18 21 ND ND 10 Sb (ppm) NR NR NR NR NR NR NA Se (ppm) ND ND ND ND ND ND ND Sr (ppm) 488 491 495 492 494 491 492 V (ppm) 58 67 59 66 65 66 63 Zn (ppm) 29 36 33 30 51 43 37 Notes: NA - Not Applicable ND - Not Detected AverageProperty 5/16/2007 5/17/2007 5/18/2007 374 B.4.8. EMISSIONS Table B.4.14.a: CPR - Emissions Time NO x (tons/ton clinker) SO 2 (tons/ton clinker) VOC (tons/ton clinker) CO (tons/ton clinker) 5/16/2007 9:00 1.03E-03 1.00E-06 1.68E-05 3.25E-04 5/16/2007 10:00 1.01E-03 1.74E-06 1.71E-05 3.03E-04 5/16/2007 11:00 9.62E-04 2.55E-07 1.72E-05 3.20E-04 5/16/2007 12:00 1.01E-03 4.89E-07 1.90E-05 3.47E-04 5/16/2007 13:00 1.09E-03 4.79E-07 2.12E-05 3.54E-04 5/16/2007 14:00 1.12E-03 6.10E-07 2.24E-05 3.61E-04 5/16/2007 15:00 1.16E-03 4.77E-07 2.57E-05 3.92E-04 5/16/2007 16:00 1.35E-03 8.58E-07 2.70E-05 4.27E-04 5/16/2007 17:00 1.28E-03 8.36E-07 2.68E-05 3.34E-04 5/16/2007 18:00 1.15E-03 5.81E-07 2.65E-05 3.52E-04 5/16/2007 19:00 1.16E-03 8.61E-07 2.54E-05 3.70E-04 5/16/2007 20:00 1.14E-03 7.48E-07 2.55E-05 3.87E-04 5/16/2007 21:00 1.02E-03 1.19E-06 2.13E-05 3.32E-04 5/16/2007 22:00 1.04E-03 9.90E-07 2.23E-05 3.82E-04 5/16/2007 23:00 1.19E-03 1.77E-06 2.49E-05 3.94E-04 5/17/2007 0:00 1.08E-03 1.07E-06 2.24E-05 3.70E-04 5/17/2007 1:00 1.19E-03 1.18E-06 2.22E-05 3.35E-04 5/17/2007 2:00 1.05E-03 1.29E-06 1.86E-05 3.20E-04 5/17/2007 3:00 1.31E-03 1.68E-06 1.99E-05 3.47E-04 5/17/2007 4:00 1.01E-03 1.76E-06 1.93E-05 3.47E-04 5/17/2007 5:00 9.02E-04 1.22E-06 1.80E-05 3.12E-04 5/17/2007 6:00 9.98E-04 1.54E-06 1.81E-05 3.53E-04 5/17/2007 7:00 1.03E-03 1.01E-06 1.78E-05 3.56E-04 5/17/2007 8:00 1.02E-03 1.56E-06 1.54E-05 2.98E-04 5/17/2007 9:00 1.12E-03 7.15E-07 1.72E-05 2.95E-04 5/17/2007 10:00 1.00E-03 2.47E-07 1.65E-05 3.41E-04 5/17/2007 11:00 1.13E-03 2.15E-07 1.52E-05 3.52E-04 5/17/2007 12:00 1.18E-03 1.37E-07 1.50E-05 2.94E-04 5/17/2007 13:00 1.06E-03 1.46E-07 1.51E-05 3.01E-04 5/17/2007 14:00 1.29E-03 1.68E-07 1.94E-05 3.88E-04 5/17/2007 15:00 1.10E-03 2.20E-07 2.05E-05 3.44E-04 5/17/2007 16:00 1.20E-03 3.15E-07 2.19E-05 3.36E-04 5/17/2007 17:00 1.09E-03 3.80E-07 2.21E-05 3.97E-04 5/17/2007 18:00 1.18E-03 7.25E-07 2.89E-05 5.11E-04 5/17/2007 19:00 9.71E-04 5.81E-07 2.42E-05 3.78E-04 5/17/2007 20:00 1.07E-03 6.11E-07 2.69E-05 3.96E-04 5/17/2007 21:00 1.05E-03 8.08E-07 2.60E-05 4.54E-04 5/17/2007 22:00 9.68E-04 6.94E-07 2.59E-05 4.12E-04 5/17/2007 23:00 9.93E-04 5.74E-07 2.62E-05 4.27E-04 375 376 Table B.4.14.b: CPR - Emissions Time NO x (tons/ton clinker) SO 2 (tons/ton clinker) VOC (tons/ton clinker) CO (tons/ton clinker) 5/18/2007 0:00 1.05E-03 9.66E-07 2.27E-05 4.20E-04 5/18/2007 1:00 1.17E-03 7.19E-07 2.09E-05 4.38E-04 5/18/2007 2:00 1.14E-03 1.15E-06 1.98E-05 4.52E-04 5/18/2007 3:00 1.12E-03 1.02E-06 1.94E-05 4.39E-04 5/18/2007 4:00 1.15E-03 1.20E-06 1.92E-05 4.27E-04 5/18/2007 5:00 9.34E-04 1.34E-06 1.76E-05 4.16E-04 5/18/2007 6:00 1.11E-03 1.99E-06 1.80E-05 4.38E-04 5/18/2007 7:00 1.04E-03 1.14E-06 1.66E-05 4.23E-04 5/18/2007 8:00 1.09E-03 1.42E-06 1.70E-05 4.29E-04 5/18/2007 9:00 1.07E-03 1.33E-06 1.80E-05 4.05E-04 5/18/2007 10:00 1.03E-03 1.05E-06 2.05E-05 3.78E-04 5/18/2007 11:00 1.18E-03 1.24E-06 2.33E-05 4.30E-04 5/18/2007 12:00 1.17E-03 7.49E-07 2.34E-05 4.39E-04 5/18/2007 13:00 1.05E-03 7.20E-07 2.27E-05 4.40E-04 5/18/2007 14:00 1.15E-03 7.20E-07 2.32E-05 4.03E-04 5/18/2007 15:00 1.11E-03 5.69E-07 2.52E-05 3.99E-04 5/18/2007 16:00 1.03E-03 4.73E-07 2.44E-05 3.75E-04 5/18/2007 17:00 1.14E-03 7.42E-07 2.67E-05 4.12E-04 5/18/2007 18:00 1.14E-03 5.49E-07 2.67E-05 3.76E-04 5/18/2007 19:00 1.19E-03 4.01E-07 2.79E-05 3.93E-04 5/18/2007 20:00 1.13E-03 4.71E-07 2.65E-05 3.75E-04 5/18/2007 21:00 1.25E-03 5.36E-07 2.71E-05 4.08E-04 5/18/2007 22:00 1.27E-03 8.87E-07 2.62E-05 3.54E-04 5/18/2007 23:00 1.25E-03 7.51E-07 2.52E-05 3.82E-04 5/19/2007 0:00 1.23E-03 7.20E-07 2.31E-05 3.61E-04 5/19/2007 1:00 1.32E-03 6.87E-07 2.31E-05 3.46E-04 5/19/2007 2:00 1.34E-03 7.42E-07 2.32E-05 3.57E-04 5/19/2007 3:00 NC NC NC 3.89E-04 5/19/2007 4:00 1.31E-03 1.03E-06 2.07E-05 3.66E-04 5/19/2007 5:00 1.27E-03 1.05E-06 2.08E-05 3.98E-04 5/19/2007 6:00 1.30E-03 1.28E-06 2.15E-05 4.02E-04 5/19/2007 7:00 1.35E-03 1.19E-06 2.15E-05 4.06E-04 5/19/2007 8:00 1.29E-03 9.39E-07 2.07E-05 4.02E-04 Average 1.13E-03 8.66E-07 2.18E-05 3.79E-04 C. V. (%) 9.8 49.8 17.0 11.6 Normality P-Value 1 0.015 <0.005 0.008 0.214 Notes: 1 Based on Anderson Darling Normality Test NC - Not Collected 377 APPENDIX B.5 RAW DATA FOR CTB BURN B.5.1. GENERAL COMMENTS ? The raw data from the CTB burn are presented in this appendix. ? Coal, scrap tires and broiler litter are the fuels used in the burn. ? The burn lasted from 9 AM on May 16, 2007 to 9 AM on May 19, 2007. B.5.2. NOTATION CPR ? Cement Plant Results ELR ? External Lab Results AUR ? Auburn University Results C. V. ? Coefficient of Variation B.5.3. CHEMICAL COMPOSITION OF RAW MATERIALS Table B.5.1: CPR - Chemical Composition of Raw Materials ne Raw Material Two Raw Material Three Raw Material Four Raw 378 Property (wt. %) Raw Material O Material Five Raw Material Six Al 2 O 3 25.50 0.92 NR 9.43 1.06 0.75 CaO 2.99 51.40 NR 38.50 0.90 43.40 Fe 2 O 3 0.50 0.00 NR 13.70 1.21 0.00 K 2 O 2.63 0.08 NR 0.12 0.15 0.09 MgO 1.02 1.70 NR 12.00 0.09 0.62 Na 2 O 0.38 0.02 NR 1.73 0.00 0.00 SiO 2 56.80 2.25 NR 23.90 95.80 2.92 SO 3 0.73 0.06 NR 0.79 1.40 47.20 Moisture 31.70 3.00 NR 4.60 4.10 26.40 LOI 7.40 43.50 NR 0.30 0.50 5.00 Notes: ND - Not Detected NR - Not Reported Table B.5.2: ELR - Chemical Composition of Raw Materials One Raw Material Two Raw Material Three Raw Material Four Raw MatProperty Raw Material erial Five Raw Material Six Al 2 O 3 (wt. %) 27.36 0.59 6.74 5.68 0.66 0.54 CaO (wt. %) 3.03 94.35 48.34 33.12 0.40 42.95 Fe 2 O 3 (wt. %) 11.57 0.39 6.58 28.39 0.72 0.32 K 2 O (wt. %) 2.76 0.12 0.64 0.06 0.12 0.13 MgO (wt. %) 1.40 2.22 4.23 12.26 0.19 0.52 Na 2 O (wt. %) 0.51 0.03 0.21 0.03 0.06 0.06 P 2 O 5 (wt. %) 0.60 0.02 0.08 0.46 0.01 0.01 SiO 2 (wt. %) 50.43 2.08 32.12 14.90 97.58 3.78 SO 3 (wt. %) 0.40 0.09 0.20 0.59 0.01 51.54 TiO 2 (wt. %) 1.45 0.00 0.42 0.27 0.17 0.01 Moisture (wt. %) 20.97 0.27 2.40 5.35 2.80 15.93 LOI (wt. %) 8.21 41.46 25.06 5.46 0.29 7.00 As (ppm) 170 3 20 9 5 ND Ba (ppm) 2400 NR NR NR NR NR Cd (ppm) ND ND ND ND ND ND Cl (ppm) 18 46 42 101 70 23 Co (ppm) 67 12 12 14 4 ND Cr (ppm) 166 20 143 2152 40 ND Cu (ppm) 186 31 32 57 24 < 5 Hg (ppm) ND ND ND ND ND ND Mn (ppm) 400 NR NR NR NR NR Mo (ppm) 18 ND 1 48 9 ND Ni (ppm) 124 ND2 37 ND ND Pb (ppm) 70 N 3ND24ND Sb (ppm) NR NR NR NR NR NR Se (ppm) 4 ND ND ND ND3 Sr (ppm) 2100 NR NR NR NR NR V (ppm) 329 17 89 592 18 16 Zn (ppm) 141 43 42 190 3 ND 379 Notes: ND - Not Detected NR - Not Reported B.5.4. CHEMICAL COMPOSITION OF KILN FEED Table B.5.3: CPR - Chemical Composition of Kiln Feed 7/14/2006 2:23 AM 2:10 PM 1:39 AM 2:02 PM 1:59 AM 2:09 PM Al 2 O 3 3.12 3.08 3.11 3.14 3.15 3.14 3.12 0.8 CaO 43.62 43.64 43.34 43.25 43.21 43.47 43.42 0.4 Fe 2 O 3 1.9 1.87 1.86 1.88 1.91 1.88 1.88 1.0 K 2 O 0.43 0.4 0.39 0.39 0.39 0.39 0.40 4.0 MgO 2.19 1.93 1.9 1.91 1.91 1.91 1.96 5.8 Na 2 O 0.04 0.03 0.05 0.05 0.05 0.05 0.05 18.6 Na 2 O eq 0.32 0.29 0.31 0.31 0.31 0.31 0.31 3.2 SiO 2 12.94 12.9 13.04 13.23 13.23 12.88 13.04 1.2 SO 3 0.22 0.21 0.21 0.22 0.23 0.24 0.22 5.3 LOI 36.62 36.35 36.08 36.02 35.99 36.2 36.21 0.7 C. V. (%)Property (wt. %) 7/11/2006 Average 380 Table B.5.4: ELR - Chemical Composition of Kiln Feed Property 3-Day Composite Al 2 O 3 (wt. %) 4.4 CaO (wt. %) 68 Fe 2 O 3 (wt. %) 3.0 K 2 O (wt. %) 0.6 MgO (wt. %) 3.1 Na 2 O (wt. %) 0.1 P 2 O 5 (wt. %) 0.1 SiO 2 (wt. %) 20 SO 3 (wt. %) 0.4 TiO 2 (wt. %) 0.2 Moisture (wt. %) 0.3 LOI (wt. %) 32.7 As (ppm) 22.9 Ba (ppm) NR Cd (ppm) ND Cl (ppm) 84 Co (ppm) 11.4 Cr (ppm) 108 Cu (ppm) 17.8 Hg (ppm) ND Mn (ppm) NR Mo (ppm) ND Ni (ppm) 7.6 Pb (ppm) 3.8 Sb (ppm) NR Se (ppm) ND Sr (ppm) NR V (ppm) 70 Zn (ppm) 118 Notes: ND - Not Detected NR - Not Reported 381 B.5.5. CHEMICAL COMPOSITION OF FUELS Table B.5.5: CPR - Chemical Composition of Coal Test Parameter Value (wt. %) Ash 18.78 Fixed Carbon 53.85 Volatile Matter 27.37 Carbon 70.28 Hydrogen 4.29 Nitrogen 1.38 Oxygen 3.61 Sulfur 2.6 Al 2 O 3 24.03 CaO 6.30 Fe 2 O 3 9.86 K 2 O 2.33 MgO 1.10 Na 2 O 0.17 SiO 2 48.1 SO 3 6.51 12169 Notes: 1 Value is Reported as BTU/lb Heat Value 1 Proximate An alysis Ul ti mate An alysis S t an d a rd Parameters 382 Table B.5.6: ELR - Proximate, Ultimate, and Combustion of Coal Test Parameter Value (wt. %) Ash 17.65 Fixed Carbon 53.61 Volatile Matter 28.73 Carbon 69.84 Hydrogen 3.59 Nitrogen 0.59 Oxygen 6.77 Sulfur 1.55 12431 Notes: 1 Value is Reported as BTU/lb Proximate Analysis Ul ti mate Analysis Heat Value 1 383 Table B.5.7: ELR - Standard Parameters of Coal Property 3-Day Composite Al 2 O 3 (wt. %) 24.27 CaO (wt. %) 7.22 Fe 2 O 3 (wt. %) 9.04 K 2 O (wt. %) 2.40 MgO (wt. %) 1.08 Na 2 O (wt. %) 0.17 P 2 O 5 (wt. %) 0.18 SiO 2 (wt. %) 47.21 SO 3 (wt. %) 7.21 TiO 2 (wt. %) 1.03 As (ppm) 94 Ba (ppm) NC Cd (ppm) < 3 Cl (ppm) 101 Co (ppm) 41 Cr (ppm) 114 Cu (ppm) 114 Hg (ppm) 0.17 Mn (ppm) NC Mo (ppm) 35 Ni (ppm) 86 Pb (ppm) 49 Sb (ppm) NC Se (ppm) 5 Sr (ppm) NC V (ppm) 213 Zn (ppm) 73 Notes: ND - Not Detected NR - Not Reported 384 Table B.5.8: ELR - Proximate, Ultimate, and Combustion Analysis of Tires Test Parameter Value (wt. %) Ash 12.21 Fixed Carbon 49.41 Moisture 1 0.09 Volatile Matter 38.28 Carbon 78.98 Hydrogen 5.44 Nitrogen 0.06 Oxygen 1.84 Sulfur 1.47 15501 2 Value is Reported as BTU/lb Ul ti mate An alysis Heat Value 2 Proximate Analysis Notes: 1 As Received 385 Table B.5.9: ELR - Standard Parameters of Tires Property 3-Day Composite Al 2 O 3 (wt. %) 6.17 CaO (wt. %) 3.17 Fe 2 O 3 (wt. %) 46.84 K 2 O (wt. %) 0.29 MgO (wt. %) 0.03 Na 2 O (wt. %) 0.63 P 2 O 5 (wt. %) 0.21 SiO 2 (wt. %) 27.09 SO 3 (wt. %) 0.48 TiO 2 (wt. %) 6.82 As (ppm) ND Ba (ppm) NR Cd (ppm) ND Cl (ppm) 568 Co (ppm) 759 Cr (ppm) 56 Cu (ppm) 408 Hg (ppm) 0.2 Mn (ppm) NR Mo (ppm) 11 Ni (ppm) 70 Pb (ppm) ND Sb (ppm) NR Se (ppm) ND Sr (ppm) NR V (ppm) 214 Zn (ppm) 0 Notes: ND - Not Detected NR - Not Reported 386 Table B.5.10: ELR - Proximate, Ultimate, and Combustion Analysis of Broiler Litter Test Parameter Value (wt. %) Ash 20.61 Fixed Carbon 33.75 Moisture 1 29.06 Volatile Matter 45.64 Carbon 40.89 Hydrogen 4.86 Nitrogen 4.30 Oxygen 28.66 Sulfur 0.68 6875 Notes: 1 As Received 2 Value is Reported as BTU/lb Proximate Analysis Ul ti mate An alysis Heat Value 2 387 Table B.5.111: ELR - Standard Parameters of Broiler Litter Property 3-Day Composite Al 2 O 3 (wt. %) 0.84 CaO (wt. %) 23.52 Fe 2 O 3 (wt. %) 0.85 K 2 O (wt. %) 20.44 MgO (wt. %) 7.73 Na 2 O (wt. %) 7.02 P 2 O 5 (wt. %) 24.54 SiO 2 (wt. %) 7.44 SO 3 (wt. %) 6.58 TiO 2 (wt. %) 0.07 As (ppm) 13 Ba (ppm) 468 Cd (ppm) ND Cl (ppm) 5843 Co (ppm) 3 Cr (ppm) 29 Cu (ppm) 2505 Hg (ppm) 0.2 Mn (ppm) 8870 Mo (ppm) 43 Ni (ppm) 44 Pb (ppm) 32 Sb (ppm) NA Se (ppm) ND Sr (ppm) 379 V (ppm) 18 Zn (ppm) 2685 Notes: ND - Not Detected NR - Not