THE UTILIZATION OF ALTERNATIVE FUELS IN 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. _______________________________________ Dustin W. Swart Certificate of Approval: _______________________________ Robert W. Barnes Associate Professor Civil Engineering _______________________________ Mary L. Hughes Assistant Professor Civil Engineering _______________________________ Anton K. Schindler, Chair Gottlieb Assistant Professor Civil Engineering _______________________________ Joe F. Pittman Interim Dean Graduate School THE UTILIZATION OF ALTERNATIVE FUELS IN THE PRODUCTION OF PORTLAND CEMENT Dustin Swart 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 August 4, 2007 iii THE UTILIZATION OF ALTERNATIVE FUELS IN THE PRODUCTION OF PORTLAND CEMENT Dustin Swart 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 Dustin Wayne Swart is the son of Roger and Marja Swart of Abilene, Texas. He was born in Abilene, Texas on December 27, 1981. He has one younger sister, Julie. Dustin graduated from Abilene Cooper High School in 2000. After high school, he attended Abilene Christian University for three years, before transferring, and ultimately receiving a Bachelor of Science degree in Civil Engineering from Auburn University in May 2005. Dustin immediately began Graduate School at Auburn University. On July 24, 2005 he married Sarah Anne (McCullough) Swart. v THESIS ABSTRACT THE UTILIZATION OF ALTERNATIVE FUELS IN THE PRODUCTION OF PORTLAND CEMENT Dustin Swart Master of Science, August 4, 2007 (B.S., Auburn University, 2005) 339 Typed Pages Directed by Anton K. Schindler The production of portland cement converts many different raw materials into clinker, in the presence of temperatures on the order of 1,500 ?C. Historically, nonrenewable fossil fuels have been used to maintain these temperatures; however, the cement industry has started to explore options to supplement nonrenewable fuels with alternative sources. These alternative fuels are generally derived from waste, and their disposal in a cement kiln could benefit the cement industry as well as the environment. The cement for this study was produced in a full-scale, operational, cement plant, where three different 3-day test burns were conducted using various combinations of alternative fuels. The fuels used in each burn period were: Coal Only; Coal plus Tires; and Coal, Tires, and Plastics. One objective of this study was to determine if the alternative fuels selected could be successfully burned while maintaining production at the cement plant. Although some vi minor problems did occur, the energy content, availability, cost, and overall compatibility made both tires and specific waste plastics viable options. Another objective was to determine if the chemical composition of the fuels directly impacted the chemical composition of the clinker and/or cement. The primary chemical compounds; Al2O3, CaO, Fe2O3, and SiO2 showed no practically significant changes. Some changes did occur in other compounds, but based on this study it was not possible to conclude that these changes were a direct result of the fuels that were burned. The main objective of this study was to determine if the fuels had a direct impact on the properties of the cement and/or concrete produced from the cement. Although the results could not be attributed directly to the fuels, some significantly different results were found relative to the baseline burn, which used Coal plus Tires as fuel. Tests of drying shrinkage development, splitting tensile strength of concrete, and concrete permeability all showed no significant changes. Paste setting times showed an acceleration of 27 percent in the Coal, Tires, and Plastics Burn, and concrete setting times showed a retardation of 40 percent in the Coal Only Burn. Additionally, the compressive strength of concrete made from the Coal Only burn period showed a decrease of as much as 20 percent. The final objective of this study was to determine if the fuels directly affected the emissions. Based on the averages, the Coal plus Tires burn was the highest, and the Coal Only was the lowest in NOx, SO2, and VOC. The CO emissions emitted by the cement plant were the highest for the Coal Only burn. The use of tires and waste plastics appear to be feasible alternative fuels for cement production and their use should be further explored. vii ACKNOWLEDGMENTS The author would like to thank a number of different people and groups. First of all, thanks to Dr. Anton Schindler who has provided instruction and guidance throughout this process. Thanks also to Billy Wilson, who has given an abundance of help, education, and friendship along the trip. The personnel at the cement plant have been a key component to this project, and without their assistance, this research could not have been completed. Thanks also go out to the McCullough family for their support and encouragement. A tremendous thank you goes out to my family, who have supported me in every way. Finally, to my wife Sarah, who has been there for me every step of the way. Without her, I wouldn?t have been able to maintain the path. viii Style Manual Used: Chicago Manual of Style, 14th Edition Computer Software Used: Microsoft Word XP for Windows; Microsoft Excel XP for Windows; Minitab 14 for Windows ix TABLE OF CONTENTS LIST OF TABLES?..???????????????????????? xiv LIST OF FIGURES????????????????????????? xviii CHAPTER 1: RESEARCH 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?????????????????????? 12 2.2.2 PYRO-PROCESSING?????????????????????. 16 2.2.3 CLINKER COOLING?????????????????????. 17 2.2.4 GRINDING AND FINISHING?????????????????... 20 2.3 ALTERNATIVE FUELS AND PORTLAND CEMENT PRODUCTION?? 20 2.3.1 ALTERNATIVE FUELS IN CEMENT KILNS???????????. 22 2.3.2 ADVANTAGES OF ALTERNATIVE FUELS???????????.. 24 2.3.3 DISADVANTAGES OF ALTERNATIVE FUELS?????????? 26 x 2.3.4 ALTERNATIVE FUEL OPTIONS????????????????. 28 2.3.4.1 TIRES AS FUEL??????????????????????. 29 2.3.4.2 PLASTIC WASTE AS FUEL?????????????????. 34 2.3.4.3 BROILER LITTER AS FUEL????????????????? 36 2.4 EMISSIONS??????????????????????????. 40 2.4.1 CARBON EMISSIONS????????????????????... 41 2.4.2 NITROGEN EMISSIONS???????????????????... 45 2.4.3 SULFUR EMISSIONS????????????????????? 47 2.4.4 OTHER PROBLEMATIC EMISSIONS??????????????. 49 2.4.5 DIOXINS AND FURANS???????????????????... 49 2.4.6 METALS??????????????????????????.. 50 2.4.7 PARTICULATES??????????????????????? 50 2.5 CEMENT KILN DUST?????????????????????... 51 2.5.1 COMPOSITION OF CEMENT KILN DUST????????????. 52 2.5.2 ALTERNATIVE FUELS AND CKD???????????????. 53 2.6 THE EFFECTS OF ELEMENTS ON CLINKER, CEMENT, AND CONCRETE?????????????????????????? 56 2.6.1 ALKALIS (SODIUM AND POTASSIUM)????????????? 60 2.6.2 ANTIMONY (Sb)??????????????????????... 62 2.6.3 ARSENIC (As)???????????????????????? 63 2.6.4 BARIUM (Ba)????????????????????????. 64 2.6.5 BERYLLIUM (Be)??????????????????????.. 65 2.6.6 BORON (B)?????????????????????????. 65 xi 2.6.7 BROMINE (Br)???????????????????????... 66 2.6.8 CADMIUM (Cd)???????????????????????. 66 2.6.9 CARBON (C)????????????????????????... 67 2.6.10 CHLORINE (Cl)??????????????????????? 68 2.6.11 CHROMIUM (Cr)??????????????????????. 69 2.6.12 COBALT (Co)???????????????????????... 78 2.6.13 COPPER (Cu)???????????????????????? 78 2.6.14 FLUORINE (F)???????????????????????.. 79 2.6.15 LEAD (Pb)?????????????????????????. 80 2.6.16 LITHIUM (Li)???????????????????????... 81 2.6.17 MAGNESIUM (Mg)?????????????????????.. 82 2.6.18 MANGANESE (Mn)?????????????????????. 83 2.6.19 MERCURY (Hg)??????????????????????... 84 2.6.20 MOLYBDENUM (Mo)????????????????????. 84 2.6.21 NICKEL (Ni)????????????????????????. 85 2.6.22 NITROGEN (N)???????????????????????. 86 2.6.23 PHOSPHORUS (P)?????????????????????? 87 2.6.24 RUBIDIUM (Rb)??????????????????????... 89 2.6.25 STRONTIUM (Sr)??????????????????????. 89 2.6.26 SULFUR (S)????????????????????????.. 90 2.6.27 THALLIUM (Tl)??????????????????????... 91 2.6.28 TITANIUM (Ti)???????????????????????. 92 2.6.29 VANADIUM (V)???............................................................................... 93 xii 2.6.30 ZINC (Zn)?????????????????????????.. 94 2.6.31 ZIRCONIUM (Zn)??????????????????????. 96 2.7 CONCLUSION????????????????????????? 96 CHAPTER 3: TEST METHODS???????????????????.. 98 3.1 INTRODUCTION???????????????????????... 98 3.1.1 DEFINITIONS????????????????????????. 101 3.2 GENERAL TEST PLANNING OVERVIEW?????????????. 101 3.2.1 COLLECTION OF MATERIALS????????????????.. 103 3.2.2 TYPES OF TESTS??????????????????????.. 104 3.3 DETAILED TEST PROCEDURE?????????????????... 107 3.3.1 PLANT LAYOUT, SAMPLE LOCATIONS, AND COLLECTION METHODS???????????????????????????... 107 3.3.2 SAMPLE PREPARATION, SHIPPING, AND STORAGE??????... 115 3.3.3 ANALYZING THE CHEMICAL COMPOSITION OF RAW MATERIALS??????????????????????????? 116 3.3.4 ANALYZING THE CHEMICAL COMPOSITION OF FUEL SOURCES... 117 3.3.5 ANALYZING THE CHEMICAL COMPOSITION OF CEMENT KILN DUST?????????????????????????????? 119 3.3.6 ANALYZING THE CHEMICAL COMPOSITION OF CLINKER???... 119 3.3.7 ANALYZING THE CHEMICAL COMPOSITION OF CEMENT???... 120 3.3.8 ANALYZING THE PHYSICAL PROPERTIES OF CEMENT?????. 121 3.3.9 ANALYZING THE PROPERTIES OF CONCRETE????????? 123 3.3.10 ANALYZING THE EMISSIONS????????????????. 126 3.4 CONCLUSION????????????????????????? 126 xiii CHAPTER 4: PRESENTATION AND ANALYSIS OF DATA???????.. 128 4.1 INTRODUCTION???????????????????????... 