Reported 388 389 Table B.5.12: AUR - Density of Broiler Litter Sample # Density (kg/m 3 ) 1 682.9 2 693.2 3 663.4 4 699.9 5 692.6 6 670.7 7 723.5 8 658.6 9 672.5 10 662.2 11 647.7 12 681.0 13 677.4 14 613.1 15 656.8 16 661.6 17 641.6 18 668.9 19 645.8 20 708.4 21 636.7 22 637.9 23 651.3 24 683.5 Average 668.0 B.5.6. CHEMICAL COMPOSITION OF CEMENT KILN DUST (CKD) Table B.5.13: CPR - Chemical Composition of Cement Kiln Dust 3:39 AM 9:22 AM 11:23 PM 7:56 AM 10:27 PM 6:47 AM 9:47 PM Al 2 O 3 3.85 3.91 3.84 3.8 3.84 3.13 4.57 3.85 CaO 45.64 45.53 45.4 45.21 45.12 43.25 43.31 44.78 Fe 2 O 3 1.83 1.85 1.86 1.84 1.91 1.9 2 1.88 K 2 O 0.52 0.51 0.5 0.5 0.52 0.39 0.63 0.51 MgO 1.27 1.25 1.26 1.28 1.43 1.9 1.33 1.39 Na 2 O 0.05 0.05 0.05 0.06 0.05 0.04 0.05 0.05 SiO 2 11.18 11.11 11.03 10.94 11.05 13.08 12.11 11.50 SO 3 0.21 0.23 0.25 0.25 0.27 0.24 0.47 0.27 6/21/2007 AverageProperty (wt. %) 6/19/2007 6/20/2007 390 Table B.5.14: ELR - Chemical Composition of Cement Kiln Dust 10:00 AM 10:00 PM 10:00 AM 10:00 PM 10:00 AM 10:00 PM Al 2 O 3 (wt. %) 6.28 5.71 5.73 5.56 6.32 6.39 6.00 CaO (wt. %) 68.45 70.76 70.85 70.81 68.58 68.19 69.60 Fe 2 O 3 (wt. %) 3.10 2.95 2.91 2.92 3.02 3.05 2.99 K 2 O (wt. %) 0.90 0.76 0.76 0.77 0.91 0.93 0.84 MgO (wt. %) 2.04 2.13 2.15 2.41 2.06 2.14 2.16 Na 2 O (wt. %) 0.11 0.08 0.09 0.06 0.07 0.09 0.08 P 2 O 5 (wt. %) 0.10 0.08 0.09 0.07 0.09 0.09 0.09 SiO 2 (wt. %) 17.88 16.64 16.53 16.46 17.74 17.90 17.19 SO 3 (wt. %) 0.64 0.43 0.41 0.46 0.72 0.71 0.56 TiO 2 (wt. %) 0.32 0.29 0.31 0.27 0.32 0.33 0.31 Moisture (wt. %) 0.18 0.28 0.28 0.31 0.21 0.19 0.24 LOI (wt. %) 34.94 35.84 36.12 35.88 34.93 34.83 35.42 As (ppm) 36 35 32 23 42 31 33 Ba (ppm) NR NR NR NR NR NR NA Cd (ppm) ND ND ND ND ND ND ND Cl (ppm) 955 198 191 185 1508 1369 734 Co (ppm) 12 13 17 14 14 17 15 Cr (ppm) 54 55 74 64 49 56 59 Cu (ppm) 70 29 42 22 30 17 35 Hg (ppm) 3.22 1.27 0.93 0.86 1.71 1.56 2 Mn (ppm) NR NR NR NR NR NR NA Mo (ppm) 4ND D2ND32 Ni (ppm) 20 13 13 12 18 13 15 Pb (ppm) 23 11 ND 21 ND 16 12 Sb (ppm) NR NR NR NR NR NR NR Se (ppm) ND ND ND ND ND ND ND Sr (ppm) NR NR NR NR NR NR NR V (ppm) 77 80 76 70 73 77 75 Zn (ppm) 74 59 64 60 68 73 66 Notes: ND - Not Detected NR - Not Reported AverageProperty 6/20/20076/19/2007 6/21/2007 391 B.5.7. CHEMICAL COMPOSITION OF CLINKER Table B.5.15.a: CPR - Chemical Composition of Clinker for 6/19/2007 9:37 AM 12:05 PM 1:59 PM 4:07 PM 5:37 PM 7:58 PM 10:09 PM 11:39 PM Al 2 O 3 5.18 5.16 5.20 5.17 5.27 5.27 5.22 5.25 CaO 64.77 64.47 64.63 64.65 64.59 64.36 64.27 64.50 Fe 2 O 3 3.16 3.13 3.06 3.18 3.18 3.10 3.08 3.23 K 2 O 0.57 0.68 0.66 0.64 0.63 0.63 0.68 0.63 MgO 3.29 3.49 3.22 3.21 3.21 3.18 3.10 3.16 Na 2 O 0.06 0.08 0.07 0.07 0.07 0.07 0.07 0.07 Na 2 O eq 0.44 0.53 0.50 0.49 0.48 0.48 0.52 0.48 SiO 2 21.48 21.25 21.41 21.37 21.46 21.38 21.20 21.41 SO 3 0.79 0.83 0.81 0.80 0.75 0.79 0.83 0.81 F CaO 0.86 1.45 1.50 1.40 1.50 1.24 1.45 0.81 C 3 A 8.40 8.40 8.60 8.30 8.60 8.70 8.60 8.40 C 4 AF 9.60 9.50 9.30 9.70 9.70 9.40 9.40 9.80 C 3 S 61.10 61.80 61.10 61.50 59.90 59.70 61.10 60.00 C 2 S 15.50 14.30 15.30 14.90 16.30 16.30 14.70 16.10 6/19/2007 Property (wt. %) 392 Table B.5.15.b: CPR - Chemical Composition of Clinker for 6/20/2007 1:39 AM 3:39 AM 4:55 AM 5:30 AM 7:56 AM 9:57 AM 12:09 PM 2:02 PM 3:55 PM 5:46 PM 7:54 PM 10:02 PM 11:44 PM Al2O3 5.25 5.30 5.33 5.29 5.38 5.30 5.26 5.30 5.28 5.30 5.25 5.26 5.30 CaO 64.48 64.31 64.31 64.31 64.16 64.27 64.17 64.14 64.03 64.21 64.17 64.32 64.36 Fe2O3 3.11 3.14 3.25 3.04 3.17 3.09 3.21 3.17 3.23 3.06 3.01 3.04 3.10 K2O 0.62 0.68 0.63 0.65 0.65 0.64 0.70 0.70 0.66 0.63 0.59 0.62 0.59 MgO 3.18 3.11 3.15 3.15 3.17 3.17 3.19 3.17 3.10 3.18 3.13 3.19 3.18 Na2O 0.08 0.07 0.08 0.08 0.08 0.08 0.09 0.08 0.12 0.08 0.09 0.08 0.08 Na2Oeq 0.49 0.52 0.49 0.51 0.51 0.50 0.55 0.54 0.55 0.49 0.48 0.49 0.47 SiO2 21.47 21.45 21.48 21.58 21.58 21.68 21.67 21.61 21.49 21.63 21.66 21.69 21.68 SO3 0.84 0.78 0.79 0.78 0.79 0.79 0.74 0.93 0.84 0.81 0.78 0.79 0.73 F CaO 0.97 1.50 1.29 1.18 0.70 0.91 0.64 0.48 0.64 0.70 0.67 C3A 8.70 8.70 8.60 8.90 8.90 8.80 8.50 8.70 8.50 8.90 8.80 8.80 8.80 C4AF 9.50 9.60 9.90 9.30 9.60 9.40 9.80 9.60 9.80 9.30 9.20 9.30 9.40 C3S 59.60 58.70 58.10 57.90 56.50 56.90 56.60 56.70 57.30 57.00 57.00 57.30 57.20 C2S 16.60 17.20 17.70 18.20 19.20 19.30 19.40 19.20 18.40 19.00 19.10 18.90 19.00 6/20/2007 Property (wt. %) 393 Table B.5.15.c: CPR - Chemical Composition of Clinker for 6/21/2007 394 3:48 AM 5:44 AM 8:02 AM 10:02 AM 11:36 AM 1:29 PM 2:18 PM 3:51 PM 5:33 PM 7:54 PM 9:46 PM 11:57 PM Al 2 O 3 5.33 5.33 5.34 5.38 4.78 5.34 5.27 5.32 5.39 5.34 5.31 5.3 CaO 64.35 64.34 64.24 64.31 62.23 64.32 64.45 64.41 64.34 64.44 64.4 64.4 Fe 2 O 3 3.13 3.12 3.18 3.21 2.79 3.14 3.08 3.11 3.18 3.17 3.15 3.22 K 2 O 0.58 0.60 0.64 0.59 0.64 0.62 0.62 0.6 0.58 0.65 0.66 0.63 MgO 3.16 3.17 3.17 3.16 2.62 3.17 3.16 3.18 3.19 3.26 3.21 3.26 Na 2 O 0.07 0.08 0.08 0.07 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 Na 2 O eq 0.45 0.47 0.50 0.46 0.5 0.49 0.49 0.47 0.46 0.51 0.51 0.49 SiO 2 21.61 21.59 21.48 21.55 20.04 21.53 21.58 21.57 21.51 21.48 21.47 21.41 SO 3 0.76 0.73 0.75 0.74 0.82 0.76 0.71 0.78 0.78 0.83 0.87 0.79 FCaO 0.54 0.59 1.03 1.07 0.7 0.75 0.86 1.13 0.97 0.54 0.54 C 3 A 8.80 8.80 8.80 8.8 7.9 8.8 8.8 8.8 8.9 8.8 8.7 8.6 C 4 AF 9.50 9.50 9.70 9.8 8.5 9.6 9.4 9.5 9.7 9.6 9.6 9.8 C 3 S 57.50 57.60 57.90 57.3 64.9 57.9 58.6 58.1 57.7 58.7 58.8 59.2 C 2 S 18.60 18.50 17.90 18.6 8.5 18.1 17.7 18 18.1 17.3 17.2 16.7 Property (wt. %) 6/21/2007 Table B.5.15.d: CPR - Chemical Composition of Clinker for 6/22/2007 1:55 AM 4:07 AM 5:28 AM 8:14 AM Al 2 O 3 5.28 5.28 5.24 5.3 5.27 1.9 0.416 CaO 64.47 64.44 64.51 64.62 64.32 0.6 <0.005 Fe 2 O 3 3.18 3.14 3.09 3.08 3.13 2.6 0.542 K 2 O 0.62 0.58 0.59 0.63 0.63 5.4 0.077 MgO 3.29 3.23 3.27 3.21 3.18 3.7 0.612 Na 2 O 0.08 0.08 0.07 0.08 0.08 11.8 <0.005 Na 2 O eq 0.49 0.46 0.46 0.49 0.49 5.3 0.413 SiO 2 21.3 21.36 21.34 21.15 21.45 1.3 0.323 SO 3 0.77 0.8 0.78 0.84 0.79 5.4 0.202 FCaO 1.45 0.81 1.18 1.29 0.98 34.2 0.374 C 3 A 8.6 8.7 8.7 8.8 8.67 2.3 0.721 C 4 AF 9.7 9.6 9.4 9.4 9.52 2.6 <0.005 C 3 S 60.6 60 60.8 62.3 58.94 3.3 0.033 C 2 S 15.4 15.9 15.3 13.6 17.03 12.7 0.807 Notes: 1 Based on Anderson-Darling Normality Test C.V. (%) Normality P-Value 1 Property (wt. %) 6/22/2007 Average wt % 395 Table B.5.16: ELR - Chemical Composition of Clinker 121212 Al 2 O 3 (wt. %) 5.00 5.13 5.05 5.11 5.05 5.06 5.06 CaO (wt. %) 64.73 64.25 64.90 64.65 64.87 65.01 64.73 Fe 2 O 3 (wt. %) 2.77 2.96 2.92 3.00 2.96 2.99 2.93 K 2 O (wt. %) 0.69 0.70 0.65 0.64 0.67 0.62 0.66 MgO (wt. %) 3.33 3.26 3.42 3.38 3.33 3.34 3.34 Na 2 O (wt. %) 0.08 0.07 0.08 0.08 0.10 0.07 0.08 P 2 O 5 (wt. %) 0.10 0.10 0.11 0.11 0.11 0.11 0.10 SiO 2 (wt. %) 22.01 22.20 21.57 21.79 21.64 21.59 21.80 SO 3 (wt. %) 0.83 0.86 0.81 0.78 0.82 0.76 0.81 TiO 2 (wt. %) 0.26 0.23 0.25 0.23 0.24 0.23 0.24 Moisture (wt. %) 0.07 0.12 0.04 0.04 0.04 0.03 0.06 LOI (wt. %) 0.35 0.24 0.32 0.29 0.49 0.30 0.33 As (ppm) 19 19 27 21 27 24 23 Ba (ppm) NR NR NR NR NR NR NA Cd (ppm) ND ND ND ND ND ND ND Cl (ppm) 288 266 214 311 455 286 303 Co (ppm) 14 11 14 8 7 8 10 Cr (ppm) 100 89 106 99 85 77 93 Cu (ppm) 16 69 29 16 30 15 29 Hg (ppm) ND ND ND ND ND ND ND Mn (ppm) NR NR NR NR NR NR NR Mo (ppm) ND 7 1 6 ND 4 3 Ni (ppm) 1912 791191 Pb (ppm) 20 20 ND 11 ND 9 10 Sb (ppm) NR NR NR NR NR NR NR Se (ppm) ND ND ND ND ND 3 0.5 Sr (ppm) NR NR NR NR NR NR NA V (ppm) 71 63 72 69 62 64 67 Zn (ppm) 107 103 100 102 92 90 99 Notes: ND - Not Detected NR - Not Reported Property 6/19/2007 620/2007 6/21/2007 Average 396 B.5.8. CHEMICAL COMPOSITION OF CEMENT Table B.5.17: CPR - Chemical Composition of Cement 10:01 AM 12:32 PM 3:41 PM 6:37 PM 9:48 PM 1:09 AM 2:12 AM 3:58 AM 6:40 AM Al 2 O 3 4.89 4.89 4.91 4.91 4.86 4.86 4.86 4.86 4.83 4.87 0.6 0.045 CaO 62.31 62.3 62.07 62.44 62.21 62.39 62.28 62.11 61.05 62.13 0.7 0.305 Fe 2 O 3 2.92 2.94 2.93 2.97 2.95 2.97 2.94 2.96 2.92 2.94 0.7 0.315 K 2 O 0.540.51 0.5 0.470.470.460.450.460.450.48 6.5<0.005 MgO 3.13 3.14 3.19 3.26 3.26 3.28 3.27 3.26 3.21 3.22 1.8 0.025 Na 2 O 0.09 0.09 0.1 0.1 0.09 0.1 0.08 0.09 0.08 0.09 8.6 <0.005 Na 2 O eq 0.45 0.43 0.43 0.4 0.4 0.4 0.38 0.39 0.38 0.41 6.0 <0.005 SiO 2 20.26 20.2 20.23 20.35 20.38 20.59 20.49 20.54 20.44 20.39 0.7 0.464 SO 3 2.59 2.6 2.542.512.652.552.572.592.522.57 1.7 0.065 F CaO 1.56 1.18 1.13 1.02 0.91 0.91 1.02 0.84 1.07 21.3 0.381 LOI 0.79 1.02 1.03 0.85 0.73 0.79 0.94 0.94 0.89 12.7 <0.005 C 3 A 8 8 8.1 8 7.9 7.9 7.9 7.9 7.9 7.96 0.9 0.738 C 4 AF 8.9 9 8.9 9 9 9 8.9 9 8.9 8.96 0.6 0.380 C 3 S 55.3 55.6 54.5 55.1 53.9 53.3 53.6 52.5 49.4 53.69 3.5 0.201 C 2 S 16.4 16 16.9 16.8 17.7 18.8 18.3 19.3 21.4 17.96 9.5 0.200 Blaine SSA (m 2 /kg) 389 377 385 365 365 338 343 368 366 366 4.7 <0.005 Notes: 1 Based on Anderson-Darling Normality Test Property (wt. %) 6/25/2007 6/26/2007 Average Normality P-Value 1 C. V. (%) 397 Table B.5.18: ELR - Chemical Composition of Cement Property 123Average Al 2 O 3 (wt. %) 4.99 4.85 4.90 4.92 CaO (wt. %) 63.77 63.99 63.61 63.79 Fe 2 O 3 (wt. %) 2.91 2.87 2.79 2.86 K 2 O (wt. %) 0.59 0.63 0.62 0.61 MgO (wt. %) 3.35 3.32 3.21 3.29 Na 2 O (wt. %) 0.08 0.15 0.12 0.12 P 2 O 5 (wt. %) 0.10 0.10 0.10 0.10 SiO 2 (wt. %) 21.10 20.91 21.46 21.16 SO 3 (wt. %) 2.62 2.70 2.75 2.69 TiO 2 (wt. %) 0.22 0.23 0.22 0.22 Moisture (wt. %) 0.00 0.00 0.00 0.00 LOI (wt. %) 0.89 0.98 0.90 0.92 C 3 S (wt. %) 54.04 57.20 51.12 54.12 C 2 S (wt. %) 19.73 16.80 22.95 19.83 C 3 A (wt. %) 8.29 7.99 8.28 8.19 C 4 AF (wt. %) 8.87 8.74 8.49 8.70 TOC (wt. %) ND ND ND ND As (ppm) 14 20 19 17 Ba (ppm) 400 500 300 400 Cd (ppm) ND ND ND ND Cl (ppm) 111 163 140 138 Co (ppm) 1381412 Cr (ppm) 96 88 87 90 Cu (ppm) 14599 Hg (ppm) 2.00 1.10 0.70 1.27 Mn (ppm) 1650 1690 1390 1577 Mo (ppm) 5 ND 3 3.93 Ni (ppm) 1271010 Pb (ppm) 23715 5 Sb (ppm) 500 500 500 500 Se (ppm) ND ND ND ND Sr (ppm) NR NR NR NR V (ppm) 69 69 62 66 Zn (ppm) 84 85 97 89 Notes: ND - Not Detected NR - Not Reported 398 B.5.9. PHYSICAL PROPERTIES OF CEMENT Table B.5.19: CPR - Physical Properties of Cement Property CPR Air in Mortar (%) 6.6 Blaine Specific Surface Area (m 2 /kg) 367 Autoclave Expansion (% Exp.) 0.15 Cube Flow (%) 127.0 Comp Str 1day (MPa) 14.9 Comp Str 3day (MPa) 23.5 Comp Str 7day (MPa) 31.1 Comp Str 28day (MPa) 42.0 Normal Consistency (%) 25.7 Gillmore Initial Set (Min) 131 Gillmore Final Set (Min) 225 Vicat Initial Set (Min) 74 Vicat Final Set (Min) 199 Notes: % Exp. - Percent Expansion Table B.5.20: AUR - Physical Properties of Cement Property AUR Autoclave Expansion (% Exp.) 0.06 Cube Flow (%) 101 Comp Str 1day (MPa) 12 Comp Str 3day (MPa) 21.5 Comp Str 7day (MPa) 26.5 Comp Str 28day (MPa) 32.9 Normal Consistency (%) 26.2 Gillmore Initial Set (Min) 102 Gillmore Final Set (Min) 202 Vicat Initial Set (Min) 75 Vicat Final Set (Min) 180 Drying Shrinkage @ 7 days (% LC) -0.035 Drying Shrinkage @ 14 days (% LC) -0.073 Drying Shrinkage @ 21 days (% LC) -0.080 Drying Shrinkage @ 28 days (% LC) -0.082 Notes: % LC - Percent Length Change % Exp. - Percent Expansion 399 B.5.10. PROPERTIES OF CONCRETE Table B.5.21: Concrete Properties 400 224 days 0.048 0.046 NC 448 days CIP CIP NC Permeability @ 91 days (Coulombs) 2730 2700 2500 Notes: CIP - Collection in Progress NC - Not Collected 1 Percentage decrease in length CPR Mix w/c=0.44 Mix w/c=0.37 Mix w/c=0.44 Total Air Content (%) 3.5 5.0 3.4 Slump (mm) 50 130 40 Unit Weight (kg/m 3 ) 2460 2410 2448 Initial Set (Min.) 154 199 NC Final Set (Min.) 231 262 273.0 Compressive Strength (MPa) 1 day 16.8 29.9 6.1 3 days 25.1 34.8 23.1 7 days 34.7 45.2 30.9 28 days 42.5 52.7 43.8 91 days 49.6 59.0 49.8 Splitting Tensile Strength (MPa) 1 day 2.2 3.0 NC 3 days 2.8 3.1 NC 7 days 3.3 3.4 NC 28 days 3.9 4.0 NC 91 days 4.2 4.3 NC Drying Shrinkage Development (% Length Change) 1 4 days 0.010 0.010 NC 7 days 0.013 0.016 NC 14 days 0.020 0.022 NC 28 days 0.028 0.033 NC 56 days 0.034 0.039 NC 112 days 0.043 0.043 NC Property AUR B.5.11. EMISSIONS Table B.5.22.a: CPR ? Emissions for 6/19/2007 ? 