128 4.2 RESEARCH CONDITIONS???????????????????... 130 4.3 DATA PRESENTATION AND ANALYSIS?????????????. 131 4.3.1 CHEMICAL COMPOSITION OF RAW MATERIALS???????? 133 4.3.2 CHEMICAL COMPOSITION OF KILN FEED???????????. 142 4.3.3 CHEMICAL COMPOSITION OF FUEL SOURCES????????? 147 4.3.4 CHEMICAL COMPOSITION OF CEMENT KILN DUST??????... 162 4.3.5 CHEMICAL COMPOSITION OF CLINKER???????????? 166 4.3.6 CHEMICAL COMPOSITION OF CEMENT????????????. 172 4.3.7 PHYSICAL PROPERTIES OF CEMENT?????????????.. 179 4.3.8 PROPERTIES OF CONCRETE?????????????????.. 289 4.3.9 EMISSIONS????????????????????????? 210 4.4 CONCLUSION????????????????????????? 218 CHAPTER 5: SUMMARY, CONCLUSIONS, AND RECOMMENDATIONS?. 223 5.1 SUMMARY??????????????????????????. 223 5.2 CONCLUSIONS????????????????????????.. 225 5.3 RECOMMENDATIONS?????????????????????. 229 REFERENCES??????????????????????????? 231 APPENDIX A: TEST PROCEDURE?????????????????? 239 APPENDIX B.1: RAW DATA ? COAL ONLY BURN??????????... 253 APPENDIX B.2: RAW DATA ? COAL PLUS TIRES BURN???????... 275 APPENDIX B.3: RAW DATA ? COAL, TIRES, AND PLASTICS BURN??... 296 xiv LIST OF TABLES Table 2.1: Typical Sources of Raw Materials (from Kosmatka et al. 2002)???. 15 Table 2.2: Classifications of Many Alternative Fuels (Greco et al. 2004)???? 30 Table 2.3: Various Properties of Tire Derived Fuel Relative to Two Coal Sources (Barlaz et al. 1993)????????????????????? 31 Table 2.4: Emissions of Coal Relative to Coal and Tires (Corti and Lombardi 2004)??????????????????????????. 33 Table 2.5: Effect on Input and Output Quantities for Tires Used as Fuel (Corti and Lombardi 2004)??????????????????????. 33 Table 2.6: Concentrations of Elements in Coal and Plastic Fuels (Miller et al. 2002)??????????????????????????. 33 Table 2.7: Concentrations in Ash From Coal and Plastic Fuels (Miller et al. 2002). 36 Table 2.8: Proximate and Ultimate Analysis of Chicken Litter and Peat (Abelha et at. 2003)????????????????????????? 37 Table 2.9: Ash Analysis of Chicken Litter (Abelha et al 2003)????????. 38 Table 2.10: CO and VOC Concentrations for Various Chicken Litter/Peat Mixtures and Burning Conditions (Abelha et al. 2003)??????? 39 Table 2.11: Elemental Analysis of Poultry Litter at Wet and Dry Moisture Conditions (D?valos et al. 2002)??????????????? 40 xv Table 2.12: Chemical Composition of CKD Produced in Various Kiln Types (Bhatty et al. 1996)????????????????????. 53 Table 2.13: Cement Plant Information (Eckert and Guo 1998)????????. 55 Table 2.14: CKD Composition (Eckert and Guo 1998)???????????. 55 Table 2.15: Elemental Composition of Clinker Produced with and without Two Alternative Fuels (Mokrzycki et al. 2003)???????????. 57 Table 2.16: Effects of Elements on Concrete Properties??????????... 59 Table 2.17: Setting Time of Cement Specimens with Various Alkali Contents (Lawrence 1998)?????..???????????????.. 62 Table 2.18: Compressive Strength of Cement Specimens with Various Alkali Contents (Lawrence 1998)????????????...????.. 62 Table 2.19: Chemical Analysis of Cement Before Addition of Dosed Elements (Stephan et al 2000)????????????...??????? 72 Table 3.1: Standard Chemical Parameters???????????????... 105 Table 3.2: Approximate Detection Limits for XRF used at the External Laboratory??????????????????????...... 106 Table 3.3: Proximate and Ultimate Analysis Details???????????... 118 Table 3.4: Cement Physical Property Tests by Auburn University??????. 122 Table 3.5: Cement Physical Property Tests by Cement Plant????????.. 122 Table 3.6: Cement Physical Property Tests by Cement Plant Specialty Lab??... 122 Table 3.7: Mix A Proportions????????????????????.. 124 Table 3.8: Mix B Proportions????????????????????.. 125 Table 3.9. Concrete Tests??????????????????????.. 126 xvi Table 4.1: CPR - Chemical Composition of Raw Materials One, Two, and Three. 134 Table 4.2: ELR - Chemical Composition of Raw Materials One, Two, and Three. 135 Table 4.3: CPR - Chemical Composition of Raw Materials Four, Five, and Six? 136 Table 4.4: ELR - Chemical Composition of Raw Materials Four, Five, and Six? 137 Table 4.5: CPR - Percent Change in Raw Materials One, Two, and Three???. 138 Table 4.6: ELR - Percent Change in Raw Materials One, Two, and Three???. 139 Table 4.7: CPR - Percent Change in Raw Materials Four, Five, and Six???? 140 Table 4.8: ELR - Percent Change in Raw Materials Four, Five, and Six???? 141 Table 4.9: CPR - Chemical Composition of Kiln Feed??????????... 142 Table 4.10: CPR - Percent Change in Mean for Kiln Feed?????????? 143 Table 4.11: ELR - Chemical Composition of Kiln Feed??????????... 144 Table 4.12: CPR - Chemical Analysis and Percent Difference for Coal????... 148 Table 4.13: ELR ? Proximate, Ultimate, and Combustion Analysis for Coal??... 149 Table 4.14: ELR ? Standard Parameters for Coal?????????????.. 151 Table 4.15: ELR - Proximate, Ultimate, and Combustion Analysis for Tires??... 154 Table 4.16: ELR - Standard Parameters for Tires?????????????.. 155 Table 4.17: ELR ? Proximate, Ultimate, and Combustions Analysis of Plastics for Burn Three???????????????????????. 157 Table 4.18: ELR - Standard Parameters of Plastics for Burn Three??????.. 158 Table 4.19: ELR ? Chemical Composition of all Fuels???????????. 161 Table 4.20: CPR ? Chemical Analysis and Percent Difference for CKD????.. 162 Table 4.21: ELR - Chemical Composition of Cement Kiln Dust???????.. 163 Table 4.22: CPR - Summary Statistics of Chemical Composition of Clinker??... 166 xvii Table 4.23: CPR ? Percent Differences and Statistical Significance for Clinker?.. 167 Table 4.24: ELR - Chemical Composition of Clinker???????????... 170 Table 4.25: SLR - Rietveld Analysis of Clinker?????????????? 172 Table 4.26: CPR - Summary Statistics for Cement Chemical Composition???. 173 Table 4.27: CPR ? Chemical Composition Percent Difference in Mean for Cement 174 Table 4.28: ELR - Chemical Composition of Cement???????????... 177 Table 4.29: SLR - Rietveld Analysis on Cement?????????????... 179 Table 4.30: CPR - Physical Properties and Percent Change for Cement????... 181 Table 4.31: AUR - Physical Properties and Percent Change for Cement????.. 182 Table 4.32: SLR - Heat of Hydration of Cement?????????????... 187 Table 4.33: AUR and CPR - Concrete Mix A Results???????????.. 191 Table 4.34: Drying Shrinkage Development of Mix A Concrete???????.. 197 Table 4.35: AUR - Concrete Results for Mix B?????????????? 202 Table 4.36: AUR - Drying Shrinkage Development of Mix B Concrete????... 207 Table 4.37: CPR - Summary Statistics for Emissions???????????... 211 Table 4.38: CPR - Percent Difference and Significance of Emissions?????.. 216 xviii LIST OF FIGURES Figure 2.1: Layout of a Typical Dry-Process Portland Cement Production Facility (Kosmatka et al. 2002)?????????????????..?? 14 Figure 2.2: Gas and Material Temperature inside a typical cement kiln (Mokrzycki and Uliasz-Boche?czyk 2003)???????????.. 19 Figure 2.3: Various fuels and their origin (Adapted from Greco et al. 2004)??? 23 Figure 2.4: Trend of Tire Use to Fuel in Cement Plants in the U.S. (PCA 2005)?. 34 Figure 2.5: Energy Content Relative to Water Content of Poultry Litter (D?valos et al. 2002)????????????..???????????... 40 Figure 2.6: Emissions Data from a Plant Burning Alternative Fuels (modified from Mokrzycki et al 2003)??????????..??????? 43 Figure 2.7: Change in Emission Levels due to Changes in Fuel Types (Prisciandaro et al. 2003)?????????????..????? 44 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)??. 54 Figure 2.9: Heat of Hydration for Cement with Various Concentrations of Cr, Ni, and Zn (Stephan et al. 2000)????????????????... 73 xix Figure 2.10: Penetration of Cements Dosed with 25,000 ppm of Cr, Ni, and Zn (Stephan et al. 2000)?????????????..??????... 74 Figure 2.11: Penetration of Cements Dosed with 5,000 ppm of Cr, Ni, and Zn (Stephan et al 2000)?????????????..??????? 75 Figure 2.12: Compressive Strength of Cements Dosed with 25,000 ppm of Cr, Ni, and Zn (Stephan et al. 2000)?????????????..???... 76 Figure 2.13: Compressive Strength of Cements Dosed with 5,000 ppm of Cr, Ni, and Zn (Stephan et al. 2000)????????????..????... 77 Figure 2.14: Effect of Various Doses of Li2CO3 on ASR Expansion (Kawamura and Fuwa 2001)??????????..???????????... 82 Figure 2.15: Compressive Strength for Different P2O5 Concentrations (Miller 1976)????????..?????????????????... 88 Figure 3.1: Overall Sampling and Testing Plan?????????????..... 100 Figure 3.2: Sampling Timeline????????????????????.. 102 Figure 3.3: Diagram of the Cement Plant????????????????.. 108 Figure 3.4: Raw Material Sample Point????????????????..... 109 Figure 3.5: Kiln Feed Sampling???????????????????..... 110 Figure 3.6: Sampling of Clinker???????????????????? 110 Figure 3.7: Automated Plunger Removing Coal Samples?????????... 111 Figure 3.8: Tires Transported to Kiln?????????????????? 112 Figure 3.9: Tires Entering Kiln????????????????????.. 113 Figure 3.10: Plastics and Broiler Litter Kiln Injection System????????.. 113 Figure 3.11: Automated Plunger Collecting Cement Samples????????.. 114 xx Figure 4.1: Percent Change in Mean for Kiln Feed????????????... 146 Figure 4.2: Percent Differences in Coal Relative to Burn Two...???????.. 152 Figure 4.3: Alternative Fuel to Total Fuel Substitution Rate by Heat Equivalency Basis?????????????????????????... 156 Figure 4.4: Percent Difference in Means of CKD Relative to Burn Two????.. 165 Figure 4.5: Percent Change in Chemical Composition Means for Clinker???... 171 Figure 4.6: Percent Difference in Chemical Composition Means for Cement??.. 178 Figure 4.7: Percent Difference in Physical Properties of Cement??????..... 183 Figure 4.8: Compressive Strength Development of Mortar Cubes from Both Testing Agencies????...????????????????. 185 Figure 4.9: AUR - Drying Shrinkage Development of Mortar Prisms?????.. 186 Figure 4.10: SLR - Particle Size Distribution of Cement??????????.. 188 Figure 4.11: Percent Difference in Mix A Concrete Results Relative to AUR Burn Two??????...???????????????????. 192 Figure 4.12: Compressive Strength for Mix A Concrete??????????... 195 Figure 4.13: AUR - Splitting Tensile Strength for Mix A Concrete??????.. 196 Figure 4.14: AUR - Drying Shrinkage Development for Mix A???????... 199 Figure 4.15: AUR - Semi Adiabatic Degree of Hydration Development for Mix A. 200 Figure 4.16: AUR - Percent Difference in Concrete Properties for Mix B???? 203 Figure 4.17: AUR - Compressive Strength for Mix B Concrete???????... 205 Figure 4.18: AUR - Splitting Tensile Strength for Mix B Concrete??????.. 206 Figure 4.19: AUR - Drying Shrinkage Development for Mix B Concrete???? 208 Figure 4.20: AUR - Semi Adiabatic Degree of Hydration Development for Mix B. 209 xxi Figure 4.21: CPR - Time History Plot of NOx Emissions??????????. 212 Figure 4.22: CPR - Time History Plot of SO2 Emissions??????????.. 213 Figure 4.23: CPR - Time History Plot of VOC Emissions?????????? 214 Figure 4.24: CPR - Time History Plot of CO Emissions??????????... 215 Figure 4.25: CPR - Percent Change in Means of Emissions Relative to Burn Two.. 217 1 Chapter 1 Research Introduction 1.1 Project Background The modern day production of portland cement is an industry composed of countless materials, complex facilities, and closely monitored processes. Each of these entities work closely together 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, and many other structures 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, which leaves the sustainability of the process lacking. Portland cement is manufactured by taking raw materials, which are generally mined from the earth, and chemically fusing them together in the presence of extremely high temperatures. The new product, known as clinker, is ground down with sulfates to a specific particle size distribution, and this final product is known as portland cement. For a more thorough discussion of the portland cement production process, see Section 2.2. 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 2 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 cement production facility to run 24 hours a day for seven days a week. With that amount of production, and 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. One aspect of alternative fuels is that they 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, there are certain situations where 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 a significantly less (or even negative) cost, it could be a particularly worthwhile financial undertaking. 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). Not all cement production facilities can consume this quantity of material, but when one considers that there are thousands of facilities worldwide, the quantities of fuels consumed can be staggering. If only a small portion of the nonrenewable resources used in this process could be replaced in many of these facilities, a significant decrease in use of nonrenewable resources could be seen. 3 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 may have a profound effect on the emissions. The primary fuel that is being used at any given cement plant may produce more emissions than 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 one (Greco et al. 2004). This 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 product that is being formed. This presents issues associated with the altering of the final chemical composition of the portland cement. In turn, these alterations of chemical composition may lead to changes in the properties of the ultimate product, concrete. For this reason, this study seeks to measure the chemical composition of all of the materials involved in the production process, along with all of the outputs from the process. Perhaps then, the effect on chemical composition due to the alternative fuels can be understood. Ultimately, this study will test the physical properties of the cement and concrete and determine if there have been any effects that can be directly associated with the implementation of the alternative fuels. In spite of all the positive aspects of the utilization of alternative fuels, if the final product suffers from deficiencies in the properties that make concrete the 4 versatile building material that it is, then the fuel in question may not be considered a viable alternative. 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 as follows: 1. Determine if the utilization of alternative fuels has an impact on the ability of the cement plant to maintain productive operation, 2. Determine if the implementation of alternative fuels has an impact on the chemical composition of clinker and/or portland cement, 3. Determine if the implementation of alternative fuels directly impacts the physical properties of the portland cement, 4. Determine if the implementation of alternative fuels directly impacts the properties of concrete made from this portland cement, and 5. Determine if the implementation of alternative fuels directly impacts the plant emissions. The first objective was not given much attention by researchers at Auburn University. It was primarily studied by the personnel at the cement plant itself. However, this objective was no less important to the study. If the utilization of a certain alternative fuel does not allow the plant to maintain production, that fuel cannot be used. 5 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 changes in chemical composition in the final product. Many physical properties of cement and concrete were measured, and the differences between the cement from each of the fuels was 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. The final objective is another one of particular concern to the cement plant. Because the emissions released by a cement plant are closely monitored and controlled, any effects that the combustion of alternative fuels may have displayed were assessed. 1.3 Research Plan Based on the objectives listed above, a complex yet thorough sampling and testing plan was developed. Researchers at Auburn University and at a cement production facility, referred to as the cement plant, partnered to complete this research plan. The research was conducted during the full-scale production process using the normal procedures utilized at the cement plant. The only change to the production process was the fuels that were used, as they applied to the study. The research plan consisted of four burn periods in which unique combinations of fuels were used. The first burn period 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 phase 6 maintained coal as the primary fuel, but replaced a portion of it with whole scrapped tires. This is the fuel combination that the cement plant uses in its everyday operations. Therefore, the second burn period was considered the reference baseline to which each of the other burns were compared. The third burn period used a combination of pulverized coal, whole tires, and recycled industrial plastics. The plastics were considered to be the first alternative fuel used. The final burn phase used coal, tires, and broiler litter. Broiler litter is a byproduct of the broiler farming industry. The broiler litter was considered to be the second alternative fuel. 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. Due to the amount of work and time necessary to install all of this equipment, the fourth burn phase had not been completed at the time this document was developed. Therefore there will be no results presented here. However, discussion of the broiler litter itself, and the testing associated with this burn will still be included. Within each of these burn periods, a thorough sampling and testing procedure was used. Each of the materials used to produce the portland cement were sampled and tested for their chemical composition. Additionally, each of the outputs from the production process were collected and tested for their chemical composition. Each of the inputs and outputs were sampled and tested at different frequencies relative to their 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 7 external laboratory for additional testing. This additional testing served to verify the results 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 determined. Many physical properties of the cement were evaluated at the cement plant. Most of the same properties were determined by personnel at Auburn University as well. Moreover, the concrete tests were conducted at both Auburn University and the concrete laboratory of the cement plant. However, the testing conducted at Auburn was more thorough than that conducted at the cement plant. At Auburn University, two different concrete mixtures were produced. The goal of producing two different mixtures was to examine the interaction of the cement with various concrete admixtures. The final aspect of the research plan was to collect and monitor the emissions during each of the burn periods. The emissions were monitored by the cement plant using a continuous emissions monitoring system. These results were then reported to Auburn University and are 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 procedure that was implemented in satisfying the objectives. 