6/20/2007 Time NO x (tons/ton clinker) SO 2 (tons/ton clinker) VOC (tons/ton clinker) CO (tons/ton clinker) 6/19/2007 9:00 8.41E-04 2.52E-07 2.15E-05 4.28E-04 6/19/2007 10:00 6.85E-04 3.84E-07 2.05E-05 4.02E-04 6/19/2007 11:00 7.45E-04 4.04E-07 2.18E-05 4.49E-04 6/19/2007 12:00 8.79E-04 5.00E-07 2.50E-05 4.69E-04 6/19/2007 13:00 8.31E-04 4.79E-07 3.00E-05 4.45E-04 6/19/2007 14:00 7.69E-04 3.16E-07 2.51E-05 4.48E-04 6/19/2007 15:00 8.71E-04 2.07E-07 2.29E-05 5.14E-04 6/19/2007 16:00 8.13E-04 1.77E-07 2.15E-05 4.48E-04 6/19/2007 17:00 8.78E-04 5.25E-07 2.68E-05 4.82E-04 6/19/2007 18:00 8.15E-04 3.66E-07 2.88E-05 4.92E-04 6/19/2007 19:00 8.13E-04 5.36E-07 3.03E-05 5.12E-04 6/19/2007 20:00 7.09E-04 3.52E-07 3.36E-05 5.87E-04 6/19/2007 21:00 6.82E-04 2.73E-07 2.42E-05 4.72E-04 6/19/2007 22:00 8.01E-04 4.28E-07 2.78E-05 4.78E-04 6/19/2007 23:00 8.77E-04 6.01E-07 3.15E-05 4.79E-04 6/20/2007 0:00 8.32E-04 1.43E-07 3.94E-05 6.31E-04 6/20/2007 1:00 7.44E-04 2.58E-07 3.54E-05 5.15E-04 6/20/2007 2:00 8.03E-04 1.86E-07 3.40E-05 4.30E-04 6/20/2007 3:00 8.47E-04 2.04E-07 3.34E-05 4.12E-04 6/20/2007 4:00 8.06E-04 2.40E-07 3.07E-05 4.17E-04 6/20/2007 5:00 8.11E-04 1.88E-07 2.93E-05 4.54E-04 6/20/2007 6:00 8.56E-04 3.26E-07 2.74E-05 4.54E-04 6/20/2007 7:00 7.41E-04 2.46E-07 2.65E-05 4.74E-04 6/20/2007 8:00 7.49E-04 1.38E-06 2.29E-05 5.13E-04 6/20/2007 9:00 7.02E-04 1.66E-06 2.14E-05 5.17E-04 6/20/2007 10:00 8.07E-04 1.76E-06 2.21E-05 5.62E-04 6/20/2007 11:00 9.02E-04 1.55E-06 2.37E-05 5.61E-04 6/20/2007 12:00 8.24E-04 1.77E-06 2.74E-05 5.35E-04 6/20/2007 13:00 6.86E-04 2.72E-06 3.14E-05 5.04E-04 6/20/2007 14:00 6.64E-04 1.81E-06 3.34E-05 4.80E-04 6/20/2007 15:00 7.25E-04 1.41E-06 3.46E-05 4.83E-04 6/20/2007 16:00 7.95E-04 1.99E-06 3.49E-05 5.36E-04 6/20/2007 17:00 7.45E-04 2.43E-06 3.36E-05 5.24E-04 6/20/2007 18:00 8.83E-04 2.39E-06 3.34E-05 5.70E-04 6/20/2007 19:00 8.27E-04 1.96E-06 2.93E-05 5.01E-04 6/20/2007 20:00 8.05E-04 1.36E-06 2.95E-05 4.73E-04 6/20/2007 21:00 6.98E-04 1.35E-06 2.94E-05 4.64E-04 6/20/2007 22:00 7.77E-04 1.41E-06 3.04E-05 4.97E-04 6/20/2007 23:00 8.06E-04 1.68E-06 2.68E-05 5.48E-04 401 402 Table B.5.22.b: CPR ? Emissions for 6/21/2007 ? 6/22/2007 Time NO x (tons/ton clinker) SO 2 (tons/ton clinker) VOC (tons/ton clinker) CO (tons/ton clinker) 6/21/2007 0:00 7.24E-04 1.43E-06 2.33E-05 4.56E-04 6/21/2007 1:00 7.09E-04 1.30E-06 2.38E-05 5.15E-04 6/21/2007 2:00 7.16E-04 1.12E-06 2.65E-05 5.02E-04 6/21/2007 3:00 7.36E-04 1.82E-06 2.12E-05 5.36E-04 6/21/2007 4:00 6.77E-04 4.47E-06 1.63E-05 5.75E-04 6/21/2007 5:00 6.38E-04 2.74E-06 1.90E-05 4.46E-04 6/21/2007 6:00 7.31E-04 3.41E-06 1.76E-05 4.88E-04 6/21/2007 7:00 7.61E-04 6.58E-06 1.81E-05 4.94E-04 6/21/2007 8:00 8.27E-04 3.98E-06 1.64E-05 5.17E-04 6/21/2007 9:00 9.22E-04 2.18E-05 1.93E-05 5.58E-04 6/21/2007 10:00 1.07E-03 5.03E-05 2.60E-05 5.62E-04 6/21/2007 11:00 8.60E-04 3.35E-05 3.08E-05 5.59E-04 6/21/2007 12:00 8.29E-04 2.63E-05 4.26E-05 5.35E-04 6/21/2007 13:00 7.02E-04 2.04E-05 6.25E-05 6.23E-04 6/21/2007 14:00 9.73E-04 1.84E-05 6.45E-05 5.72E-04 6/21/2007 15:00 9.56E-04 5.72E-05 7.72E-05 5.54E-04 6/21/2007 16:00 7.26E-04 2.81E-05 8.03E-05 5.69E-04 6/21/2007 17:00 8.85E-04 2.40E-05 8.26E-05 5.42E-04 6/21/2007 18:00 8.35E-04 1.35E-05 7.51E-05 5.11E-04 6/21/2007 19:00 9.00E-04 9.63E-06 5.95E-05 5.36E-04 6/21/2007 20:00 9.41E-04 3.67E-05 8.11E-05 5.00E-04 6/21/2007 21:00 8.98E-04 2.72E-05 8.72E-05 4.62E-04 6/21/2007 22:00 9.05E-04 2.19E-06 5.86E-05 5.33E-04 6/21/2007 23:00 8.71E-04 2.06E-06 5.01E-05 4.70E-04 6/22/2007 0:00 7.70E-04 1.73E-06 3.78E-05 4.56E-04 6/22/2007 1:00 7.87E-04 1.70E-06 3.82E-05 4.46E-04 6/22/2007 2:00 8.07E-04 1.13E-06 4.95E-05 4.38E-04 6/22/2007 3:00 7.95E-04 9.00E-07 4.45E-05 4.31E-04 6/22/2007 4:00 8.18E-04 1.54E-06 4.33E-05 4.18E-04 6/22/2007 5:00 9.55E-04 1.98E-06 5.11E-05 4.60E-04 6/22/2007 6:00 9.88E-04 1.37E-06 4.47E-05 5.31E-04 6/22/2007 7:00 9.74E-04 1.60E-06 2.76E-05 5.67E-04 6/22/2007 8:00 9.70E-04 3.92E-06 2.78E-05 5.37E-04 Average 8.13E-04 6.25E-06 3.55E-05 5.01E-04 C. V. (%) 11.0 189.5 48.9 10.2 Normality P-Value 1 0.269 <0.005 <0.005 0.378 Notes: 1 Based on Anderson Darling Normality Test NC - Not Collected 403 APPENDIX B.6 RAW DATA FOR CT3 BURN B.6.1. GENERAL COMMENTS ? The raw data from the CT3 burn are presented in this appendix. ? Coal and scrap tires are the fuels used in the burn. ? The burn lasted from 9 AM on August 13, 2007 to 9 AM on August 16, 2007. ? Cement and concrete results not collected for the burn. B.6.2. NOTATION CPR ? Cement Plant Results ELR ? External Lab Results AUR ? Auburn University Results C. V. ? Coefficient of Variation 404 B.6.3. Property (wt. %) Raw Material O Material Five Raw Material Six Al 2 O 3 21.90 0.85 NR 10.60 10.60 0.78 CaO 7.23 52.60 NR 33.90 33.90 41.00 Fe 2 O 3 3.79 NR NR 14.20 14.20 NR K 2 O 1.87 0.10 NR 0.05 0.05 0.12 MgO 1.46 1.80 NR 12.20 12.20 0.58 Na 2 O 0.30 NR NR NR NR NR SiO 2 52.20 2.12 NR 23.30 23.30 3.21 SO 3 0.65 0.11 NR 0.94 0.94 46.90 Moisture 13.20 3.60 NR 7.20 7.20 25.30 LOI 8.60 42.40 NR 2.20 2.20 7.30 Notes: NR - Not Reported CHEMICAL COMPOSITION OF RAW MATERIALS Table B.6.1: CPR - Chemical Composition of Raw Materials ne Raw Material Two Raw Material Three Raw Material Four Raw Table B.6.2: ELR - Chemical Composition of Raw Materials Property Raw Material One Raw Material Two Raw Material Three Raw Material Four Raw Material Five Raw Material Six Al 2 O 3 (wt. %) 26.84 0.63 4.72 6.77 0.50 0.85 CaO (wt. %) 3.00 94.36 64.97 31.36 0.35 40.41 Fe 2 O 3 (wt. %) 12.12 0.27 2.65 29.08 0.42 0.38 K 2 O (wt. %) 2.54 0.11 0.46 0.06 0.10 0.15 MgO (wt. %) 1.45 2.02 1.76 13.77 0.16 0.55 Na 2 O (wt. %) 0.49 0.12 0.13 0.01 0.02 0.06 P 2 O 5 (wt. %) 0.61 0.00 0.05 0.50 0.00 0.01 SiO 2 (wt. %) 50.92 2.27 24.62 13.55 98.21 4.47 SO 3 (wt. %) 0.26 0.14 0.24 0.56 0.00 52.97 TiO 2 (wt. %) 1.31 0.00 0.29 0.30 0.19 0.02 Moisture (wt. %) 15.83 2.37 1.98 4.35 4.33 9.00 LOI (wt. %) 9.41 43.42 35.36 2.59 0.21 13.76 As (ppm) 165 ND 16 7 ND ND Ba (ppm) 2095 204 289 191 196 199 Cd (ppm) ND ND ND ND ND ND Cl (ppm) 91 35 37 133 12 19 Co (ppm) 64 4 8 15 ND ND Cr (ppm) 170 24 42 2188 5 10 Cu (ppm) 146 46 39 16 78 14 Hg (ppm) 3.42 1.92 1.31 0.96 0.68 0.52 Mn (ppm) 698 102 289 39916 295 100 Mo (ppm) 17 ND 2 45 ND ND Ni (ppm) 114 26 13 53 9 ND Pb (ppm) 58 ND 10 ND 14 ND Sb (ppm) NR NR NR NR NR NR Se (ppm) 2 ND ND 4 ND ND Sr (ppm) 1896 510 481 286 98 1095 V (ppm) 314 34 54 678 16 12 Zn (ppm) 146 9 67 164 13 ND Notes: ND - Not Detected NR- Not Reported 405 406 B.6.4. CHEMICAL COMPOSITION OF KILN FEED Table B.6.3: CPR - Chemical Composition of Kiln Feed 8/16/2007 2:05 AM 2:08 PM 1:29 AM 2:00 PM 2:05 AM 1:47 PM 2:06 AM Al 2 O 3 2.99 2.94 3.04 2.92 2.95 2.88 3.08 2.97 2.4 CaO 43.44 43.53 43.57 43.68 42.91 43.37 43.34 43.41 0.6 Fe 2 O 3 1.85 1.93 1.96 2.03 2.01 2.02 2.08 1.98 3.8 K 2 O 0.31 0.27 0.29 0.29 0.27 0.27 0.3 0.29 5.7 MgO 1.87 1.91 1.9 1.94 1.89 1.93 2.1 1.93 4.0 Na 2 O 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.0 Na 2 O eq 0.23 0.21 0.22 0.29 0.21 0.21 0.23 0.23 12.5 SiO 2 13.16 13.32 13.23 13.07 12.96 12.89 13 13.09 1.2 SO 3 0.22 0.25 0.26 0.27 0.26 0.27 0.28 0.26 7.5 LOI 35.31 34.97 35 35 35 35 35 35.04 0.3 Notes: NR - Not Reported NA - Not Applicable C. V. (%)Property (wt. %) 8/13/2007 8/14/2007 8/15/2007 Average Table B.6.4: ELR - Chemical Composition of Kiln Feed Property 3-Day Composite Al 2 O 3 (wt. %) 4.46 CaO (wt. %) 63.62 Fe 2 O 3 (wt. %) 3.03 K 2 O (wt. %) 0.42 MgO (wt. %) 3.41 Na 2 O (wt. %) 0.08 P 2 O 5 (wt. %) 0.07 SiO 2 (wt. %) 23.84 SO 3 (wt. %) 0.53 TiO 2 (wt. %) 0.27 Moisture (wt. %) 0.14 LOI (wt. %) 34.70 As (ppm) 23 Ba (ppm) 295 Cd (ppm) ND Cl (ppm) 105 Co (ppm) 10 Cr (ppm) 106 Cu (ppm) 56 Hg (ppm) 0.53 Mn (ppm) 1969 Mo (ppm) ND Ni (ppm) 16 Pb (ppm) 17 Sb (ppm) NR Se (ppm) ND Sr (ppm) 492 V (ppm) 72 Zn (ppm) 300 Notes: NR - Not Reported ND - Not Detected 407 B.6.5. CHEMICAL COMPOSITION OF FUELS Table B.6.5: CPR - Chemical Composition of Coal Test Parameter Value (wt. %) Ash 23.28 Fixed Carbon 55.74 Volatile Matter 26.00 Carbon 59.85 Hydrogen 4.06 Nitrogen 1.27 Oxygen 3.32 Sulfur 2.56 Al 2 O 3 23.26 CaO 6.94 Fe 2 O 3 7.66 K 2 O 2.81 MgO 1.12 Na 2 O 0.14 SiO 2 50.31 SO 3 6.41 11481 Heat Value 1 Proximate Analysis Ul ti mate Analysis St andard Par a m e t e r s Notes: 1 Value is Reported as BTU/lb 408 Table B.6.6: ELR - Proximate, Ultimate, and Combustion Analysis of Coal Test Parameter Value (wt. %) Ash 26.20 Fixed Carbon 47.39 Volatile Matter 26.41 Carbon 63.96 Hydrogen 3.57 Nitrogen 1.45 Oxygen 3.55 Sulfur 1.27 11,204 Notes: 1 Value is Reported as BTU/lb Proximate Analysis Ul ti mate An aly s is Heat Value 1 409 Table B.6.7: ELR - Standard Parameters of Coal Property 3-Day Composite Al 2 O 3 (wt. %) 25.24 CaO (wt. %) 4.74 Fe 2 O 3 (wt. %) 6.56 K 2 O (wt. %) 3.25 MgO (wt. %) 1.34 Na 2 O (wt. %) 0.17 P 2 O 5 (wt. %) 0.14 SiO 2 (wt. %) 53.36 SO 3 (wt. %) 3.97 TiO 2 (wt. %) 3.97 As (ppm) 72 Ba (ppm) 1100 Cd (ppm) ND Cl (ppm) 89 Co (ppm) 29 Cr (ppm) 109 Cu (ppm) 81 Hg (ppm) 0.150 Mn (ppm) 300 Mo (ppm) 24 Ni (ppm) 68 Pb (ppm) 43 Sb (ppm) NC Se (ppm) 7 Sr (ppm) 500 V (ppm) 226 Zn (ppm) 81 Notes: NR - Not Reported ND - Not Detected 410 Table B.6.8: ELR - Proximate, Ultimate, and Combustion Analysis of Tires Test Parameter Value (wt. %) Ash 18.90 Fixed Carbon 41.88 Moisture 1 0.07 Volatile Matter 39.15 Carbon 69.49 Hydrogen 4.96 Nitrogen 1.74 Oxygen 3.15 Sulfur 1.77 14972 Ul ti mate An alysis Heat Value 2 Proximate Analysis Notes: 1 As Received 2 Value is Reported as BTU/lb 411 412 Table B.6.9: ELR - Standard Parameters for Tires Property 3-Day Composite Al 2 O 3 (wt. %) 0.16 CaO (wt. %) 1.61 Fe 2 O 3 (wt. %) 85.88 K 2 O (wt. %) 0.19 MgO (wt. %) 0.08 Na 2 O (wt. %) 0.21 P 2 O 5 (wt. %) 0.07 SiO 2 (wt. %) 2.76 SO 3 (wt. %) 0.30 TiO 2 (wt. %) 0.34 As (ppm) 4 Ba (ppm) 0 Cd (ppm) ND Cl (ppm) 946 Co (ppm) 1191 Cr (ppm) 260 Cu (ppm) 1068 Hg (ppm) ND Mn (ppm) 