8 The second chapter of this document is where background research for this study is presented. Literature from other studies pertaining to this research was 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 they 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. A thorough explanation of the methods used to research the problem at hand is presented in Chapter Three. Each of the inputs and outputs to the production of portland cement were sampled and tested in various manners. Chapter Three expands on this sampling and testing procedure. Chapter Four includes presentation, analysis, and discussion of results of this study. 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 data presented in the literature cited in Chapter Two. A summary, several conclusions, and recommendations for this study are presented in the final chapter of this document. There is a summary of the reasons why this study is important, along with the way this study was conducted. The objectives are 9 restated, and conclusions pertaining to each one are given. In some cases definitive conclusions could not be made, but in such cases, reasons for this condition 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 given. A set of appendices follows Chapter Five. Appendix A presents the sampling and testing plan in tabular form. Chapter Three discusses the plan in more detail. The final section of this document is Appendix B. This appendix has three parts. Each part serves to present all of the raw data associated with each burn period. For instance, Appendix B.1 presents all of the data for the Coal Only burn. This appendix consists of tabulated data only. 10 Chapter 2 Literature Review 2.1 Introduction Modern concrete is made from three primary materials, namely: water, aggregate (gravel and/or sand), and cementitious material, that, when mixed with the water, hardens with time. There are many different types of cementing material, however, the most common is known as portland cement. ?The invention of portland cement is generally credited to Joseph Aspdin, an English mason. In 1824, he obtained a patent for his product, which he named portland cement because when set, it resembled the color of the natural limestone quarried on the Isle of Portland in the English Channel? (Kosmatka et al. 2002). The technology of cement production has progressed dramatically from the days of Aspdin. One of the most significant advances was the addition of extremely high temperatures, which causes the raw materials to ?melt? together, forming a relatively uniform product. The temperatures required to produce modern cement are on the order of 1500?C, making the production of portland cement an extremely fuel-intensive process (Jackson 1998). In many cases, the costs associated with fuels may be as much as 30 to 40% of the total production costs (Mokrzycki et al. 2003). In an attempt to reduce this cost, many cement production facilities are turning towards the utilization of alternative 11 fuels (Mound and Colbert 2004). The reason for the reduced cost of alternative fuels is that they are typically a byproduct of some other industry. Some examples of alternative fuels are scrap tires, waste wood, biomass, used oils, and spent solvents (Wurst and Prey 2002). The environment can also benefit from alternative fuel utilization. There are three primary ways in which the use of alternative fuels are beneficial in this way: 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). Care must be taken, however, to select alternative fuels that do not produce adverse side effects. Increased emissions and changes to product chemistry and performance are the potential negative effects that are of greatest concern (Mokrzycki and Uliasz-Boche?czyk 2003). As with any process-related decision, it is necessary to compare the advantages with the disadvantages in order to determine if the implementation of alternative fuels is appropriate for each portland cement facility. The goal of this document is to identify and examine all of the parameters that have significant bearing on the feasibility of introducing alternative fuels to the portland cement industry. 2.2 Portland Cement Production Simply put, the modern-day production of portland cement occurs when raw materials consisting of appropriate proportions of calcium, silica, alumina, and iron are fused together at approximately 1500?C to form a product known as clinker. Once the clinker is cooled, it is interground with an appropriate quantity of sulfate to a predetermined fineness to form portland cement (Taylor 1997). Due to the high level of 12 complexity of the production process, and the desire to be as economical as possible, the exact process varies from one facility to another (Jackson 1998). One fundamental difference is the choice between a wet or dry process. In the dry process, grinding and blending are done on dry raw materials. The wet process completes these procedures with the raw materials suspended in water to form a slurry. Other than that, both processes are similar (Kosmatka et al. 2002). The dry process is more energy efficient, and is therefore utilized more in modern kilns. A schematic of a typical dry process is shown in Figure 2.1. The raw materials are first proportioned in the appropriate ratios. They are then sent to a grinder, which reduces each of the materials to a uniform size. From the grinder, the raw materials are sent to a blending silo, where they are thoroughly mixed. If the mixed raw materials are not immediately used, they may be sent to a storage silo. The raw material feed is then sent to the preheater, where it is calcinated before entering the kiln. Once in the kiln, the raw material feed is fused together into clinker. Once the clinker exits the kiln, it is cooled before being stored in silos. Finally, the clinker is mixed with gypsum and ground into cement. The cement is then stored, packaged, or shipped to the consumer. Throughout the process, dust is removed and collected at various locations. 2.2.1 Raw Materials The selection and processing of raw materials is a major component of the portland cement manufacturing process. In fact, raw material processing accounts for 10 percent of the energy cost in an average facility (Chatterjee 1979). 13 The raw materials used in the manufacture of portland cement primarily consist of a combination of a calcareous (high CaCO3 content) material and an argillaceous (high silica and alumina content) material (Kosmatka et al. 2002). Table 2.1 shows the wide variety of sources from which raw materials may be acquired. Because the calcareous material is the one used in the greatest quantities, and the fact that approximately one third of the carbon mass is lost as CO2 during the process, portland cement plants are typically located near a calcareous raw material source (EPA 1995). This helps keep transportation costs down. Due to the variable nature of the chemical composition of the raw materials, it is often necessary to operate a facility in a location where the calcareous and argillaceous materials alone do not provide the appropriate composition. In such cases, as long as one component has a calcium carbonate composition of at least 80 to 85 percent, the correct composition may be achieved by the introduction of other materials, such as those shown in Table 2.1 (Jackson 1998). Figure 2.1: Layout of a Typical Dry-Process Portland Cement Production Facility (Kosmatka et al. 2002) 14 15 Once the cement plant has obtained all the necessary raw materials, they must be crushed and proportioned so that the appropriate chemical composition of the raw material feed is met (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. In order to achieve the lowest possible temperature in the kiln, and therefore lower fuel consumption, it is imperative that the feedstock is ground to the appropriate fineness (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 16 2.2.2 Pyro-processing Pyro-processing is the utilization of heat to change the chemical composition of a material. Once the raw materials have been proportioned and mixed, they are ready to be fused together on a chemical level. It was mentioned previously that there are two types of processes, wet and dry. While that is fundamentally true, there are actually five types of processes. In the wet process and the long dry process, all of the activity occurs within the kiln itself. The semidry process, the dry process with a preheater, and the dry process with a preheater/precalciner each heat the raw materials before they enter the kiln (EPA 1995). The purpose of a preheater and/or precalciner is to heat the raw material mix from ambient temperature to approximately 850?C before it is fed into the kiln. In the process, some of the carbon is removed as CO2, which leaves a material with a higher CaO content (Jackson 1998). This process makes clinkerization much more fuel and cost efficient. Whether or not a preheater and/or precalciner is used, the raw material passes through the kiln at a rate determined by the slope and rotational speed of the kiln (Kosmatka et al. 2002). Although the mechanisms inside the preheater (when present) and kiln are very complex, the progression of activity is basically as follows (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 17 4. Calcination of carbonate materials, 700?C-850?C 5. Formation of C2S, aluminates and ferrites, 800?C-1250?C 6. Formation of liquid phase melt, >1250?C 7. Formation of C3S, 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 these mechanisms, C3S (alite), C2S (belite), C3A (aluminate), and C4AF (ferrite) are known as Bogue Compounds, which are the major clinker phases. When portland cement is 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 (dotted line), and the material temperature (solid line) as they progress through the various parts of the kiln system. Additionally, the retention times in each area of the system are shown. 2.2.3 Clinker Cooling Before the clinker can be ground into the final product, it must be cooled. The cooling of clinker takes place in two locations: 1) while it is still in the kiln, but past the burning zone, and 2) in a clinker cooler (Manias 2004). Because the latter is the primary mode of cooling, the former will not be discussed in detail here. The cooling of clinker halts the further reaction of the raw materials (Jackson 1998). In order for cement to exhibit its best strength-giving properties, the clinker from 18 which it is produced must be cooled rapidly from the temperature at the burning zone to about 1200?C, otherwise some of the clinker phases may further react into a form that inhibits strength gain as well as other cementitious properties (Jackson 1998; Mosci 2004). Once the reactions have been halted, it must be cooled to approximately 93?C so that it may be handled with traditional conveying equipment (EPA 1995). Clinker coolers are also designed to recover and return to the system as much heat as secondary or tertiary air (Mosci 2004). As much as 30 percent of the heat input to the kiln may be recovered (EPA 1995). The degree to which heat recovery can be made, as well as efficiency in cooling, is based primarily on the type of cooler used. A number of different types of coolers have been implemented over the years, including planetary, rotary, shaft, and traveling grate coolers (Mosci 2004). The latter type is most commonly used today. Figure 2.2: Gas and Material Temperature inside a typical cement kiln (Mokrzycki and Uliasz-Boche?czyk 2003) 19 20 2.2.4 Grinding and Finishing The final step before packaging and shipping is the grinding of clinker and gypsum together. Up to five percent (by weight) gypsum, or other sulfate source, is added to the clinker after it has cooled (EPA 1995). The amount of gypsum is adjusted to regulate cement properties such as setting time and shrinkage and strength development (Kosmatka et al. 2002). There are many types of grinders that may be used in the finishing milling. Typically, the process is accomplished using a ball mill, roller mill, roll press, or a combination of these (Strohman 2004). Today, however, finish milling is done almost exclusively by ball mills (EPA 1995). A ball mill consists of a tube rotating about its horizontal axis, filled with 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). The final size of the cement is determined by its desired application. Typically, the finished product will be ground so that almost every particle will pass through a 45 micrometer sieve (Kosmatka et al. 2002). Whatever the desired fineness, it is imperative that uniformity is maintained as much as possible (Strohman 2004). Once grinding is completed, the finished product is portland cement. 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- 21 sustainable, and very rapid.? The exothermic component of this reaction is, of course, that with which the cement industry is primarily concerned. Clinker production is a fuel-intensive process (Jackson 1998). The efficiency with which a facility runs is highly variable. However, an average cement plant burning coal consumes 120 kg of fuel in the process of producing 1 ton of portland cement (Mokrzycki and Uliasz-Boche?czyk 2003). The least productive plants are typically those that employ the wet kiln process. At these facilities it is possible to produce clinker at a rate of 2,000 tons per day. The most productive plants are generally those utilizing a precalciner system. In a location using this type of kiln, production may be as high as 10,000 tons per day (Manias 2004). At this rate, it is possible to consume as much as 1,200 tons of coal on a daily basis. This amounts to 30 to 40 percent of the total production costs (Mokrzycki et al. 2003). The significant contribution to operating cost made by fuels, means ?the appropriate selection and use of a fuel has always been and still is a matter of great concern for the cement industry? (Greco et al. 2004). Many different types of fuel exist. Figure 2.3 shows some of these fuel types, and the means by which they are derived. Some of the more traditional fuels commonly used in cement manufacturing today are natural gas, furnace oil, petroleum coke, and miscellaneous coals (Wurst and Prey 2002). However, due to the potentially environmentally friendly aspect, in combination with the possibility of substantial decrease in (or even negative) cost, the cement industry is increasingly turning to alternative fuels (Bhatty 2004). Some typical alternative fuels used are (see Section 3.4): tires, waste wood, used oils, and spent solvents, which may replace some or all of the traditional fuels mentioned above (PCA 22 2004). 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, alternative fuels will refer to anything used as a substitute for traditional fuels. 2.3.1 Alternative Fuels in Cement Kilns The unique environment that is present within a cement kiln makes it a very conducive atmosphere for the implementation of alternative fuels (Mokrzycki and Uliasz- Boche?czyk 2003). The following kiln characteristics render it amenable to alternative fuels (Greco et al. 2004): ? The temperatures in the kiln, upwards of 1500?C, are substantially higher than the threshold above which waste fuels must be incinerated, as established by environmental regulations ? The high alkalinity atmosphere readily absorbs most acidic gases released by the oxidation of sulfur and chlorides. ? Most of the non-fuel compounds, such as metallic oxides, are not deleterious to the production of clinker. ? The majority of the noncombustible products, particularly metals, are either incorporated into the clinker itself, or trapped by and recycled with the cement kiln dust. 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 R e s i d u a lC o n v e n t i o n a l N o n - c o n v e n t i o n a l Methanol Ethanol Lean gas Synthetic Renewable Fuel Origin of Fuel Non-renewable fuel Fossil derived synthetic fuel Fossil Biomass derivedNon- biomass derived Biomass Figure 2.3: Various fuels and their origin (Adapted from Greco et al. 2004) 23 24 Because most of the noncombustible products are incorporated into the final product, it is necessary to establish that the performance of the cement is not inhibited by the altered chemical composition. A thorough discussion of the elements and their possible effects on the product can be found in Section 6. Similarly, a discussion of the cement kiln dust and the impact of altered compositions can be found in Section 5. 2.3.2 Advantages of Alternative Fuels The advantages of using alternative fuels in the cement industry are numerous. According to Greco et al. (2004), the four primary advantages that are simultaneously gained by burning alternative fuels are: reduction of production costs, preservation of fossil fuel resources, reduction in the volume of wastes that must be disposed of by other means, and a decrease in global greenhouse effect. The latter is based on the fact that the emission of CO2 from what would normally be two separate processes is combined into a single process. With energy demands in a wet process kiln as substantial as 6 million BTUs per day, it is easy to see that the implementation of low-cost alternative fuels offers significant economic advantages (Barger 1994). Although the unit costs of alternative fuels are less than those of traditional fuels, another aspect of acquisition that must be evaluated in order to accurately estimate the potential for cost savings is availability. A systematic view of the conditions concerning actual fuel availability as well as the short- and medium-term new trends of availability of new fuel types must be conducted (Greco et al. 2004). A substantial portion of the acquisition cost of fuels is intertwined with availability, transportation, and processing costs. 25 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 product-based life styles, so too do the manufacturing wastes that must be disposed of (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 quantities of land that may become unsightly and environmentally detrimental. Equally strenuous on the environment are waste incinerators, which have only a single purpose. Incinerators burn garbage, but do not use the heat generated; whereas a cement plant does the same thing only it uses the heat generated to manufacture portland cement. Therefore, unlike incinerators, a cement facility serves a dual purpose (Mokrzycki and Uliasz-Boche?czyk 2003). Another significant environmental advantage of alternative fuel substitution is the preservation of nonrenewable energy sources (Trezza and Scian 2000). The process of mining coal, for instance, negatively influences 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 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). For instance, 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). One secondary advantage in the case of some alternative fuels is the reduction in required quantities of certain raw materials. 