3900 Mo (ppm) 21 Ni (ppm) 215 Pb (ppm) 10 Sb (ppm) NR Se (ppm) ND Sr (ppm) 0 V (ppm) 20 Zn (ppm) 0 ND - Not Detected Notes: NR - Not Reported 413 B.6.6. CHEMICAL COMPOSITION OF CEMENT KILN DUST (CKD) Table B.6.10: CPR - Chemical Composition of Cement Kiln Dust (CKD) 8/16/07 8:53 AM 9:34 AM 7:27 PM 7:18 AM 8:33 PM 8:13 AM 6:48 PM 6:33 AM Al 2 O 3 3.58 3.65 3.93 3.63 3.91 3.73 4 3.76 3.77 CaO 46.3 46.26 44.95 45.61 44.96 45.32 45.03 45.48 45.49 Fe 2 O 3 1.8 1.83 1.91 1.81 1.95 1.91 1.97 1.91 1.89 K 2 O 0.35 0.35 0.38 0.35 0.41 0.39 0.42 0.41 0.38 MgO 1.17 1.19 1.23 1.22 1.33 1.38 1.37 1.4 1.29 Na 2 O 0.07 0.06 0.08 0.08 0.07 0.08 0.06 0.05 0.07 SiO 2 10.62 10.76 11.54 10.68 11.38 11.07 11.38 11.04 11.06 SO 3 0.25 0.25 0.3 0.3 0.27 0.27 0.32 0.39 0.29 8/13/07 8/15/07 AverageProperty (wt. %) 8/14/07 Table B.6.11: ELR - Chemical Composition of Cement Kiln Dust 121212 Al 2 O 3 (wt. %) 5.94 5.44 5.61 6.02 5.71 5.75 5.75 CaO (wt. %) 68.66 69.77 70.12 68.79 69.70 69.69 69.46 Fe 2 O 3 (wt. %) 2.89 2.68 2.75 2.95 2.91 2.91 2.85 K 2 O (wt. %) 0.55 0.50 0.48 0.60 0.57 0.57 0.55 MgO (wt. %) 2.09 2.06 2.17 2.23 2.31 2.35 2.20 Na 2 O (wt. %) 0.08 0.08 0.08 0.10 0.08 0.08 0.08 P 2 O 5 (wt. %) 0.10 0.09 0.10 0.09 0.09 0.09 0.09 SiO 2 (wt. %) 18.50 16.69 17.54 18.10 17.56 17.30 17.61 SO 3 (wt. %) 0.63 2.19 0.59 0.58 0.57 0.77 0.89 TiO 2 (wt. %) 0.35 0.32 0.34 0.34 0.32 0.32 0.33 Moisture (wt. %) 0.21 0.17 0.17 0.18 0.15 0.16 0.17 LOI (wt. %) 35.72 36.33 36.19 35.73 36.05 36.33 36.06 As (ppm) 24 28 27 27 27 33 27 Ba (ppm) 494 297 395 394 393 395 394 Cd (ppm) ND ND ND ND ND ND ND Cl (ppm) 152 164 129 133 168 182 155 Co (ppm) 89138101310 Cr (ppm) 66 64 83 54 70 60 66 Cu (ppm) 43 22 39 19 45 19 31 Hg (ppm) 0.60 0.63 0.53 0.59 0.53 0.62 0.6 Mn (ppm) 987 990 1085 985 982 986 1003 Mo (ppm) 2 NDNDND 3 1 1 Ni (ppm) 14 11 18 16 11 13 14 Pb (ppm) 8 18183818 417 Sb (ppm) NR NR NR NR NR NR NR Se (ppm) ND ND ND ND ND ND ND Sr (ppm) 592 594 592 591 589 592 592 V (ppm) 75 73 76 78 75 73 75 Zn (ppm) 260 245 237 187 169 192 215 Notes: ND - Not Detected NR - Not Reported NA - Not Applicable 8/13/2007 8/14/2007 8/15/2007 Property Average 414 415 B.6.7. 2:04 AM 4:08 AM 5:27 AM 8:01 AM 10:05 AM 11:53 AM 1:25 PM 2:08 PM 4:03 PM 5:30 PM 7:28 PM 9:38 PM 11:38 PM Al 2 O 3 5.08 5.36 5.34 4.95 5.25 5.28 5.39 4.98 5.47 5.53 5.33 5.38 5.45 CaO 64.84 64.46 64.65 63.36 64.59 64.50 64.31 63.32 64.27 64.33 64.48 64.52 64.29 Fe 2 O 3 3.13 3.17 3.19 2.85 3.20 3.34 3.26 2.91 3.39 3.41 3.31 3.34 3.41 K 2 O 0.57 0.52 0.57 0.52 0.50 0.52 0.52 0.50 0.51 0.51 0.52 0.50 0.52 MgO 3.37 3.29 3.40 2.90 3.37 3.36 3.35 2.94 3.42 3.33 3.35 3.31 3.25 Na 2 O 0.07 0.07 0.08 0.08 0.07 0.08 0.10 0.09 0.09 0.09 0.08 0.09 0.10 Na 2 O e CHEMICAL COMPOSITION OF CLINKER Table B.6.12.a: CPR - Chemical Composition of Clinker for 8/13/2007 q 0.45 0.42 0.45 0.42 0.41 0.43 0.44 0.42 0.42 0.42 0.42 0.42 0.45 SiO 2 21.40 21.20 21.33 20.80 21.66 21.59 21.55 20.61 21.54 21.47 21.48 21.31 21.32 SO 3 0.78 0.75 0.75 0.78 0.68 0.72 0.78 0.81 0.77 0.72 0.65 0.74 0.76 F CaO 1.21 1.09 1.33 0.36 0.54 1.75 1.39 1.09 0.79 1.27 1.39 1.15 1.15 C 3 A 8.20 8.80 8.70 8.30 8.50 8.40 8.80 8.30 8.80 8.90 8.50 8.60 8.70 C 4 AF 9.50 9.60 9.70 8.70 9.70 10.10 9.90 8.90 10.30 10.40 10.10 10.10 10.40 C 3 S 62.70 60.70 60.70 62.50 58.50 58.20 57.10 63.50 56.30 56.70 58.70 59.80 58.20 C 2 S 14.10 15.00 15.40 12.50 17.90 18.00 18.70 11.20 19.30 18.80 17.30 16.00 17.20 Property (wt. %) 8/13/07 Table B.6.12.b: CPR - Chemical Composition of Clinker for 8/14/2007 1:33 AM 3:40 AM 5:38 AM 7:53 AM 10:00 AM 11:52 AM 2:01 PM 4:00 PM 5:38 PM 8:03 PM 10:07 PM 11:42 PM Al 2 O 3 5.37 5.35 5.25 5.28 5.20 5.36 5.33 5.23 5.36 5.37 5.39 5.33 CaO 64.59 64.64 64.62 64.59 64.64 64.40 64.46 64.50 64.47 64.44 64.48 64.37 Fe 2 O 3 3.35 3.38 3.34 3.42 3.39 3.45 3.49 3.44 3.50 3.49 3.46 3.46 K 2 O 0.50 0.49 0.50 0.47 0.51 0.49 0.49 0.49 0.50 0.52 0.52 0.54 MgO 3.30 3.29 3.29 3.22 3.32 3.26 3.24 3.28 3.27 3.28 3.28 3.29 Na 2 O 0.08 0.09 0.10 0.10 0.09 0.10 0.09 0.09 0.09 0.09 0.08 0.10 Na 2 O eq 0.41 0.41 0.42 0.41 0.43 0.43 0.41 0.41 0.42 0.43 0.43 0.46 SiO 2 21.40 21.32 21.37 21.29 21.40 21.34 21.45 21.45 21.44 21.37 21.35 21.34 SO 3 0.74 0.64 0.71 0.72 0.80 0.72 0.72 0.75 0.78 0.85 0.80 0.82 F CaO 1.03 1.21 1.33 1.21 1.75 1.45 1.09 0.36 0.42 1.33 1.15 0.91 C 3 A 8.60 8.50 8.30 8.20 8.00 8.40 8.20 8.00 8.30 8.30 8.40 8.30 C 4 AF 10.20 10.30 10.20 10.40 10.30 10.50 10.60 10.50 10.60 10.60 10.50 10.50 C 3 S 59.50 60.40 60.60 60.70 60.70 59.00 58.60 59.60 58.50 58.90 59.10 59.10 C 2 S 16.50 15.60 15.60 15.20 15.50 16.70 17.30 16.60 17.30 16.90 16.60 16.60 8/14/07 Property (wt. %) 416 Table B.6.12.c: CPR - Chemical Composition of Clinker for 8/15/2007 417 1:52 AM 4:03 AM 5:30 AM 8:09 AM 9:53 AM 11:39 AM 1:52 PM 3:39 PM 5:35 PM 8:18 PM 10:13 PM 11:52 PM Al 2 O 3 5.32 5.31 5.26 5.28 5.18 5.33 5.21 5.06 5.35 5.24 5.19 5.34 CaO 64.57 64.43 64.41 64.58 64.53 64.55 64.77 64.94 64.59 64.85 64.73 64.64 Fe 2 O 3 3.38 3.48 3.45 3.55 3.47 3.65 3.53 3.33 3.55 3.31 3.43 3.61 K 2 O 0.53 0.53 0.59 0.47 0.54 0.53 0.51 0.47 0.52 0.53 0.53 0.53 MgO 3.27 3.31 3.31 3.25 3.32 3.32 3.34 3.25 3.38 3.18 3.40 3.44 Na 2 O 0.09 0.09 0.09 0.09 0.10 0.07 0.06 0.07 0.07 0.07 0.07 0.08 Na 2 O eq 0.44 0.44 0.48 0.40 0.45 0.42 0.40 0.38 0.41 0.42 0.42 0.43 SiO 2 21.27 21.39 21.32 21.36 21.38 21.31 21.35 21.37 21.36 21.32 21.32 21.28 SO 3 0.86 0.85 0.91 0.74 0.91 0.86 0.80 0.79 0.96 0.83 0.84 0.65 F CaO 1.33 0.85 1.45 0.48 0.60 1.45 1.88 0.91 0.60 0.79 1.15 1.09 C 3 A 8.40 8.20 8.10 8.00 7.80 7.90 7.80 7.80 8.20 8.30 8.00 8.10 C 4 AF 10.30 10.60 10.50 10.80 10.60 11.10 10.80 10.10 10.80 10.10 10.40 11.00 C 3 S 60.70 59.20 59.90 60.00 60.50 59.80 61.30 63.20 59.60 62.10 61.70 60.40 C 2 S 15.20 16.70 15.90 16.00 15.70 16.00 14.90 13.60 16.30 14.30 14.50 15.50 Property (wt. %) 8/15/07 Table B.6.12.d: CPR - Chemical Composition of Clinker for 8/16/2007 2:06 AM 3:55 AM 5:28 AM 7:46 AM Al 2 O 3 5.26 5.38 5.28 5.27 5.29 2.2 <0.005 CaO 64.67 64.52 64.70 64.69 64.49 0.5 0.303 Fe 2 O 3 3.50 3.59 3.52 3.55 3.39 4.9 0.121 K 2 O 0.52 0.54 0.54 0.50 0.52 4.9 0.011 MgO 3.39 3.47 3.46 3.46 3.31 3.4 0.685 Na 2 O 0.07 0.07 0.07 0.07 0.08 13.8 <0.005 Na 2 O eq 0.41 0.43 0.43 0.40 0.42 4.3 0.035 SiO 2 21.28 21.27 21.35 21.38 21.34 0.8 <0.005 SO 3 0.80 0.97 0.85 0.83 0.79 9.8 0.080 F CaO 1.15 0.97 0.91 0.85 1.08 34.3 0.374 C 3 A 8.00 8.20 8.00 8.00 8.29 3.5 0.012 C 4 AF 10.70 10.90 10.70 10.80 10.31 4.9 <0.005 C 3 S 61.20 59.80 60.60 60.30 59.97 2.7 0.213 C 2 S 14.80 15.90 15.50 15.80 15.96 9.9 <0.005 Notes: 1 Based on Anderson-Darling Normality Test Average 8/16/07 Property (wt. %) C. V. (%) Normality P-Value 1 418 Table B.6.13: ELR - Chemical Composition of Clinker 1212 1 2 Al 2 O 3 (wt. %) 6.01 5.29 5.24 5.31 5.18 5.23 5.38 CaO (wt. %) 63.27 64.21 64.46 64.28 64.47 64.46 64.19 Fe 2 O 3 (wt. %) 3.05 3.28 3.29 3.27 3.35 3.35 3.27 K 2 O (wt. %) 0.51 0.46 0.45 0.47 0.41 0.45 0.46 MgO (wt. %) 2.98 3.46 3.40 3.41 3.56 3.54 3.39 Na 2 O (wt. %) 0.07 0.07 0.09 0.13 0.08 0.07 0.08 P 2 O 5 (wt. %) 0.07 0.07 0.08 0.07 0.07 0.07 0.07 SiO 2 (wt. %) 22.79 21.87 21.74 21.78 21.57 21.47 21.87 SO 3 (wt. %) 0.76 0.74 0.68 0.74 0.76 0.81 0.75 TiO 2 (wt. %) 0.26 0.28 0.28 0.27 0.27 0.27 0.27 Moisture (wt. %) 0.07 0.00 0.80 0.00 0.06 0.06 0.17 LOI (wt. %) 0.67 0.16 0.13 0.13 0.16 0.15 0.23 As (ppm) 15 18 20 20 15 18 18 Ba (ppm) 391 397 488 389 294 389 391 Cd (ppm) ND ND ND ND ND ND ND Cl (ppm) 133 168 114 54 277 172 153 Co (ppm) 11 9 10 7 13 11 10 Cr (ppm) 86 202 106 104 106 107 119 Cu (ppm) 22 34 20 14 41 18 25 Hg (ppm) 0.25 0.22 0.23 0.16 0.22 0.20 0.21 Mn (ppm) 1466 1784 1952 1943 1962 2044 1859 Mo (ppm) 1NDND2 5 6 2 Ni (ppm) 8 121113 10 151 Pb (ppm) 34 15 < 4 15 < 4 18 20 Sb (ppm) NC NC NC NC NC NC NC Se (ppm) ND ND ND ND ND ND ND Sr (ppm) 489 496 488 486 490 487 489 V (ppm) 65 60 77 69 72 71 69 Zn (ppm) 214 251 367 361 366 357 319 Notes: NA - Not Applicable ND - Not Detected Property 8/13/2007 8/14/2007 8/15/2007 Average 419 B.6.8. EMISSIONS Table B.6.14.a: CPR - Emissions Time NO x (tons/ton clinker) SO 2 (tons/ton clinker) VOC (tons/ton clinker) CO (tons/ton clinker) 5/16/2007 9:00 1.03E-03 1.00E-06 1.68E-05 3.25E-04 5/16/2007 10:00 1.01E-03 1.74E-06 1.71E-05 3.03E-04 5/16/2007 11:00 9.62E-04 2.55E-07 1.72E-05 3.20E-04 5/16/2007 12:00 1.01E-03 4.89E-07 1.90E-05 3.47E-04 5/16/2007 13:00 1.09E-03 4.79E-07 2.12E-05 3.54E-04 5/16/2007 14:00 1.12E-03 6.10E-07 2.24E-05 3.61E-04 5/16/2007 15:00 1.16E-03 4.77E-07 2.57E-05 3.92E-04 5/16/2007 16:00 1.35E-03 8.58E-07 2.70E-05 4.27E-04 5/16/2007 17:00 1.28E-03 8.36E-07 2.68E-05 3.34E-04 5/16/2007 18:00 1.15E-03 5.81E-07 2.65E-05 3.52E-04 5/16/2007 19:00 1.16E-03 8.61E-07 2.54E-05 3.70E-04 5/16/2007 20:00 1.14E-03 7.48E-07 2.55E-05 3.87E-04 5/16/2007 21:00 1.02E-03 1.19E-06 2.13E-05 3.32E-04 5/16/2007 22:00 1.04E-03 9.90E-07 2.23E-05 3.82E-04 5/16/2007 23:00 1.19E-03 1.77E-06 2.49E-05 3.94E-04 5/17/2007 0:00 1.08E-03 1.07E-06 2.24E-05 3.70E-04 5/17/2007 1:00 1.19E-03 1.18E-06 2.22E-05 3.35E-04 5/17/2007 2:00 1.05E-03 1.29E-06 1.86E-05 3.20E-04 5/17/2007 3:00 1.31E-03 1.68E-06 1.99E-05 3.47E-04 5/17/2007 4:00 1.01E-03 1.76E-06 1.93E-05 3.47E-04 5/17/2007 5:00 9.02E-04 1.22E-06 1.80E-05 3.12E-04 5/17/2007 6:00 9.98E-04 1.54E-06 1.81E-05 3.53E-04 5/17/2007 7:00 1.03E-03 1.01E-06 1.78E-05 3.56E-04 5/17/2007 8:00 1.02E-03 1.56E-06 1.54E-05 2.98E-04 5/17/2007 9:00 1.12E-03 7.15E-07 1.72E-05 2.95E-04 5/17/2007 10:00 1.00E-03 2.47E-07 1.65E-05 3.41E-04 5/17/2007 11:00 1.13E-03 2.15E-07 1.52E-05 3.52E-04 5/17/2007 12:00 1.18E-03 1.37E-07 1.50E-05 2.94E-04 5/17/2007 13:00 1.06E-03 1.46E-07 1.51E-05 3.01E-04 5/17/2007 14:00 1.29E-03 1.68E-07 1.94E-05 3.88E-04 5/17/2007 15:00 1.10E-03 2.20E-07 2.05E-05 3.44E-04 5/17/2007 16:00 1.20E-03 3.15E-07 2.19E-05 3.36E-04 5/17/2007 17:00 1.09E-03 3.80E-07 2.21E-05 3.97E-04 5/17/2007 18:00 1.18E-03 7.25E-07 2.89E-05 5.11E-04 5/17/2007 19:00 9.71E-04 5.81E-07 2.42E-05 3.78E-04 5/17/2007 20:00 1.07E-03 6.11E-07 2.69E-05 3.96E-04 5/17/2007 21:00 1.05E-03 8.08E-07 2.60E-05 4.54E-04 5/17/2007 22:00 9.68E-04 6.94E-07 2.59E-05 4.12E-04 5/17/2007 23:00 9.93E-04 5.74E-07 2.62E-05 4.27E-04 420 421 Table B.6.14.b: CPR - Emissions Time NO x (tons/ton clinker) SO 2 (tons/ton clinker) VOC (tons/ton clinker) CO (tons/ton clinker) 5/18/2007 0:00 1.05E-03 9.66E-07 2.27E-05 4.20E-04 5/18/2007 1:00 1.17E-03 7.19E-07 2.09E-05 4.38E-04 5/18/2007 2:00 1.14E-03 1.15E-06 1.98E-05 4.52E-04 5/18/2007 3:00 1.12E-03 1.02E-06 1.94E-05 4.39E-04 5/18/2007 4:00 1.15E-03 1.20E-06 1.92E-05 4.27E-04 5/18/2007 5:00 9.34E-04 1.34E-06 1.76E-05 4.16E-04 5/18/2007 6:00 1.11E-03 1.99E-06 1.80E-05 4.38E-04 5/18/2007 7:00 1.04E-03 1.14E-06 1.66E-05 4.23E-04 5/18/2007 8:00 1.09E-03 1.42E-06 1.70E-05 4.29E-04 5/18/2007 9:00 1.07E-03 1.33E-06 1.80E-05 4.05E-04 5/18/2007 10:00 1.03E-03 1.05E-06 2.05E-05 3.78E-04 5/18/2007 11:00 1.18E-03 1.24E-06 2.33E-05 4.30E-04 5/18/2007 12:00 1.17E-03 7.49E-07 2.34E-05 4.39E-04 5/18/2007 13:00 