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 26 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 substitution of alternative fuels in the production of portland cement, the disadvantages must be examined and weighed against the advantages. 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 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, lead, as well as others (Martinez 1996). A detailed discussion of emissions can be found in Section 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. 27 One potentially devastating constraint of the implementation of alternative fuels is the final clinker composition (Mound and Colbert 2004). Because the cement clinkering process incorporates the combustion byproducts into the clinker, any undesirable compounds present in the fuels may be deposited into the cement itself. If any of these compounds produces a decrease in quality of the cement, the benefits of alternative fuel substitution could be negated. A detailed discussion of elements that could alter the properties of cement and/or concrete can be found in Section 2.6. 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). 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 as well, and it must be done at a lesser cost than the savings that might be gained from use of cheaper fuels. 28 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 is 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 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 ? Sulfur content ? less than 2.5 percent ? Polychlorinated Biphenyls (PCBs) content ? less than 50 parts per million (ppm) ? Heavy metals content ? less than 2500 ppm. It is evident from this list of criteria that the door is wide open for the types of materials that may be considered as a viable alternative fuel. Alternative fuels are categorized by the phase in which they exist. Therefore, the three classifications of fuels are solid, liquid, and gas (Peray 1986). There is a wide variety of fuels that fall into each 29 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, scrap tires, waste plastics, and broiler litter are considered as fuels. All these alternative fuels can be classified as solids. Therefore, liquid and gaseous alternative fuels will not be discussed here. For a comprehensive discussion of these classifications, see Greco et al. (2004). Solid fuels are the most commonly used, and in terms of particular fuels, 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 with which this study is primarily concerned are: scrap tires, industrial plastics, and broiler litter. 2.3.4.1 Tires as Fuel Scrap tires first gained notoriety as a serious waste problem 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 of 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 used tires ?represent considerable 30 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) Gaseous waste Landfill gas Cleansing solvents Paint sludges Solvent contaminated waters "Slope" - residual washing liquid from oil and oil products storage tanks Used cutting and machining oils Waste solvents from chemical industry Municipal waste Plastic shavings Residual sludge from pulp and paper production Rubber shavings Sawdust and wood chips Sewage treatment plant sludge Tannery waste Tars and bituminus Used catalyst Used tires Solid or pasty waste Liquid waste 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 sulfur, which leads to material melting and build-ups in the kiln and preheater 31 (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 sulfur, one to two percent zinc, and an energy value of 26987 to 33472 kJ/kg (11602 to 14390 BTUs/lb) (Jackson 1998). Wurst and Prey (2002) report average energy values of tires to be 25104 to 29288 kJ/kg (10793 to 12592 BTUs/lb), with zinc and sulfur as the primary elements of concern. Table 2.3 shows the energy value of tire derived fuel (TDF) relative to two sources of coal. Sulfur, 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. 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 106/kJ ) 0.35 0.74 0.30 Nitrogen (%) 0.24 1.76 1.76 Nitrogen Production (kg x 106/kJ ) 0.07 0.65 0.65 Chlorine (%) 0.15 0.08 0.08 Chlorine Production (kg x 106/kJ ) 0.04 0.03 0.03 Energy Source 32 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). 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 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. 33 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 show the tremendous possibilities for tire derived fuel usage in cement plants. Figure 2.4 shows the rate of increase in facilities 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. 34 Figure 2.4: Trend of Tire Use as Fuel in Cement Plants in the U.S. (PCA 2005) 2.3.4.2 Plastic Waste 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 28870 kJ/kg (12412 BTUs/lb). Additionally, the elements that are deemed the most 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 35 mm. 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 Table 2.6 and Table 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 36 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. 37 Table 2.8: Proximate and Ultimate Analysis of Chicken Litter and Peat (Abelha et at. 2003) 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. 38 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 (6211 BTUs/lb), and a sample has a calorific value of 4,000 kJ/kg (1720 BTUs/lb) when its water content 39 reaches 78 percent. These data clearly illustrate the detrimental effect that increasing moisture content has on the heating value of broiler litter. Table 2.10: CO and VOC Concentrations for Various Chicken Litter/Peat Mixtures and Burning Conditions (Abelha et al. 2003) 40 Table 2.11: Elemental Analysis of Poultry Litter at Wet and Dry Moisture Conditions (D?valos et al. 2002) En erg y C on ten t (k J/k g) En erg y C on ten t (k J/k g) Figure 2.5: Energy Content Relative to Water Content of Poultry Litter (D?valos et al. 2002) 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 41 process (Jackson 1998). The primary components of these gaseous emissions are CO2, NOx, and SOx. 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 document, 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 (CO2) and carbon monoxide (CO) are major emission components with which portland cement production facilities must be concerned. CO2 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 CO2 emissions from portland cement production were estimated at 829 million metric tons, which accounts for 3.4 percent of all CO2 emissions for that year (Hanle et al. 2004). On a more regional scale, in 1999 the portland cement industry in the United 42 States was responsible for 22.3 million metric tons of carbon dioxide emissions, which accounted for 4 percent of all that year?s CO2 emissions (Bhatty 2004). Carbon dioxide emissions come from combustion of fossil fuels and the calcination of limestone, each of which contribute approximately half of the CO2 during production (Worrell et al. 2001). Calcining is the process of heating limestone and converting CaCO3 into CO2 and CaO. This process is typically carried out in a preheater, which may also be known as a precalciner. The CO2 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 CO2 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. 43 0 100 200 300 400 500 600 700 800 CO NO2 SO2 Emission Type Em iss ion s t o A ir (% ) Allowable Without PASr Fuel With PASr Fuel 2NO2 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 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. Figure 2.7: Change in Emission Levels due to Changes in Fuel Types (Prisciandaro et al. 2003) 44 45 2.4.2 Nitrogen Emissions Nitrogen Oxides (NOx) 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 NO2. Typically, more than 95 percent of exhaust gases produced by a cement kiln are NO, with the remainder of the gases generally comprised of NO2 (Gardeik et al. 1984; Greer 1989). Just like carbon-based emissions, NOx concentrations are also susceptible to the temperamental nature of cement kilns. The independent variables which have the greatest influence on NOx 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 NOx is formed in the kiln. In order of decreasing contribution to overall concentration, they are thermal NOx, fuel NOx, and feed NOx (Young 2002). Thermal NOx (primarily NO) is the most abundant source of NOx 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 NOx begins to form is commonly thought to be around 1400?C, above which NO levels increase dramatically. The majority of the thermal NOx are formed in the burning zone where flame temperatures easily reach 1600?C (Bhatty 2004; Greer 1989; Marengo et al. 2006; Young 2002). Fuel NOx 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 46 ignition temperature of the fuel, fuel NOx is being formed (Gardeik et al. 1984). The quantity of nitrogen present in fuel is significantly less than that present in the combustion air, which means that the contribution of fuel NOx 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 NOx formation. This allows fuel NOx to be the primary contributor at this location (Young 2002). Greer (1986) stated that if all the other factors controlling NOx formation are held constant, the total amount of NOx can be altered by controlling the content of nitrogen in the fuel (Greer 1986). The final source of NOx, is the raw material feeds. Feed NOx is similar to fuel NOx 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- 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 NOx. 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 NOx to the overall NOx production in the kiln is minimal (Young 2002). There are two major implications of large volumes of NOx emitted into the atmosphere. The first is that NO2 combines with moisture in the atmosphere to form either nitrous acid or nitric acid. These two compounds are the primary components of 47 acid rain (Bhatty 2004). Although the majority of the NOx produced in the kiln system is NO, it is largely converted into NO2 in the atmosphere (Greer 1989). The second product that forms when NOx is released into the atmosphere is smog. Smog is formed when NOx combines with hydrocarbons in the presence of solar radiation (Bhatty 2004; Greer 1989). Therefore, it is important that all NOx levels are monitored and limited throughout the portland cement industry. Because the majority of the NOx produced in cement kilns comes from thermal NOx, alternative fuels cannot change its concentration substantially in either direction. However, the nitrogen concentration of fuels does have some effect on the amount of NOx produced. The results of the study conducted by Mokrzycki et al. (2003) show that NO2 emissions were decreased by 81 percent between traditional fuels and the PASr fuel (see Figure 6). The study conducted by Prisciandaro et al. (2003) shows an increase in NOx emissions in Plant 1, and a decrease in NOx emission at Plant 2 (see Figure 2.7). 2.4.3 Sulfur Emissions Sulfur Oxides (SOx) are a family of sulfur-based compounds that are commonly released as emissions from industrial applications. In the portland cement industry, SO2 and SO3 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 SOx emissions are in the form of SO2 (Marengo et al. 2006). The SO2 that is released from the kiln system is produced by the oxidation of sulfur compounds 48 that enter the kiln in either the fuel or the raw materials. The quantity of SO2 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 sulfur are released via emissions, the majority of sulfur that enters the kiln is either 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 sulfur that enters the kiln either remains in the kiln or is incorporated into the clinker. When SOx are emitted into the atmosphere, they typically takes one of two forms. SO2 readily combines with the moisture in the atmosphere to form H2SO4, also known as sulfuric acid, which is a major contributor to acid rain (Bhatty 2004). SOx 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 NOx and carbon-based emissions, the type of fuels used have a direct effect on the amount of SOx 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 SO2 emissions by 7 percent between traditional fuel and PASr fuel (see Figure 2.6). 49 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 NOx, SOx, and carbon-based emissions, the concentrations of each are affected, to some extent, by the type and quantities of fuels being used. Due to 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. 50 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 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 51 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 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 52 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. 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), stabilization of soils (Bhatty et al. 1996), and waste stabilization/solidification (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). Table 2.12 shows the chemical composition, as a percentage of total weight, of the CKD produced in three different types of kilns (Bhatty et al. 1996). Figure 2.8 shows 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 (Todres et al. 1992). 53 Table 2.12: 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 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 2.13 provides information about each of the plants, which includes whether it used waste-derived fuels as its primary (P) or alternate (A) fuel source. 54 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) Table 2.14 shows the results for seven of the seventeen kilns studied. 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. 55 Table 2.13: 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 2.14: CKD Composition (Eckert and Guo 1998) 56 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. It has previously been shown that many materials must be fed into the kiln in order to produce cement. The 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 to 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 separate tests in which two different alternative fuels were used. Table 2.15 shows the change in chemical composition of the clinker based on changes only in fuel types. It is evident from this 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 57 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 2.15: Elemental Composition of Clinker Produced with and without Two Alternative Fuels (Mokrzycki et al. 2003) Table 2.16 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. 58 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. The following sections discuss the source, resulting destination, and effect on the properties of the product for many selected elements. Table 2.16: Effects of Elements on Concrete Properties 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 barb4upbarb4up ? ? 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 barb4down ? ? Manganese barb4up, barb4down ?, ? barb4down Effects color of clinker/cement Mercury Y Molybdenum ?,? ? Nickel ??,? ?? ?? ? Produces brown color in clinker/cement Nitrogen Phosphorus ?? ?? ?? ?? ? ? ? Rubidium ? ? ? ? ? Strontium ? ? ? ? ? Sulfur ? ? ? ?, ? Thallium Y Titanium ?, ? barb4up ? ? 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 barb4upbarb4up barb4up barb4downbarb4downbarb4downbarb4downbarb4downbarb4downbarb4downbarb4down barb4down Single Source ?? ? ?? ? Key Property Element 59 60 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 typical 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 sulfur 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 sulfur. 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 condense in the cooler parts (Jackson 1998). This produces clogs in the preheater (when present) and rings in the kiln (Gartner 1980). 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 61 present at levels too large to completely combine with sulfur, 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 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 2.17 and 2.18 as reported by Lawrence (1998). Table 2.17 shows the initial and final setting times, in minutes, for concrete with various concentrations of alkalis. In this study, it was found that as the concentration of Na2O increased, so did both initial and final setting times. This contradicts what Jackson (1998) reported. As the concentration of K2O increased, both initial and final setting times decreased. Table 2.18 shows the variation in compressive strength, at four ages, for the same concrete specimens as in Table 2.17. As the concentration of Na2O increased, the compressive strength decreased at all ages. The compressive strength for the various concentrations of K2O was more variable. For the concrete with 0.88 percent K2O, the compressive strength, relative to the control sample, was increased at 1 and 3 days, but decreased at 7 and 28 days. The concrete with 1.48 percent K2O was decreased at 1 and 3 days, and increased at 7 and 28 days relative to the concrete with 0.88 percent K2O. This is consistent with what Gartner (1980) and Taylor (1997) reported. 62 Table 2.17: Setting Time of Cement Specimens with Various Alkali Contents (Lawrence 1998) H2O (%) Initial Final Control 25 180 215 0.72% Na2O in clinker 25 185 290 1.26% Na2O in clinker 25 295 360 0.88% K2O in clinker 25 150 205 1.48% K2O in clinker 25 50 135 Setting Time (min)Cement + sodium or potassium oxide in clinker Table 2.18: 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% Na2O in clinker 19.5 39.8 59.6 68.7 1.26% Na2O in clinker 18.4 39.2 57.5 68.2 0.88% K2O in clinker 21.9 44.8 60.7 72.1 1.48% K2O in clinker 20.0 43.1 61.0 73.2 Cement + sodium or potassium oxide in clinker Compressive strength (MPa) 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). 63 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. 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. 64 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. 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). 65 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 possible 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). 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 66 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 67 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, it is something that anyone placing concrete high in cadmium levels should be aware of its consequences. 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. 