1.05E-03 7.20E-07 2.27E-05 4.40E-04 5/18/2007 14:00 1.15E-03 7.20E-07 2.32E-05 4.03E-04 5/18/2007 15:00 1.11E-03 5.69E-07 2.52E-05 3.99E-04 5/18/2007 16:00 1.03E-03 4.73E-07 2.44E-05 3.75E-04 5/18/2007 17:00 1.14E-03 7.42E-07 2.67E-05 4.12E-04 5/18/2007 18:00 1.14E-03 5.49E-07 2.67E-05 3.76E-04 5/18/2007 19:00 1.19E-03 4.01E-07 2.79E-05 3.93E-04 5/18/2007 20:00 1.13E-03 4.71E-07 2.65E-05 3.75E-04 5/18/2007 21:00 1.25E-03 5.36E-07 2.71E-05 4.08E-04 5/18/2007 22:00 1.27E-03 8.87E-07 2.62E-05 3.54E-04 5/18/2007 23:00 1.25E-03 7.51E-07 2.52E-05 3.82E-04 5/19/2007 0:00 1.23E-03 7.20E-07 2.31E-05 3.61E-04 5/19/2007 1:00 1.32E-03 6.87E-07 2.31E-05 3.46E-04 5/19/2007 2:00 1.34E-03 7.42E-07 2.32E-05 3.57E-04 5/19/2007 3:00 NC NC NC 3.89E-04 5/19/2007 4:00 1.31E-03 1.03E-06 2.07E-05 3.66E-04 5/19/2007 5:00 1.27E-03 1.05E-06 2.08E-05 3.98E-04 5/19/2007 6:00 1.30E-03 1.28E-06 2.15E-05 4.02E-04 5/19/2007 7:00 1.35E-03 1.19E-06 2.15E-05 4.06E-04 5/19/2007 8:00 1.29E-03 9.39E-07 2.07E-05 4.02E-04 Average 1.13E-03 8.66E-07 2.18E-05 3.79E-04 C. V. (%) 9.8 49.8 17.0 11.6 Normality P-Value 1 0.015 <0.005 0.008 0.214 Notes: 1 Based on Anderson Darling Normality Test NC - Not Collected 422 APPENDIX B.7 RAW DATA FOR CTW BURN B.7.1. GENERAL COMMENTS ? The raw data from the CTW burn are presented in this appendix. ? Coal, scrap tires and woodchips are the fuels used in the burn. ? The burn lasted from 9 AM on October 16, 2007 to 9 AM on October 19, 2007. B.7.2. NOTATION CPR ? Cement Plant Results ELR ? External Lab Results AUR ? Auburn University Results C. V. ? Coefficient of Variation B.7.3. CHEMICAL COMPOSITION OF RAW MATERIALS 423 Property (wt. %) Raw Material One Raw Material Five Raw Material Six Al 2 O 3 25.50 0.40 0.43 6.16 1.15 2.50 CaO 2.74 51.85 56.13 33.15 1.60 31.47 Fe 2 O 3 7.15 0.00 0.00 27.49 1.70 0.30 K 2 O 2.26 0.07 0.08 0.02 0.20 0.25 MgO 1.03 0.97 0.89 11.53 0.20 3.25 Na 2 O 0.38 0.13 0.06 0.11 NR 0.22 SiO 2 50.10 2.00 2.33 12.92 95.85 13.60 SO 3 0.27 0.13 0.12 0.67 0.20 32.95 Moisture 31.70 3.50 NR NR 3.50 10.11 LOI 8.80 42.20 41.50 4.33 0.40 11.52 Notes: ND - Not Detected NR - Not Reported Table B.7.1: CPR - Chemical Composition of Raw Materials Raw Material Two Raw Material Three Raw Material Four 424 Table B.7.2: ELR - Chemical Composition of Raw Materials Property Raw Material One Raw Material Two Raw Material ThreeRaw Material Four Raw Material Five Raw Material Six Al 2 O 3 (wt. %) 23.49 0.30 4.10 5.57 0.63 0.68 CaO (wt. %) 2.95 53.59 39.28 66.01 0.36 32.92 Fe 2 O 3 (wt. %) 9.49 0.16 1.88 2.91 0.31 0.47 K 2 O (wt. %) 2.34 0.06 0.69 0.64 0.15 0.14 MgO (wt. %) 1.11 1.00 3.29 1.96 0.06 0.86 Na 2 O (wt. %) 0.43 0.02 0.04 0.08 0.02 0.12 P 2 O 5 (wt. %) 0.52 0.00 0.01 0.04 0.00 0.01 SiO 2 (wt. %) 42.85 1.20 14.56 17.70 97.92 3.97 SO 3 (wt. %) 0.17 0.09 0.28 0.31 0.15 43.53 TiO 2 (wt. %) 1.20 0.00 0.14 0.28 0.19 0.03 Moisture (wt. %) 21.90 2.85 3.91 7.15 2.96 0.00 LOI (wt. %) 15.07 43.53 35.68 4.38 0.18 17.13 As (ppm) 137 ND 10 13 ND ND Ba (ppm) 2000 100 200 300 200 200 Cd (ppm) ND ND ND ND ND ND Cl (ppm) 36 40 62 134 96 11 Co (ppm) 6426744 Cr (ppm) 220 76 82 146 58 79 Cu (ppm) 145NDNDNDNDND Hg (ppm) 0.10 0.10 0.10 0.20 0.10 0.05 Mn (ppm) 400 100 100 800 100 400 Mo (ppm) 30 ND 3 ND 1 ND Ni (ppm) 113 ND 10 7 ND ND Pb (ppm) 73 17 4 22 ND ND Sb (ppm) NR NR NR NR NR NR Se (ppm) 3 NDNDNDNDND Sr (ppm) 1400 300 200 400 0 700 V (ppm) 3091350681522 Zn (ppm) 142 ND 31 37 ND ND Notes: ND - Not Detected NR - Not Reported Table B.7.3: CPR - Chemical Composition of Kiln Feed 1:44 PM 2:04 AM 1:46 PM 1:59 AM 1:41 PM 2:12 AM 1:41 PM Al 2 O 3 2.96 3.05 2.99 2.94 2.93 2.85 3.08 2.97 2.6 CaO 42.98 42.99 42.93 43.02 43.01 43.09 43.17 43.03 0.2 Fe 2 O 3 1.92 1.95 1.83 1.87 1.94 1.92 1.97 1.91 2.5 K 2 O 0.31 0.32 0.36 0.36 0.34 0.34 0.38 0.34 7.1 MgO 1.96 1.94 1.91 1.94 1.99 2.04 1.95 1.96 2.2 Na 2 O 0.18 0.16 0.16 0.14 0.15 0.16 0.16 0.16 7.7 Na 2 O eq 0.38 0.4 0.38 0.37 0.38 0.41 0.39 3.9 SiO 2 13.69 13.62 13.47 13.43 13.27 13.36 13.23 13.44 1.3 SO 3 0.22 0.21 0.21 0.2 0.2 0.21 0.2 0.21 3.6 LOI 35 35 35 35 35 35 35 35.00 0.0 C. V. (%)Property (wt. %) 10/16/2007 10/17/2007 10/18/2007 Average B.7.4. CHEMICAL COMPOSITION OF KILN FEED 425 Table B.7.4: ELR - Chemical Composition of Kiln Feed Property 3-Day Composite Al 2 O 3 (wt. %) 2.96 CaO (wt. %) 41.36 Fe 2 O 3 (wt. %) 1.83 K 2 O (wt. %) 0.32 MgO (wt. %) 2.04 Na 2 O (wt. %) 0.05 P 2 O 5 (wt. %) 0.02 SiO 2 (wt. %) 13.26 SO 3 (wt. %) 0.21 TiO 2 (wt. %) 0.15 Moisture (wt. %) 0.23 LOI (wt. %) 38 As (ppm) 17 Ba (ppm) 200 Cd (ppm) ND Cl (ppm) 192 Co (ppm) 8 Cr (ppm) 159 Cu (ppm) ND Hg (ppm) 0 Mn (ppm) 1100 Mo (ppm) 3 Ni (ppm) ND Pb (ppm) 12 Sb (ppm) NR Se (ppm) ND Sr (ppm) 200 V (ppm) 61 Zn (ppm) 33 Notes: ND - Not Detected NR - Not Reported 426 B.7.5. CHEMICAL COMPOSITION OF FUELS Table B.7.5: CPR - Chemical Composition of Coal Test Parameter Value (wt. %) Ash 18.78 Fixed Carbon 53.48 Volatile Matter 27.74 Carbon 53.48 Hydrogen 4.39 Nitrogen 1.31 Oxygen 3.23 Sulfur 1.41 Al 2 O 3 28.92 CaO 0.95 Fe 2 O 3 7.48 K 2 O 3.26 MgO 1.20 Na 2 O 0.43 SiO 2 55.55 SO 3 1.01 12321 Notes: 1 Value is Reported as BTU/lb Heat Value 1 Proximate Analysis Ul ti mate Analysis S t an d a rd Parameters 427 Table B.7.6: ELR - Proximate, Ultimate, and Combustion of Coal Test Parameter Value (wt. %) Ash 17.59 Fixed Carbon 53.8 Volatile Matter 28.61 Carbon 71.06 Hydrogen 4.16 Nitrogen 1.48 Oxygen 4.57 Sulfur 1.14 12445 Proximate Analysis Ul ti mate An aly s is Heat Value 1 Notes: 1 Value is Reported as BTU/lb 428 Table B.7.7: ELR - Standard Parameters of Coal Property 3-Day Composite Al 2 O 3 (wt. %) 24.6 CaO (wt. %) 9.3 Fe 2 O 3 (wt. %) 7.5 K 2 O (wt. %) 2.2 MgO (wt. %) 1.1 Na 2 O (wt. %) 0.2 P 2 O 5 (wt. %) 0.2 SiO 2 (wt. %) 47.2 SO 3 (wt. %) 6.4 TiO 2 (wt. %) 1.2 As (ppm) 86 Ba (ppm) 1096 Cd (ppm) ND Cl (ppm) 105 Co (ppm) 54 Cr (ppm) 190 Cu (ppm) 70 Hg (ppm) 0.2 Mn (ppm) 498 Mo (ppm) 31 Ni (ppm) 79 Pb (ppm) 47 Sb (ppm) NR Se (ppm) 6 Sr (ppm) 598 V (ppm) 214 Zn (ppm) 63 NR - Not Reported Notes: ND - Not Detected 429 Table B.7.8: ELR - Proximate, Ultimate, and Combustion Analysis of Tires Test Parameter Value (wt. %) Ash 14.99 Fixed Carbon 23.56 Moisture 1 0.36 Volatile Matter 61.45 Carbon 77.6 Hydrogen 5.9 Nitrogen 0.1 Oxygen 0.31 Sulfur 1.10 15098 Notes: 1 As Received 2 Value is Reported as BTU/lb Ul ti mate An alysis Heat Value 2 Proximate An alysis 430 Table B.7.9: ELR - Standard Parameters of Tires Property 3-Day Composite Al 2 O 3 (wt. %) 4.42 CaO (wt. %) 3.00 Fe 2 O 3 (wt. %) 57.72 K 2 O (wt. %) 0.48 MgO (wt. %) 0.36 Na 2 O (wt. %) 1.49 P 2 O 5 (wt. %) 0.43 SiO 2 (wt. %) 12.89 SO 3 (wt. %) 4.15 TiO 2 (wt. %) 3.74 As (ppm) ND Ba (ppm) ND Cd (ppm) ND Cl (ppm) 515 Co (ppm) 642 Cr (ppm) 133 Cu (ppm) 3762 Hg (ppm) 0.1 Mn (ppm) 3754 Mo (ppm) 8 Ni (ppm) 8 Pb (ppm) 30 Sb (ppm) NR Se (ppm) ND Sr (ppm) 36 V (ppm) 117 Zn (ppm) 0 Notes: ND - Not Detected NR - Not Reported 431 Table B.7.10: ELR - Proximate, Ultimate, and Combustion Analysis of Woodchips Test Parameter Value (wt. %) Ash 0.82 Fixed Carbon 16.94 Moisture 1 36.46 Volatile Matter 82.24 Carbon 52.64 Hydrogen 5.83 Nitrogen 0.15 Oxygen 40.53 Sulfur 0.02 8388 Notes: 1 As Received 2 Value is Reported as BTU/lb Ul ti mate Analysis Heat Value 2 Proximate Analysis 432 Table B.7.11: ELR - Standard Parameters of Woodchips Property 3-Day Composite Al 2 O 3 (wt. %) 0.93 CaO (wt. %) 54.61 Fe 2 O 3 (wt. %) 1.79 K 2 O (wt. %) 17.28 MgO (wt. %) 9.83 Na 2 O (wt. %) 0.38 P 2 O 5 (wt. %) 2.80 SiO 2 (wt. %) 3.27 SO 3 (wt. %) 3.33 TiO 2 (wt. %) 0.02 As (ppm) 12 Ba (ppm) 9692 Cd (ppm) ND Cl (ppm) 425 Co (ppm) 64 Cr (ppm) 16 Cu (ppm) 126 Hg (ppm) 0.1 Mn (ppm) 43581 Mo (ppm) 65 Ni (ppm) 169 Pb (ppm) 60 Sb (ppm) NR Se (ppm) ND Sr (ppm) 4230 V (ppm) 172 Zn (ppm) 959 Notes: ND - Not Detected NR - Not Reported 433 434 Table B.7.12: AUR - Density of Woodchips Sample # Density (kg/m 3 ) 1 251.4 2 291.5 3 253.5 4 261.1 5 258.4 6 275.6 7 267.7 8 263.1 9 269.3 10 256.6 11 251.1 12 276.4 13 276.7 14 273.8 15 256.1 16 261.8 17 259.6 18 253.2 19 265.2 20 254.6 21 256.6 22 262.3 23 255.4 24 254.6 Average 262.7 B.7.6. CHEMICAL COMPOSITION OF CEMENT KILN DUST (CKD) Table B.7.13: CPR - Chemical Composition of Cement Kiln Dust 9:16 AM 7:15 PM 7:47 AM 7:06 PM 8:40 AM 7:16 PM 9:10 AM Al 2 O 3 4.02 3.91 3.86 4.01 4.45 4.62 4 4.12 CaO 44.97 45.1 45.43 44.99 43.95 42.96 44.76 44.59 Fe 2 O 3 2.04 2.03 2 2.03 2.12 2.21 2.04 2.07 K 2 O 0.51 0.51 0.5 0.51 0.57 0.6 0.5 0.53 MgO 1.33 1.35 1.32 1.27 1.35 1.36 1.37 1.34 Na 2 O 0.04 0.03 0.03 0.03 0.04 0.04 0.04 0.04 SiO 2 11.96 12.26 11.89 12.07 12.53 12.71 11.75 12.17 SO 3 0.2 0.22 0.2 0.2 0.42 0.4 0.2 0.26 10/18/2007 AverageProperty (wt. %) 10/17/200710/16/2007 435 Table B.7.14: ELR - Chemical Composition of Cement Kiln Dust 5:16 PM 3.6 3.77 4.02 3.82 4.21 Al 2 O 3 (wt. %) 3.72 3.60 3.77 4.02 3.82 4.21 3.86 CaO (wt. %) 44.12 44.44 43.58 42.85 43.09 43.76 43.64 Fe 2 O 3 (wt. %) 1.99 1.96 1.87 1.94 1.98 2.20 1.99 K 2 O (wt. %) 0.40 0.42 0.42 0.47 0.41 0.38 0.42 MgO (wt. %) 1.30 1.36 1.30 1.35 1.26 1.33 1.32 Na 2 O (wt. %) 0.06 0.04 0.03 0.10 0.04 0.06 0.06 P 2 O 5 (wt. %) 0.03 0.03 0.03 0.04 0.04 0.04 0.04 SiO 2 (wt. %) 11.76 11.72 12.24 12.46 11.32 12.22 11.95 SO 3 (wt. %) 0.22 0.20 0.20 0.19 0.34 0.36 0.25 TiO 2 (wt. %) 0.20 0.18 0.17 0.20 0.20 0.23 0.20 Moisture (wt. %) 0.25 0.23 0.30 0.20 0.20 17.83 3.17 LOI (wt. %) 36.10 35.95 36.29 36.28 37.40 35.10 36.19 As (ppm) 14 13 18 12 18 19 16 Ba (ppm) 300 100 200 300 100 300 217 Cd (ppm) ND ND ND ND ND ND ND Cl (ppm) 167 171 190 171 1173 1354 538 Co (ppm) 985 412110 Cr (ppm) 153 112 71 136 109 102 114 Cu (ppm) ND ND ND ND ND ND ND Hg (ppm) 0.60 0.60 0.50 0.40 1.40 1.70 1 Mn (ppm) 500 600 500 400 600 500 517 Mo (ppm) ND ND 11 5 5 ND 4 Ni (ppm) 5 911810109 Pb (ppm) < 416183531 92 Sb (ppm) NR NR NR NR NR NR ND Se (ppm) ND ND ND ND ND ND ND Sr (ppm) 300 300 300 300 300 300 300 V (ppm) 65 59 59 73 70 70 66 Zn (ppm) 35 33 36 39 44 42 38 Notes: ND - Not Detected NR - Not Reported AverageProperty 10/16/2007 10/17/2007 10/18/2007 436 B.7.7. CHEMICAL COMPOSITION OF CLINKER Table B.7.15.a: CPR - Chemical Composition of Clinker for 10/16/2007 5:47 AM 7:51 AM 9:37 AM 11:47 AM 1:44 PM 3:35 PM 5:43 PM 7:59 PM 10:00 PM Al 2 O 3 5.08 5.24 5.15 5.22 5.32 5.10 5.13 5.07 5.12 CaO 64.39 64.22 64.44 64.47 64.20 64.69 64.38 64.07 64.44 Fe 2 O 3 3.50 3.53 3.38 3.40 3.42 3.24 3.27 3.31 3.28 K 2 O 0.43 0.45 0.48 0.45 0.47 0.45 0.50 0.46 0.41 MgO 3.27 3.24 3.24 3.25 3.23 3.24 3.19 3.14 3.20 Na 2 O 0.07 0.07 0.08 0.07 0.07 0.07 0.08 0.07 0.06 Na 2 O eq 0.35 0.37 0.39 0.37 0.38 0.37 0.41 0.37 0.33 SiO 2 21.57 21.43 21.48 21.57 21.45 21.51 21.47 21.30 21.42 SO 3 0.93 0.86 0.98 0.79 0.92 0.58 1.04 1.66 0.49 F CaO 0.33 0.58 1.05 0.75 2.24 1.74 1.68 1.57 0.97 C 3 A 7.50 7.90 7.90 8.10 8.30 8.00 8.10 7.80 8.00 C 4 AF 10.70 10.70 10.30 10.40 10.40 9.90 9.90 10.10 10.00 C 3 S 59.10 58.40 59.70 58.60 57.70 61.00 59.80 60.20 60.40 C 2 S 17.30 17.40 16.60 17.70 18.00 15.70 16.50 15.70 15.90 Property (wt. %) 10/16/2007 437 Table B.7.15.b: CPR - Chemical Composition of Clinker for 10/17/2007 438 12:00 AM 1:07 AM 1:57 AM 3:54 AM 5:29 AM 7:43 AM 9:40 AM 11:32 AM 12:44 PM 1:46 PM 3:44 PM 5:37 PM Al 2 O 3 5.13 5.12 5.00 5.05 5.04 5.01 4.94 4.93 4.86 4.91 4.95 5.01 CaO 64.40 64.69 64.97 64.94 64.72 64.82 65.19 64.54 64.92 64.96 65.01 64.78 Fe 2 O 3 3.16 3.17 3.05 3.16 3.09 3.06 3.12 2.94 3.02 3.12 3.26 3.15 K 2 O 0.69 0.60 0.59 0.56 0.58 0.57 0.55 0.79 0.57 0.58 0.58 0.67 MgO 3.25 3.34 3.33 3.30 3.29 3.31 3.29 3.23 3.37 3.25 3.30 3.30 Na 2 O 0.06 0.05 0.05 0.05 0.05 0.05 0.05 0.06 0.05 0.05 0.05 0.05 Na 2 O eq 0.51 0.45 0.44 0.42 0.43 0.42 0.41 0.58 0.43 0.43 0.43 0.49 SiO 2 20.91 21.51 21.57 21.57 21.75 21.65 21.51 21.37 21.69 21.74 21.58 21.42 SO 3 2.17 1.01 0.69 0.49 0.87 0.81 0.50 1.49 0.75 0.55 0.44 1.00 F CaO 2.40 1.38 1.32 1.44 0.78 0.90 1.44 1.74 0.84 0.78 0.66 1.38 C 3 A 8.25 8.20 8.11 8.05 8.11 8.08 7.82 8.09 7.77 7.72 7.61 7.95 C 4 AF 9.62 9.65 9.27 9.61 9.41 9.32 9.49 8.95 9.20 9.49 9.91 9.59 C 3 S 64.27 61.00 62.55 61.97 59.94 61.30 64.20 63.01 62.48 61.85 62.74 62.77 C 2 S 11.46 15.64 14.66 15.09 17.13 15.83 13.24 13.74 15.05 15.67 14.54 14.06 Property (wt. %) 10/17/2007 Table B.7.15.c: CPR - Chemical Composition of Clinker for 10/18/2007 439 11:53 PM 1:51 AM 4:03 AM 5:34 AM 6:35 AM 7:39 AM 8:40 AM 9:49 AM 11:53 AM 1:46 PM 3:23 PM 5:31 PM Al 2 O 3 4.99 5.00 5.04 4.98 5.00 4.97 4.95 4.95 4.93 4.97 4.95 4.89 CaO 65.23 64.94 64.75 64.78 64.85 64.96 64.89 65.01 64.99 64.98 64.76 64.98 Fe 2 O 3 3.18 3.25 3.26 3.19 3.27 3.24 3.11 3.15 3.33 3.11 3.09 3.13 K 2 O 0.49 0.57 0.60 0.56 0.56 0.58 0.58 0.60 0.56 0.57 0.68 0.61 MgO 3.34 3.34 3.26 3.30 3.30 3.32 3.32 3.33 3.28 3.27 3.26 3.29 Na 2 O 0.04 0.05 0.05 0.05 0.05 0.05 0.06 0.05 0.05 0.05 0.05 0.05 Na 2 O eq 0.37 0.43 0.44 0.42 0.42 0.43 0.44 0.45 0.42 0.43 0.50 0.45 SiO 2 21.55 21.63 21.59 21.54 21.49 21.47 21.45 21.50 21.56 21.56 21.50 21.62 SO 3 0.35 0.51 0.89 1.04 0.85 0.67 0.89 0.55 0.52 0.82 1.04 0.64 F CaO 1.32 1.32 0.60 0.78 1.20 1.68 1.32 1.62 1.50 0.84 0.78 C 3 A 7.83 7.73 7.82 7.81 7.72 7.69 7.86 7.79 7.42 7.89 7.89 7.66 C 4 AF 9.68 9.90 9.93 9.70 9.97 9.85 9.45 9.59 10.13 9.48 9.40 9.52 C 3 S 63.73 61.77 61.04 62.00 62.41 63.29 63.42 63.50 62.84 62.83 62.57 62.89 C 2 S 13.70 15.41 15.84 14.98 14.53 13.80 13.67 13.73 14.41 14.41 14.44 14.54 Property (wt. %) 10/18/2007 Table B.7.15.d: CPR - Chemical Composition of Clinker for 10/19/2007 440 7:15 PM 8:13 PM 10:06 PM 11:52 PM 2:03 AM 3:47 AM 5:32 AM 7:37 AM 10:18 AM Al 2 O 3 5.00 5.20 5.07 5.04 5.08 5.20 5.05 5.02 5.02 5.04 2.0 0.032 CaO 65.08 64.92 64.91 64.98 65.02 64.82 64.96 65.09 65.03 64.79 0.6 0.311 Fe 2 O 3 3.20 3.17 3.11 3.17 3.17 3.23 3.19 3.16 3.20 3.20 6.1 <0.005 K 2 O 0.61 0.68 0.66 0.60 0.66 0.65 0.63 0.61 0.61 0.57 4.6 0.177 MgO 3.07 3.16 3.13 3.19 3.22 3.25 3.17 3.24 3.28 3.26 3.3 0.572 Na 2 O 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.06 5.8 <0.005 Na 2 O eq 0.45 0.50 0.48 0.45 0.48 0.48 0.46 0.45 0.45 0.43 4.4 0.253 SiO 2 21.53 21.39 21.47 21.52 21.35 21.42 21.49 21.48 21.44 21.50 1.2 0.304 SO 3 0.67 0.83 0.83 0.75 0.81 0.77 0.74 0.65 0.69 0.82 21.1 <0.005 F CaO 0.72 0.72 0.60 1.17 41.0 0.374 C 3 A 7.84 8.42 8.17 7.99 8.10 8.31 7.99 7.96 7.89 7.93 5.4 0.031 C 4 AF 9.74 9.65 9.46 9.65 9.65 9.83 9.71 9.62 9.74 9.75 6.2 0.102 C 3 S 63.15 62.26 62.57 62.60 63.78 61.54 62.64 63.49 63.49 61.92 3.9 <0.005 C 2 S 14.09 14.36 14.35 14.47 13.10 14.99 14.36 13.69 13.57 14.94 16.4 0.007 Notes: 1 Based on Anderson-Darling Normality Test C. V. (%) 10/19/2007 Property (wt. %) Normality P-Value 1 Average Table B.7.16: ELR - Chemical Composition of Clinker 12 1 2 1 2 Al 2 O 3 (wt. %) 4.98 5.09 5.06 5.11 4.97 5.15 5.06 CaO (wt. %) 64.03 64.12 64.51 64.60 64.84 64.45 64.43 Fe 2 O 3 (wt. %) 3.07 3.09 3.10 3.11 3.00 3.05 3.07 K 2 O (wt. %) 0.61 0.55 0.53 0.51 0.51 0.54 0.54 MgO (wt. %) 3.33 3.29 3.40 3.37 3.35 3.34 3.35 Na 2 O (wt. %) 0.06 0.07 0.08 0.05 0.06 0.11 0.07 P 2 O 5 (wt. %) 0.06 0.06 0.03 0.05 0.05 0.05 0.05 SiO 2 (wt. %) 22.03 22.28 22.25 22.17 22.15 21.90 22.13 SO 3 (wt. %) 1.12 0.67 0.45 0.43 0.50 0.65 0.64 TiO 2 (wt. %) 0.25 0.26 0.25 0.25 0.24 0.26 0.25 Moisture (wt. %) 0.06 0.04 0.00 0.04 0.00 0.04 0.03 LOI (wt. %) 0.15 0.18 0.09 0.10 0.07 0.25 0.14 As (ppm) 18 21 15 15 21 20 18 Ba (ppm) 300 400 300 300 300 300 317 Cd (ppm) ND ND ND ND ND ND ND Cl (ppm) 290 753 21 58 70 557 292 Co (ppm) 913 9 9 9 9 Cr (ppm) 111 113 98 86 90 89 98 Cu (ppm) 14 22 21 13 14 7 15 Hg (ppm) 0.05 0.16 0.13 0.11 0.14 0.08 0.11 Mn (ppm) 2400 2500 1900 1900 2000 1900 2100 Mo (ppm) 66 2NDNDND5 Ni (ppm) 812 8 6 5 7 8 Pb (ppm) 29 ND 11 ND ND 12 17 Sb (ppm) NR NR NR NR NR NR NA Se (ppm) ND ND ND ND ND ND ND Sr (ppm) 400 400 400 400 400 400 400 V (ppm) 72 73 63 61 64 63 66 Zn (ppm) 79 70 82 88 77 51 75 Property 10/16/2007 10/17/2007 10/18/2007 Average Notes: NA - Not Applicable ND - Not Detected 441 B.7.8. CHEMICAL COMPOSITION OF CEMENT Table B.7.17: CPR - Chemical Composition of Cement 442 7:07 AM 10:12 AM 11:34 AM 1:09 PM 2:39 PM 4:01 PM 6:43 PM 9:54 PM 1:13 AM 4:12 AM 11:53 AM Al 2 O 3 4.68 4.67 4.65 4.63 4.64 4.64 4.59 4.6 4.57 4.62 4.71 4.64 0.9 0.216 CaO 63.86 63.44 63.79 63.75 63.37 63.74 63.64 63.66 63.87 63.5 63.63 63.66 0.3 0.150 Fe 2 O 3 3.19 3.14 3.13 3.11 3.1 3.13 3.2 3.22 3.21 3.13 3.12 3.15 1.4 <0.005 K 2 O 0.52 0.51 0.51 0.5 0.5 0.51 0.5 0.52 0.53 0.52 0.52 0.51 2.0 0.100 MgO 3.13 3.14 3.14 3.13 3.12 3.11 3.16 3.15 3.11 3.11 3.18 3.13 0.7 <0.005 Na 2 O 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.07 0.06 5.0 <0.005 Na 2 O eq 0.41 0.39 0.39 0.39 0.39 0.39 0.39 0.4 0.41 0.41 0.41 0.40 2.5 <0.005 SiO 2 20.36 20.27 20.48 20.46 20.43 20.55 20.45 20.36 20.38 20.22 20.44 20.40 0.5 0.148 SO 3 2.73 2.62 2.64 2.63 2.57 2.7 2.67 2.71 2.73 2.61 2.57 2.65 2.2 0.126 F CaO 1.08 1.26 1.08 NR 0.9 1.02 0.9 1.2 1.14 1.14 0.96 1.07 11.5 0.139 LOI 0.92 1.3 NR 1.24 1.17 1.21 1.27 1.25 1.22 1.43 0.97 1.20 12.6 <0.005 C 3 A 7.01 7.06 7.04 7.01 7.06 7 6.76 6.75 6.69 6.94 7.21 6.96 2.3 0.310 C 4 AF 9.72 9.56 9.52 9.45 9.43 9.54 9.74 9.8 9.77 9.54 9.49 9.60 1.4 0.251 C 3 S 61.39 60.9 60.82 61.02 59.71 59.91 60.62 61.18 62.04 61.92 60.26 60.89 1.2 0.323 C 2 S 12.07 12.17 12.82 12.62 13.54 13.72 12.9 12.22 11.63 11.25 13.13 12.55 6.1 <0.005 Blaine SSA (m 2 /kg) 385 387 384 NR 389 385 383 386 379 386 371 384 1.3 0.143 Notes: 1 Based on Anderson-Darling Normality Test NR- Not Reported Property (wt. %) Average Normality P-Value 1 C. V. (%) 10/22/2007 10/23/2007 Table B.7.18: ELR - Chemical Composition of Cement Property 123Average Al 2 O 3 (wt. %) 4.82 4.75 4.82 4.80 CaO (wt. %) 62.85 62.89 62.81 62.85 Fe 2 O 3 (wt. %) 2.94 2.86 2.93 2.91 K 2 O (wt. %) 0.50 0.57 0.51 0.53 MgO (wt. %) 3.24 3.31 3.24 3.26 Na 2 O (wt. %) 0.06 0.07 0.06 0.06 P 2 O 5 (wt. %) 0.05 0.06 0.04 0.05 SiO 2 (wt. %) 21.12 21.07 21.24 21.14 SO 3 (wt. %) 2.97 2.83 2.59 2.80 TiO 2 (wt. %) 0.24 0.23 0.24 0.24 Moisture (wt. %) 0.19 0.18 0.22 0.20 LOI (wt. %) 0.95 1.08 1.25 1.09 C 3 S (wt. %) 50.29 51.82 50.32 50.81 C 2 S (wt. %) 22.61 21.31 22.94 22.29 C 3 A (wt. %) 7.80 7.75 7.82 7.79 C 4 AF (wt. %) 8.95 8.70 8.92 8.86 TOC (wt. %) ND ND ND ND As (ppm) 17 19 12 16 Ba (ppm) 300 400 300 333 Cd (ppm) ND ND ND ND Cl (ppm) 52 105 71 76 Co (ppm) 7119 9 Cr (ppm) 100 96 94 97 Cu (ppm) ND ND ND ND Hg (ppm) 0.06 0.09 0.07 0.07 Mn (ppm) 2000 2100 2000 2033 Mo (ppm) ND ND 3 1 Ni (ppm) 7777 Pb (ppm) ND 12 13 12 Sb (ppm) NR NR NR NR Se (ppm) ND ND ND ND Sr (ppm) 400 400 400 400 V (ppm) 63 68 54 62 Zn (ppm) 84 75 90 83 Notes: ND - Not Detected NR - Not Reported 443 B.7.9. PHYSICAL PROPERTIES OF CEMENT Table B.7.19: CPR - Physical Properties of Cement Property Average Air in Mortar (%) 6.4 Blaine Specific Surface Area (m 2 /kg) 372 Autoclave Expansion (% Exp.) 0.06 Cube Flow (%) 130.0 Comp Str 1day (MPa) 14.3 Comp Str 3day (MPa) 23.9 Comp Str 7day (MPa) 30.6 Comp Str 28day (MPa) 43.3 Normal Consistency (%) 25.2 Gillmore Initial Set (Min) NR Gillmore Final Set (Min) NR Vicat Initial Set (Min) 71 Vicat Final Set (Min) 228 Notes: % Exp. - Percent Expansion Table B.7.20: AUR - Physical Properties of Cement Property Composite Autoclave Expansion (% Exp.) 0.05 Cube Flow (%) 106 Comp Str 1day (MPa) 10.9 Comp Str 3day (MPa) 22.8 Comp Str 7day (MPa) 28.3 Comp Str 28day (MPa) 35.1 Normal Consistency (%) 26.2 Gillmore Initial Set (Min) 108 Gillmore Final Set (Min) 205 Vicat Initial Set (Min) 84 Vicat Final Set (Min) 150 Drying Shrinkage @ 7 days (% LC) -0.045 Drying Shrinkage @ 14 days (% LC) -0.070 Drying Shrinkage @ 21 days (% LC) -0.080 Drying Shrinkage @ 28 days (% LC) -0.088 Notes: % LC - Percent Length Change % Exp. - Percent Expansion 444 B.7.10. PROPERTIES OF CONCRETE Table B.7.21: Concrete Properties 445 448 days CIP CIP Permeability @ 91 days (Coulombs) 2550 2350 1 Percentage decrease in length Notes: CIP - Collection in Progress NC - Not Collected Mix w/c=0.44 Mix w/c=0.37 Total Air Content (%) 5.00 3.0 Slump (mm) 80 180 Unit Weight (kg/m 3 ) 2370 2440 Initial Set (Min.) 216 230 Final Set (Min.) 269 288 Compressive Strength (MPa) 1 day 14.8 23.3 3 days 22.4 32.5 7 days 32.5 37.2 28 days 42.4 48.8 91 days 47.2 53.8 Splitting Tensile Strength (MPa) 1 day 1.8 2.6 3 days 2.1 3.1 7 days 2.7 3.4 28 days 3.1 3.8 91 days 3.9 4.2 Drying Shrinkage Development (% Length Change) 1 4 days 0.010 0.009 7 days 0.018 0.013 14 days 0.025 0.019 28 days 0.032 0.026 56 days 0.038 0.032 112 days 0.045 CIP 224 days CIP CIP Property AUR B.7.11. EMISSIONS Table B.7.22.a: CPR ? Emissions for 10/16/2007 ? 10/18/2007 Time NO x (tons/ton clinker) SO 2 (tons/ton clinker) VOC (tons/ton clinker) CO (tons/ton clinker) 10/16/2007 9:00 8.70E-04 1.84E-06 2.13E-05 6.93E-04 10/16/2007 10:00 1.03E-03 8.96E-06 2.45E-05 7.54E-04 10/16/2007 11:00 1.02E-03 6.44E-06 2.68E-05 7.43E-04 10/16/2007 12:00 1.07E-03 6.30E-06 3.17E-05 8.52E-04 10/16/2007 13:00 1.10E-03 6.79E-06 2.85E-05 7.20E-04 10/16/2007 14:00 1.07E-03 6.60E-06 3.00E-05 7.91E-04 10/16/2007 15:00 7.42E-04 4.46E-06 3.31E-05 8.41E-04 10/16/2007 16:00 6.58E-04 7.03E-06 2.41E-05 7.26E-04 10/16/2007 17:00 9.26E-04 1.06E-05 2.71E-05 5.81E-04 10/16/2007 18:00 6.69E-04 4.57E-06 3.88E-05 7.75E-04 10/16/2007 19:00 7.60E-04 6.13E-06 3.99E-05 7.57E-04 10/16/2007 20:00 8.32E-04 6.16E-06 3.71E-05 6.71E-04 10/16/2007 21:00 9.27E-04 6.92E-06 3.32E-05 6.24E-04 10/16/2007 22:00 9.56E-04 6.78E-06 3.45E-05 7.08E-04 10/16/2007 23:00 8.32E-04 7.51E-06 3.35E-05 7.00E-04 10/17/2007 0:00 7.42E-04 6.52E-06 3.25E-05 7.12E-04 10/17/2007 1:00 8.69E-04 5.48E-06 2.65E-05 6.16E-04 10/17/2007 2:00 9.92E-04 6.76E-06 2.88E-05 6.22E-04 10/17/2007 3:00 9.53E-04 5.31E-06 3.12E-05 6.42E-04 10/17/2007 4:00 7.96E-04 7.33E-06 3.49E-05 7.14E-04 10/17/2007 5:00 7.53E-04 7.35E-06 3.18E-05 5.52E-04 10/17/2007 6:00 1.05E-03 8.65E-06 3.28E-05 5.73E-04 10/17/2007 7:00 1.09E-03 8.23E-06 3.29E-05 5.66E-04 10/17/2007 8:00 9.28E-04 7.33E-06 2.63E-05 5.23E-04 10/17/2007 9:00 1.01E-03 7.42E-06 2.62E-05 5.39E-04 10/17/2007 10:00 7.16E-04 2.90E-06 2.15E-05 5.53E-04 10/17/2007 11:00 8.03E-04 2.27E-06 2.35E-05 5.71E-04 10/17/2007 12:00 1.02E-03 2.40E-06 2.67E-05 5.85E-04 10/17/2007 13:00 1.16E-03 2.74E-06 3.31E-05 7.58E-04 10/17/2007 14:00 9.76E-04 3.79E-06 3.64E-05 6.80E-04 10/17/2007 15:00 7.50E-04 1.72E-06 3.96E-05 6.61E-04 10/17/2007 16:00 1.16E-03 2.47E-06 4.16E-05 6.46E-04 10/17/2007 17:00 7.06E-04 2.14E-06 3.31E-05 5.84E-04 10/17/2007 18:00 9.74E-04 1.65E-06 3.75E-05 6.41E-04 10/17/2007 19:00 7.47E-04 2.54E-06 2.99E-05 5.60E-04 10/17/2007 20:00 8.86E-04 2.42E-06 2.91E-05 5.43E-04 10/17/2007 21:00 9.89E-04 1.75E-06 3.51E-05 5.75E-04 10/17/2007 22:00 7.12E-04 2.70E-06 3.35E-05 6.56E-04 10/17/2007 23:00 7.79E-04 2.97E-06 2.78E-05 5.46E-04 10/18/2007 0:00 8.53E-04 2.72E-06 2.32E-05 5.07E-04 10/18/2007 1:00 9.51E-04 3.19E-06 2.19E-05 4.87E-04 10/18/2007 2:00 8.11E-04 2.82E-06 2.25E-05 5.92E-04 10/18/2007 3:00 7.16E-04 3.80E-06 2.28E-05 6.84E-04 10/18/2007 4:00 7.44E-04 2.12E-06 2.27E-05 5.61E-04 10/18/2007 5:00 8.09E-04 3.18E-06 2.29E-05 6.09E-04 10/18/2007 6:00 8.03E-04 2.60E-06 1.75E-05 6.07E-04 10/18/2007 7:00 8.09E-04 1.97E-06 1.19E-05 4.49E-04 10/18/2007 8:00 9.29E-04 4.11E-06 1.39E-05 5.57E-04 446 447 Table B.7.22.b: CPR ? Emissions for 10/18/2007 ? 10/19/2007 Time NO x (tons/ton clinker) SO 2 (tons/ton clinker) VOC (tons/ton clinker) CO (tons/ton clinker) 10/18/2007 9:00 7.17E-04 3.61E-06 1.17E-05 5.46E-04 10/18/2007 10:00 9.87E-04 2.52E-06 2.05E-05 5.93E-04 10/18/2007 11:00 1.17E-03 5.20E-06 1.94E-05 5.64E-04 10/18/2007 12:00 1.10E-03 8.51E-06 1.83E-05 4.37E-04 10/18/2007 13:00 9.93E-04 5.27E-06 2.03E-05 4.98E-04 10/18/2007 14:00 1.16E-03 3.76E-06 2.39E-05 5.76E-04 10/18/2007 15:00 1.04E-03 1.91E-06 2.39E-05 5.47E-04 10/18/2007 16:00 8.67E-04 8.77E-07 2.00E-05 4.57E-04 10/18/2007 17:00 1.07E-03 5.78E-07 2.12E-05 5.19E-04 10/18/2007 18:00 1.05E-03 2.93E-07 1.97E-05 4.29E-04 10/18/2007 19:00 1.17E-03 3.64E-07 2.19E-05 5.26E-04 10/18/2007 20:00 1.08E-03 3.65E-07 2.24E-05 4.70E-04 10/18/2007 21:00 1.07E-03 1.78E-07 1.87E-05 5.47E-04 10/18/2007 22:00 1.06E-03 1.75E-07 1.65E-05 4.62E-04 10/18/2007 23:00 1.06E-03 5.11E-07 1.85E-05 5.57E-04 10/19/2007 0:00 1.40E-03 7.52E-07 2.49E-05 6.57E-04 10/19/2007 1:00 9.76E-04 9.66E-07 1.63E-05 3.18E-04 10/19/2007 2:00 8.72E-04 8.99E-07 1.28E-05 2.69E-04 10/19/2007 3:00 8.28E-04 6.36E-07 1.20E-05 2.93E-04 10/19/2007 4:00 9.02E-04 6.32E-07 1.37E-05 4.67E-04 10/19/2007 5:00 1.08E-03 2.85E-07 1.69E-05 6.05E-04 10/19/2007 6:00 1.13E-03 5.98E-07 2.39E-05 5.29E-04 10/19/2007 7:00 1.02E-03 4.20E-07 2.99E-05 4.75E-04 10/19/2007 8:00 1.20E-03 3.95E-07 3.76E-05 4.51E-04 Average 9.37E-04 3.72E-06 2.61E-05 5.89E-04 C. V. (%) 16.7 73.4 29.1 19.7 Normality P-Value 1 0.011 <0.005 0.065 0.278 Notes: 1 Based on Anderson Darling Normality Test NC - Not Collected 448 APPENDIX B.8 RAW DATA FOR CTS BURN B.8.1. GENERAL COMMENTS ? The raw data from the CTS burn are presented in this appendix. ? Coal, scrap tires and switchgrass are the fuels used in the burn. ? The burn lasted for only two days from 9 AM on November 27, 2007 to 9 AM on November 29, 2007. B.8.2. NOTATION CPR ? Cement Plant Results ELR ? External Lab Results AUR ? Auburn University Results C. V. ? Coefficient of Variation B.8.3. CHEMICAL COMPOSITION OF RAW MATERIALS Table B.8.1: CPR - Chemical Composition of Raw Materials Property (wt. %) Raw Material One Raw Material Two Raw Material Three Raw Material Four Raw Material Five Raw Material Six Al 2 O 3 NR NR NR NR NR NR CaO NR NR NR NR NR NR Fe 2 O 3 NR NR NR NR NR NR K 2 O NR NR NR NR NR NR MgO NR NR NR NR NR NR Na 2 O NR NR NR NR NR NR SiO 2 NR NR NR NR NR NR SO 3 NR NR NR NR NR NR Moisture NR NR NR NR NR NR LOI NR NR NR NR NR NR Notes: ND - Not Detected NR - Not Reported 449 Table B.8.2: ELR - Chemical Composition of Raw Materials Property Raw Material One Raw Material Two Raw Material Three Raw Material Four Raw Material Five Raw Material Six Al 2 O 3 (wt. %) 25.84 0.26 5.89 3.11 0.85 NR CaO (wt. %) 2.51 53.71 33.82 35.77 0.16 NR Fe 2 O 3 (wt. %) 10.39 0.10 2.63 30.11 0.15 NR K 2 O (wt. %) 2.40 0.05 0.91 0.01 0.14 NR MgO (wt. %) 1.23 1.38 1.87 13.04 0.08 NR Na 2 O (wt. %) 0.78 0.11 0.27 0.12 0.37 NR P 2 O 5 (wt. %) 0.54 0.00 0.03 0.65 0.00 NR SiO 2 (wt. %) 47.69 0.67 23.94 12.65 97.65 NR SO 3 (wt. %) 0.14 0.11 0.14 0.41 0.08 NR TiO 2 (wt. %) 1.21 0.00 0.24 0.24 0.20 NR Moisture (wt. %) 23.10 1.63 6.12 4.35 1.86 NR LOI (wt. %) 6.88 43.58 30.17 0.38 0.30 NR As (ppm) 181 4 14 7 ND NR Ba (ppm) 2000 100 300 100 200 NR Cd (ppm) ND ND ND ND ND NR Cl (ppm) 77 47 45 97 87 NR Co (ppm) 74 4 17 19 9 NR Cr (ppm) 157 44 53 2454 25 NR Cu (ppm) 139 ND ND ND ND NR Hg (ppm) 0.05 0.08 0.07 0.31 0.06 NR Mn (ppm) 600 100 300 34900 100 NR Mo (ppm) 6NDND52ND Ni (ppm) 129 22 23 6430 < 5 NR Pb (ppm) 106 6 31 < 4 24 NR Sb (ppm) NR NR NR NR NR NR Se (ppm) ND ND ND ND ND NR Sr (ppm) 1300 200 100 200 0 NR V (ppm) 332 16 61 772 11 NR Zn (ppm) 152 ND 35 97 ND NR Notes: ND - Not Detected NR - Not Reported 450 Table B.8.3: CPR - Chemical Composition of Kiln Feed 2:23 AM 2:10 PM 1:39 AM 2:02 PM Al 2 O 3 3.12 3.22 3.08 3.03 3.11 2.6 CaO 42.79 42.88 42.57 42.55 42.70 0.4 Fe 2 O 3 2.04 2.03 2.03 2 2.03 0.9 K 2 O 0.37 0.38 0.38 0.4 0.38 3.3 MgO 1.89 1.87 1.91 1.9 1.89 0.9 Na 2 O 0.04 0.05 0.05 0.06 0.05 16.3 Na 2 O eq 0.28 0.3 0.3 0.32 0.30 5.4 SiO 2 13.79 13.72 13.63 13.67 13.70 0.5 SO 3 0.2 0.21 0.2 0.21 0.21 2.8 LOI 35 35 35 35 35.00 0.0 C. V. (%)Property (wt. %) 11/27/2008 11/28/2007 Average B.8.4. CHEMICAL COMPOSITION OF KILN FEED 451 Table B.8.4: ELR - Chemical Composition of Kiln Feed Property 3-Day Composite Al 2 O 3 (wt. %) 3.26 CaO (wt. %) 42.69 Fe 2 O 3 (wt. %) 2.00 K 2 O (wt. %) 0.37 MgO (wt. %) 2.07 Na 2 O (wt. %) 0.20 P 2 O 5 (wt. %) 0.05 SiO 2 (wt. %) 13.95 SO 3 (wt. %) 0.33 TiO 2 (wt. %) 0.14 Moisture (wt. %) 0.18 LOI (wt. %) 34.81 As (ppm) 26 Ba (ppm) 200 Cd (ppm) ND Cl (ppm) 182 Co (ppm) 14 Cr (ppm) 107 Cu (ppm) ND Hg (ppm) 0.06 Mn (ppm) 1000 Mo (ppm) 15 Ni (ppm) 1640 Pb (ppm) ND Sb (ppm) NR Se (ppm) ND Sr (ppm) 300 V (ppm) 66 Zn (ppm) 34 Notes: NR - Not Reported ND- Not Detected 452 B.8.5. CHEMICAL COMPOSITION OF FUELS Table B.8.5: CPR - Chemical Composition of Coal Test Parameter Value (wt. %) Ash 17.78 Fixed Carbon 54.51 Volatile Matter 27.71 Carbon 72.51 Hydrogen 4.37 Nitrogen 1.33 Oxygen 2.65 Sulfur 1.36 Al 2 O 3 22.74 CaO 8.16 Fe 2 O 3 7.94 K 2 O 2.66 MgO 1.07 Na 2 O 0.16 SiO 2 48.84 SO 3 7.02 12495 Notes: 1 Value is Reported as BTU/lb Heat Value 1 Proximate Analysis Ul ti mate Analysis St andard Par a m e t e r s 453 Table B.8.6: ELR - Proximate, Ultimate, and Combustion of Coal Test Parameter Value (wt. %) Ash 16.45 Fixed Carbon 55.19 Volatile Matter 28.36 Carbon 71.33 Hydrogen 3.75 Nitrogen 0.96 Oxygen 6.41 Sulfur 1.1 12664 Notes: 1 Value is Reported as BTU/lb Proximate Analysis Ul ti mate An aly s is Heat Value 1 454 Table B.8.7: ELR - Standard Parameters of Coal Property 3-Day Composite Al 2 O 3 (wt. %) 23.87 CaO (wt. %) 12.81 Fe 2 O 3 (wt. %) 7.77 K 2 O (wt. %) 2.56 MgO (wt. %) 1.31 Na 2 O (wt. %) 0.57 P 2 O 5 (wt. %) 0.12 SiO 2 (wt. %) 49.44 SO 3 (wt. %) 0.33 TiO 2 (wt. %) 1.04 As (ppm) 114 Ba (ppm) 1100 Cd (ppm) ND Cl (ppm) 236 Co (ppm) 43 Cr (ppm) 132 Cu (ppm) 103 Hg (ppm) 0.076 Mn (ppm) 500 Mo (ppm) 29 Ni (ppm) 78 Pb (ppm) ND Sb (ppm) NR Se (ppm) 7 Sr (ppm) 400 V (ppm) 228 Zn (ppm) 9 Notes: NR - Not Reported ND- Not Detected 455 Table B.8.8: ELR - Proximate, Ultimate, and Combustion Analysis of Tires Test Parameter Value (wt. %) Ash 24.40 Fixed Carbon 19.82 Moisture 1 1.00 Volatile Matter 55.78 Carbon 72.63 Hydrogen 0.23 Nitrogen 0.39 Oxygen 1.06 Sulfur 1.29 13239 Notes: 1 As Received 2 Value is Reported as BTU/lb Ul ti mate An alysis Heat Value 2 Proximate An alysis 456 Table B.8.9: ELR - Standard Parameters of Tires Property 3-Day Composite Al 2 O 3 (wt. %) 0.53 CaO (wt. %) 2.94 Fe 2 O 3 (wt. %) 77.06 K 2 O (wt. %) 0.25 MgO (wt. %) 0.20 Na 2 O (wt. %) 0.13 P 2 O 5 (wt. %) 0.20 SiO 2 (wt. %) 5.38 SO 3 (wt. %) 2.25 TiO 2 (wt. %) 0.10 As (ppm) ND Ba (ppm) 0 Cd (ppm) ND Cl (ppm) 1696 Co (ppm) 724 Cr (ppm) 129 Cu (ppm) 0 Hg (ppm) NR Mn (ppm) 4300 Mo (ppm) 11 Ni (ppm) 332 Pb (ppm) 8 Sb (ppm) NR Se (ppm) ND Sr (ppm) 20 V (ppm) 10 Zn (ppm) 0 Notes: NR - Not Reported ND- Not Detected 457 Table B.8.10: ELR - Proximate, Ultimate, and Combustion Analysis of Switchgrass Test Parameter Value (wt. %) Ash 5.27 Fixed Carbon 17.02 Moisture 1 9.87 Volatile Matter 77.72 Carbon 50.25 Hydrogen 5.70 Nitrogen 1.22 Oxygen 37.37 Sulfur 0.19 8162 Notes: 1 As Received 2 Value is Reported as BTU/lb Ul ti mate An alysis Heat Value 2 Proximate An alysis 458 Table B.8.11: ELR - Standard Parameters of Switchgrass Property 3-Day Composite Al 2 O 3 (wt. %) 1.57 CaO (wt. %) 13.99 Fe 2 O 3 (wt. %) 1.06 K 2 O (wt. %) 24.72 MgO (wt. %) 9.02 Na 2 O (wt. %) 0.96 P 2 O 5 (wt. %) 8.49 SiO 2 (wt. %) 34.86 SO 3 (wt. %) 4.53 TiO 2 (wt. %) 0.14 As (ppm) 11 Ba (ppm) 739 Cd (ppm) ND Cl (ppm) 819 Co (ppm) 6 Cr (ppm) 22 Cu (ppm) 56 Hg (ppm) 0.1 Mn (ppm) 5511 Mo (ppm) 146 Ni (ppm) 145 Pb (ppm) 47 Sb (ppm) NR Se (ppm) ND Sr (ppm) 267 V (ppm) 82 Zn (ppm) 1118 Notes: NR - Not Reported ND- Not Detected 459 460 Table B.8.12: AUR - Density of Switchgrass Sample # Density (kg/m3) 1 70.2 2 76.8 3 76.1 4 70.0 5 73.0 6 77.3 7 70.5 8 68.7 9 69.1 10 72.4 11 75.3 12 76.0 13 78.0 14 74.2 15 76.3 16 68.5 Average 73.3 B.8.6. CHEMICAL COMPOSITION OF CEMENT KILN DUST (CKD) Table B.8.13: CPR - Chemical Composition of Cement Kiln Dust 11/27/2007 11/29/2007 6:47 PM 9:23 AM 6:48 PM 9:11 AM Al 2 O 3 3.9 3.8 4.05 4.11 3.97 CaO 44.49 44.77 44.08 44.07 44.35 Fe 2 O 3 1.96 1.96 2.05 2.02 2.00 K 2 O 0.58 0.56 0.58 0.6 0.58 MgO 1.3 1.32 1.36 1.34 1.33 Na 2 O 0.05 0.05 0.05 0.05 0.05 SiO 2 12.11 11.89 12.36 12.24 12.15 SO 3 0.19 0.13 0.23 0.26 0.20 AverageProperty (wt. %) 11/28/2007 461 Table B.8.14: ELR - Chemical Composition of Cement Kiln Dust 10:00 AM 10:00 PM 10:00 AM 10:00 PM Al 2 O 3 (wt. %) 3.49 4.42 3.72 3.94 3.89 CaO (wt. %) 44.65 43.07 44.20 44.16 44.02 Fe 2 O 3 (wt. %) 2.04 2.13 1.86 1.97 2.00 K 2 O (wt. %) 0.76 0.57 0.49 0.50 0.58 MgO (wt. %) 1.35 1.33 1.37 1.42 1.37 Na 2 O (wt. %) 0.04 0.08 0.09 0.15 0.09 P 2 O 5 (wt. %) 0.11 0.05 0.05 0.06 0.07 SiO 2 (wt. %) 10.57 12.82 11.25 11.66 11.58 SO 3 (wt. %) 0.23 0.36 0.27 0.30 0.29 TiO 2 (wt. %) 0.15 0.20 0.15 0.16 0.17 Moisture (wt. %) 0.28 0.21 0.22 0.23 0.24 LOI (wt. %) 36.50 34.86 36.45 35.59 35.85 As (ppm) 19 19 19 29 22 Ba (ppm) 300 300 200 200 250 Cd (ppm) ND ND ND ND ND Cl (ppm) 172 602 224 214 303 Co (ppm) 19 16 14 15 16 Cr (ppm) 51 65 60 102 70 Cu (ppm) 19 ND ND ND 5 Hg (ppm) 0.48 0.30 0.12 0.10 0 Mn (ppm) 600 500 500 600 550 Mo (ppm) 22 5 ND 5 8 Ni (ppm) 28 1336 8 971 586 Pb (ppm) 12 27 11 ND 13 Sb (ppm) NR NR NR NR NR Se (ppm) ND ND ND ND ND Sr (ppm) 300 300 300 300 300 V (ppm) 47 72 66 81 67 Zn (ppm) 38 34 33 30 34 Notes: ND - Not Detected NR - Not Reported AverageProperty 11/27/2007 11/28/2007 462 B.8.7. CHEMICAL COMPOSITION OF CLINKER Table B.8.15.a: CPR - Chemical Composition of Clinker for 11/27/2007 9:59 AM 11:41 AM 2:05 PM 3:51 PM 5:24 PM 7:51 PM 9:47 PM 11:50 PM Al 2 O 3 5.28 5.20 5.18 5.25 5.19 5.17 5.31 5.20 CaO 64.77 64.82 64.65 64.62 64.59 64.62 64.64 64.48 Fe 2 O 3 3.44 3.43 3.45 3.44 3.43 3.36 3.44 3.41 K 2 O 0.61 0.52 0.64 0.65 0.64 0.64 0.63 0.60 MgO 3.04 2.98 2.98 3.07 3.09 3.13 3.16 3.15 Na 2 O 0.09 0.09 0.10 0.10 0.10 0.09 0.09 0.09 Na 2 O eq 0.49 0.43 0.52 0.53 0.52 0.51 0.50 0.48 SiO 2 21.52 21.64 21.61 21.59 21.55 21.46 21.45 21.36 SO 3 0.66 0.50 0.74 0.75 0.81 0.71 0.59 0.62 F CaO 0.84 0.24 0.30 0.36 0.42 1.20 1.50 1.80 C 3 A 8.17 7.98 7.89 8.09 7.95 8.02 8.25 8.01 C 4 AF 10.47 10.44 10.50 10.47 10.44 10.22 10.47 10.38 C 3 S 59.74 59.56 59.22 58.80 59.39 60.44 59.54 60.35 C 2 S 16.63 17.11 17.28 17.54 16.98 15.93 16.58 15.71 Property (wt. %) 11/27/2007 463 Table B.8.15.b: CPR - Chemical Composition of Clinker for 11/28/2007 464 1:43 AM 4:01 AM 5:38 AM 8:01 AM 10:03 AM 11:41 AM 1:58 PM 3:50 PM 5:38 PM 7:52 PM 9:01 PM 11:00 PM Al 2 O 3 5.16 5.15 5.15 5.17 5.13 5.10 5.07 4.99 5.08 5.04 5.06 4.97 CaO 64.61 64.69 64.58 64.72 64.85 64.75 64.86 64.76 64.58 64.80 64.83 64.92 Fe 2 O 3 3.36 3.50 3.48 3.29 3.35 3.42 3.40 3.43 3.40 3.33 3.34 3.43 K 2 O 0.60 0.62 0.65 0.71 0.61 0.65 0.60 0.64 0.64 0.67 0.65 0.58 MgO 3.18 3.20 3.15 3.14 3.15 3.14 3.18 3.18 3.17 3.22 3.24 3.22 Na 2 O 0.10 0.09 0.10 0.09 0.09 0.09 0.09 0.09 0.09 0.10 0.10 0.09 Na 2 O eq 0.49 0.50 0.53 0.56 0.49 0.52 0.48 0.51 0.51 0.54 0.53 0.47 SiO 2 21.54 21.53 21.48 21.36 21.50 21.54 21.56 21.55 21.34 21.39 21.36 21.48 SO 3 0.75 0.52 0.73 0.66 0.45 0.55 0.48 0.54 0.58 0.74 0.74 0.49 F CaO 0.96 0.84 0.78 2.58 1.14 0.72 0.54 0.60 0.90 1.80 1.98 0.90 C 3 A 7.99 7.73 7.76 8.13 7.93 7.73 7.68 7.42 7.71 7.72 7.76 7.37 C 4 AF 10.22 10.65 10.59 10.01 10.19 10.41 10.35 10.44 10.35 10.13 10.16 10.44 C 3 S 59.85 60.12 60.08 61.70 61.35 60.74 61.27 61.43 61.73 62.62 62.82 62.75 C 2 S 16.60 16.37 16.26 14.69 15.36 15.93 15.59 15.44 14.61 14.09 13.85 14.25 Property (wt. %) 10/28/2007 465 Table B.8.15.c: CPR - Chemical Composition of Clinker for 11/29/2007 Property (wt. %) 11/29/2007 Average C. V. (%) Normality P-Value 1 12:05 AM 1:48 AM 3:58 AM 5:41 AM 7:48 AM 9:40 AM Al 2 O 3 4.90 4.83 4.94 5.02 5.01 4.88 5.09 2.4 <0.005 CaO 64.95 64.60 64.82 64.92 64.87 64.99 64.74 0.2 0.093 Fe 2 O 3 3.36 3.27 3.31 3.32 3.32 3.30 3.39 1.8 0.177 K 2 O 0.56 0.70 0.70 0.70 0.67 0.69 0.64 7.1 0.412 MgO 3.13 3.16 3.17 3.21 3.20 3.20 3.15 2.1 0.625 Na 2 O 0.09 0.10 0.10 0.10 0.09 0.09 0.09 5.3 0.179 Na 2 O eq 0.46 0.56 0.56 0.56 0.53 0.54 0.51 6.4 <0.005 SiO 2 21.58 21.38 21.30 21.35 21.54 21.50 21.48 0.4 0.226 SO 3 0.53 0.74 0.91 0.68 0.61 0.56 0.64 18.3 <0.005 F CaO 0.48 0.96 1.44 1.68 0.60 0.66 1.01 58.3 <0.005 C 3 A 7.30 7.27 7.49 7.69 7.66 7.35 7.77 3.6 0.021 C 4 AF 10.22 9.95 10.07 10.10 10.10 10.04 10.30 1.9 <0.005 C 3 S 62.68 63.37 64.08 63.56 61.98 63.67 61.26 2.6 0.143 C 2 S 14.58 13.49 12.72 13.26 15.00 13.61 15.36 8.9 0.107 Notes: 1 Based on Anderson-Darling Normality Test Table B.8.16: ELR - Chemical Composition of Clinker 1212 Al 2 O 3 (wt. %) 4.64 5.10 5.15 4.41 4.83 CaO (wt. %) 65.95 64.31 64.44 66.65 65.34 Fe 2 O 3 (wt. %) 3.57 3.11 3.18 3.50 3.34 K 2 O (wt. %) 0.60 0.67 0.56 0.54 0.59 MgO (wt. %) 3.42 3.25 3.27 3.44 3.35 Na 2 O (wt. %) 0.09 0.16 0.10 0.12 0.12 P 2 O 5 (wt. %) 0.07 0.09 0.07 0.06 0.07 SiO 2 (wt. %) 20.47 21.94 21.71 19.98 21.03 SO 3 (wt. %) 0.58 0.80 0.84 0.60 0.71 TiO 2 (wt. %) 0.23 0.20 0.22 0.21 0.22 Moisture (wt. %) 0.00 0.00 0.00 0.00 0.00 LOI (wt. %) 0.16 0.16 0.24 0.26 0.21 As (ppm) 20 32 27 23 26 Ba (ppm) 300 300 400 300 325 Cd (ppm) ND ND ND ND ND Cl (ppm) 166 388 829 212 399 Co (ppm) 18 17 12 17 16 Cr (ppm) 108 104 97 108 104 Cu (ppm) 94 49 57 68 67 Hg (ppm) 0.05 0.05 0.08 0.04 0.05 Mn (ppm) 1600 1400 1500 1600 1525 Mo (ppm) 17 25 ND 11 13 Ni (ppm) 62 418 15 52 137 Pb (ppm) ND ND 18 ND 5 Sb (ppm) NR NR NR NR NR Se (ppm) ND ND ND ND NA Sr (ppm) 400 400 400 400 400 V (ppm) 72 78 70 64 71 Zn (ppm) 83 97 61 81 81 Property 10/27/2007 10/28/2007 Average Notes: NA - Not Applicable ND - Not Detected B.8.8. CHEMICAL COMPOSITION OF CEMENT Table B.8.17: CPR - Chemical Composition of Cement 5:35 PM 7:36 PM 10:05 PM 12:54 AM 4:01 AM 6:53 AM Al 2 O 3 4.79 4.79 4.77 4.77 4.81 4.82 4.79 0.4 0.123 CaO 63.25 63.31 63.12 63.01 63.29 63.22 63.20 0.2 0.100 Fe 2 O 3 3.18 3.19 3.17 3.17 3.17 3.18 3.18 0.3 0.165 K 2 O 0.56 0.56 0.56 0.55 0.56 0.57 0.56 1.1 1 0.052 MgO 3.24 3.26 3.23 3.24 3.26 3.29 3.25 0.7 0.352 Na 2 O 0.08 0.08 0.07 0.07 0.07 0.08 0.08 7.3 1 <0.005 Na 2 O eq 0.45 0.45 0.44 0.43 0.44 0.46 0.45 2.4 1 <0.005 SiO 2 20.46 20.4 20.2 20.2 20.31 20.28 20.31 0.5 0.192 SO 3 2.58 2.66 2.64 2.6 2.66 2.69 2.64 1.6 0.224 F CaO 1.2 1.14 1.02 1.02 1.08 1.2 1.11 7.5 0.341 LOI 1.18 0.84 1.12 1.3 1.12 1.02 1.10 14.2 1 <0.005 C 3 A 7.3 7.3 7.28 7.29 7.39 7.4 58.67 0.7 0.412 C 4 AF 9.69 9.71 9.65 9.65 9.66 9.68 13.96 0.3 0.278 C 3 S 57.89 58.36 59.32 58.98 58.86 58.63 7.33 0.9 0.524 C 2 S 14.99 14.46 13.16 13.42 13.81 13.91 9.67 4.8 1 <0.005 Blaine SSA (m 2 /kg) 373 381 387 376 374 361 375.33 2.3 0.729 Property (wt. %) Average Normality P-Value 1 C. V. (%) 12/12/2007 12/13/2007 Notes: 1 Based on Anderson-Darling Normality Test 2 Data not normally distributed 467 Table B.8.18: ELR - Chemical Composition of Cement Property 11/27/2007 11/28/2007 Average Al 2 O 3 (wt. %) 3.99 4.93 4.46 CaO (wt. %) 65.78 62.98 64.38 Fe 2 O 3 (wt. %) 3.35 3.05 3.20 K 2 O (wt. %) 0.58 0.58 0.58 MgO (wt. %) 3.14 3.18 3.16 Na 2 O (wt. %) 0.10 0.13 0.12 P 2 O 5 (wt. %) 0.06 0.07 0.07 SiO 2 (wt. %) 18.86 20.99 19.93 SO 3 (wt. %) 2.51 2.99 2.75 TiO 2 (wt. %) 0.21 0.20 0.21 Moisture (wt. %) 0.06 0.39 0.23 LOI (wt. %) 1.20 0.70 0.95 C 3 S (wt. %) 85.70 50.86 48.40 C 2 S (wt. %) -10.58 21.81 25.17 C 3 A (wt. %) 4.91 7.90 7.80 C 4 AF (wt. %) 10.19 9.28 9.46 TOC (wt. %) 0.1 2.29 1.20 As (ppm) 13 31 22 Ba (ppm) 300 400 350 Cd (ppm) ND ND ND Cl (ppm) 73 91 82 Co (ppm) 21 8 15 Cr (ppm) 104 103 104 Cu (ppm) 22 33 28 Hg (ppm) 0.03 0.07 0.05 Mn (ppm) 1500 1400 1450 Mo (ppm) 29 30 30 Ni (ppm) 32 315 174 Pb (ppm) 13 ND 7 Sb (ppm) NR NR NR Se (ppm) ND ND ND Sr (ppm) 400 400 400 V (ppm) 68 68 68 Zn (ppm) 83 66 75 Notes: ND - Not Detected NR - Not Reported 468 B.8.9. PHYSICAL PROPERTIES OF CEMENT Table B.8.19: CPR - Physical Properties of Cement Property Value Air in Mortar (%) 5.2 Blaine Specific Surface Area (m 2 /kg) 373 Autoclave Expansion (% Exp.) 0.06 Cube Flow (%) 105.0 Comp Str 1day (MPa) 15.4 Comp Str 3day (MPa) 24.6 Comp Str 7day (MPa) 31.6 Comp Str 28day (MPa) 41.3 Normal Consistency (%) 25.0 Gillmore Initial Set (Min) 120 Gillmore Final Set (Min) 240 Vicat Initial Set (Min) 66 Vicat Final Set (Min) 225 Notes: % Exp. - Percent Expansion Table B.8.20: AUR - Physical Properties of Cement Property Composite Autoclave Expansion (% Exp.) 0.05 Cube Flow (%) 106 Comp Str 1day (MPa) 10.5 Comp Str 3day (MPa) 21.3 Comp Str 7day (MPa) 26.3 Comp Str 28day (MPa) 32.7 Normal Consistency (%) 26.2 Gillmore Initial Set (Min) 110 Gillmore Final Set (Min) 210 Vicat Initial Set (Min) 94 Vicat Final Set (Min) 180 Drying Shrinkage @ 7 days (% LC) -0.047 Drying Shrinkage @ 14 days (% LC) -0.071 Drying Shrinkage @ 21 days (% LC) -0.082 Drying Shrinkage @ 28 days (% LC) -0.090 Notes: % LC - Percent Length Change % Exp. - Percent Expansion 469 B.8.10. PROPERTIES OF CONCRETE Table B.8.21: Concrete Properties 470 224 days CIP CIP 448 days CIP CIP Permeability @ 91 days (Coulombs) 2750 CIP Notes: CIP - Collection in Progress 1 Percentage decrease in length Mix w/c=0.44 Mix w/c=0.37 Total Air Content (%) 4.00 5.0 Slump (mm) 60 150 Unit Weight (kg/m 3 ) 2441 2395 Initial Set (Min.) 154 200 Final Set (Min.) 227 259 Compressive Strength (MPa) 1 day 16.5 23.0 3 days 20.9 31.2 7 days 30.1 38.2 28 days 40.1 49.8 91 days 48.5 CIP Splitting Tensile Strength (MPa) 1 day 1.7 2.8 3 days 2.0 3.3 7 days 2.5 3.8 28 days 3.4 4.2 91 days 4.0 CIP Drying Shrinkage Development (% Length Change) 1 4 days 0.009 0.010 7 days 0.012 0.018 14 days 0.019 0.022 28 days 0.024 0.030 56 days 0.032 0.036 112 days CIP CIP Property AUR TABLE B.8.22: CPR ? EMISSIONS FOR 11/27/2007 ? 11/29/2007 Time NO x (tons/ton clinker) SO 2 (tons/ton clinker) VOC (tons/ton clinker) CO (tons/ton clinker) 11/27/2007 9:00 1.31E-03 8.81E-06 1.87E-05 4.29E-04 11/27/2007 10:00 1.54E-03 7.30E-06 2.24E-05 4.48E-04 11/27/2007 11:00 1.81E-03 7.12E-06 2.30E-05 3.56E-04 11/27/2007 12:00 1.77E-03 7.53E-06 2.42E-05 3.85E-04 11/27/2007 13:00 1.61E-03 5.58E-06 2.32E-05 3.83E-04 11/27/2007 14:00 1.43E-03 4.67E-06 2.27E-05 3.70E-04 11/27/2007 15:00 1.27E-03 4.74E-06 2.15E-05 3.37E-04 11/27/2007 16:00 1.44E-03 4.69E-06 2.38E-05 3.70E-04 11/27/2007 17:00 1.55E-03 6.05E-06 2.30E-05 3.59E-04 11/27/2007 18:00 1.65E-03 7.36E-06 2.24E-05 4.20E-04 11/27/2007 19:00 1.46E-03 6.85E-06 2.07E-05 3.96E-04 11/27/2007 20:00 1.23E-03 7.03E-06 1.85E-05 3.92E-04 11/27/2007 21:00 1.27E-03 7.69E-06 2.16E-05 3.75E-04 11/27/2007 22:00 1.28E-03 8.87E-06 2.28E-05 4.01E-04 11/27/2007 23:00 1.13E-03 6.02E-06 2.06E-05 3.88E-04 11/28/2007 0:00 2.06E-03 7.80E-06 2.03E-05 4.26E-04 11/28/2007 1:00 1.56E-03 8.37E-06 1.94E-05 4.08E-04 11/28/2007 2:00 1.67E-03 9.35E-06 2.14E-05 3.78E-04 11/28/2007 3:00 1.51E-03 8.72E-06 2.04E-05 3.48E-04 11/28/2007 4:00 1.53E-03 6.96E-06 2.06E-05 3.28E-04 11/28/2007 5:00 1.55E-03 6.64E-06 2.12E-05 3.36E-04 11/28/2007 6:00 1.61E-03 8.84E-06 2.33E-05 3.56E-04 11/28/2007 7:00 1.42E-03 5.26E-06 2.48E-05 4.28E-04 11/28/2007 8:00 1.18E-03 8.55E-06 1.76E-05 3.56E-04 11/28/2007 9:00 1.16E-03 6.32E-06 1.88E-05 3.38E-04 11/28/2007 10:00 1.17E-03 4.71E-06 1.94E-05 3.59E-04 11/28/2007 11:00 1.03E-03 4.82E-06 1.93E-05 3.46E-04 11/28/2007 12:00 1.47E-03 4.93E-06 2.13E-05 4.01E-04 11/28/2007 13:00 1.36E-03 3.85E-06 2.12E-05 3.60E-04 11/28/2007 14:00 1.31E-03 4.01E-06 2.20E-05 3.43E-04 11/28/2007 15:00 1.26E-03 2.79E-06 2.20E-05 3.75E-04 11/28/2007 16:00 1.32E-03 4.29E-06 2.14E-05 3.61E-04 11/28/2007 17:00 1.36E-03 5.16E-06 1.85E-05 3.81E-04 11/28/2007 18:00 1.08E-03 6.17E-06 1.71E-05 3.42E-04 11/28/2007 19:00 1.20E-03 6.25E-06 1.71E-05 3.43E-04 11/28/2007 20:00 1.25E-03 7.34E-06 1.82E-05 3.45E-04 11/28/2007 21:00 1.16E-03 8.03E-06 1.65E-05 3.41E-04 11/28/2007 22:00 1.44E-03 8.71E-06 1.83E-05 3.44E-04 11/28/2007 23:00 1.84E-03 8.40E-06 1.72E-05 3.26E-04 11/29/2007 0:00 1.56E-03 6.41E-06 1.77E-05 3.02E-04 11/29/2007 1:00 1.44E-03 3.35E-06 1.98E-05 3.25E-04 11/29/2007 2:00 1.32E-03 3.97E-06 2.07E-05 3.32E-04 11/29/2007 3:00 1.45E-03 5.35E-06 2.07E-05 3.22E-04 11/29/2007 4:00 1.36E-03 3.43E-06 1.84E-05 3.45E-04 11/29/2007 5:00 1.39E-03 5.33E-06 2.04E-05 3.78E-04 11/29/2007 6:00 1.63E-03 4.36E-06 2.19E-05 4.15E-04 11/29/2007 7:00 1.58E-03 3.64E-06 2.33E-05 3.33E-04 11/29/2007 8:00 1.59E-03 4.46E-06 2.06E-05 3.50E-04 Average 1.43E-03 6.18E-06 2.06E-05 3.66E-04 C. V. (%) 14.9 29.0 10.1 9.1 Normality P-Value 1 0.169 <0.005 0.09 0.314 Notes: 1 Based on Anderson Darling Normality Test 471