68 Almost without exception, any carbon that is introduced into the kiln will be released through the stack emissions as CO2. This is one of the most significant problems 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 17th 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 CaCO3 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 69 no preheater stacks are present, these compounds are generally incorporated into the CKD, if they don?t form kiln rings (Bhatty 2004). Jackson (1998) also claimed that chlorides will end up in emissions. 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. 70 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 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 a decrease in 28-day strength (Bhatty 2004; Gartner 1980; Miller 197;, 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 Cr2O3, NiO, and ZnO, ranging 71 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 2.19. 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 Cr2O3 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. 72 Table 2.19: Chemical Analysis of Cement before Addition of Dosed Elements (Stephan et al. 2000) Oxide Portland Cement SiO2 (wt.%) 14.1 Al2O3 (wt.%) 3.5 Fe2O3 (wt.%) 2.2 CaO (wt.%) 41.3 MgO (wt.%) 1.7 K2O (wt.%) 1.1 SO3 (wt.%) 0.6 Cr (ppm) 51 Ni (ppm) 15 Zn (ppm) 88 Specific surface (m2/cm3) 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 effects from concrete manufactured with portland cement with high concentrations of chromium. Figure 2.9: Heat of Hydration for Cement with Various Concentrations of Cr, Ni, and Zn (Stephan et al. 2000) 73 Figure 2.10: Penetration of Cements Dosed with 25,000 ppm of Cr, Ni, and Zn (Stephan et al. 2000) 74 Figure 2.11: Penetration of Cements Dosed with 5,000 ppm of Cr, Ni, and Zn (Stephan et al. 2000) 75 Figure 2.12: Compressive Strength of Cements Dosed with 25,000 ppm of Cr, Ni, and Zn (Stephan et al. 2000) 76 Figure 2.13: Compressive Strength of Cements Dosed with 5,000 ppm of Cr, Ni, and Zn (Stephan et al. 2000) 77 78 2.6.12 Cobalt (Co) Cobalt is the 27th 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 29th 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). 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 79 (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 9th 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 80 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 81 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 decreased as the quantity of Li2CO3 increased. 82 Figure 2.14: Effect of Various Doses of Li2CO3 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. 83 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. However, it can lead to destructive expansion of concrete. 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 Mn2O3 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 84 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).? 2.6.19 Mercury (Hg) Mercury is the 80th 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 85 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 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, 86 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- 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 87 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. 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 P2O5. 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). P2O5 is not a volatile compound in the kiln process, and will usually be incorporated into the clinker. A typical concentration for P2O5 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 P2O5 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 P2O5 levels above 2.5 percent. Concrete hardening becomes slower with high levels of 88 P2O5. Figure 2.15 shows the effect of P2O5 content on compressive strength (Miller 1976). From this figure, it can be seen that there is an optimum P2O5 content at approximately 2.5 percent, above which compressive strength decreases. However, based on the P2O5 concentrations reported by Taylor (1997) and Jackson (1998), it may be concluded that most cements will contain less than this optimum P2O5 concentration. Figure 2.15: Compressive Strength for Different P2O5 Concentrations (Miller 1976) 89 2.6.24 Rubidium (Rb) Rubidium is 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 promote clogging throughout the system. 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 38th element and a metal. The presence of Sr is not uncommon in the raw materials, particularly in CaCO3 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). 90 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.? 2.6.26 Sulfur (S) Sulfur is a nonmetal and element number 16. Sulfur 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 sulfur (Gartner 1980). Limestone, clayey sediments, and marl also contain appreciable quantities of sulfur (Bhatty 2004). The primary source of SO3 in cement is the addition of gypsum during grinding of the clinker. The levels of SO3 added are closely monitored in order to produce the desired effects in the cement, such as control of setting times. The optimum quantity of SO3 added is on the order of three to five percent (Taylor 1997). ASTM C150 limites the amount of gypsum that may be added. Some sulfur in the form of SO2 is released through the stack emissions. A detailed discussion of sulfur emissions can be found in Section 2.4.3. The most common place for sulfur to be found is in the clinker. This is likely to occur because sulfur prefers to combine with alkalis (Gartner 1980), which are readily available in most kiln systems. 91 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 sulfur in clinker has no deleterious effects, so long as it is maintained at acceptable concentrations. Otherwise, it may retard setting time and inhibit strength gain. If SO3 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 sulfur 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 SO3 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 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). 92 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. 2.6.28 Titanium (Ti) Titanium is the 22nd 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 been found in certain auxiliary raw materials such as slag (Miller 1976). Bhatty (2004) reported TiO2 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 TiO2 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 TiO2 produces improved cement strengths. Jackson (1998) reported TiO2 93 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 give the cement a yellow color (Miller 1976). Taylor (1997) claimed the color change associated with Ti is of a darker nature. 2.6.29 Vanadium (V) Vanadium is the 23rd 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 V2O5. 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; 94 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, 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 95 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 Zn2+ 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, there are no profound affects 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, Figure 2.12 and 2.13 show the effect of zinc on compressive strength. At both concentrations reported, the effects were negligible. 96 2.6.31 Zirconium (Zr) Zirconium is the 40th 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. 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 97 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 cooperation with one another. For a detailed discussion of the portland cement production process, see Section 2.2. 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 four distinct collection and testing periods, which are referred to as burn periods. They are as follows: 1. Burn period one utilized only coal as fuel. 2. Burn period two utilized coal and tires. This is the standard fuel combination used at the cement plant, and was therefore considered the baseline for comparison purposes. 3. Burn period three used coal, tires, and recycled post-industrial plastics. These plastics were considered alternative fuel one. 4. Burn period four used coal, tires, and broiler litter. The broiler litter was considered alternative fuel two. 99 In each burn period, 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 step 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. For the sake of simplicity, as well as to reduce the amount of additional work required of the cement plant personnel, 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. 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. Just as with the sampling of the materials, one goal of the testing portion of the program was 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. Raw Materials: Chemical Composition Emissions: NOx, SO2, VOC, CO Concrete: Fresh Properties, Physical Properties, Durability Sampling and Testing Plan Fuels: Chemical Composition, Combustion Properties Cement Kiln Dust: Chemical Composition Clinker: Chemical Composition, Cement: Chemical Composition, Physical Properties Figure 3.1: Overall Sampling and Testing Plan 10 0 101 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 the material collected at various times and locations 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 using discrete samples taken 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 presented 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. 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; namely, whether the discrete samples collected at the plant were tested, or if composite specimens were prepared from the discrete samples collected. Discussion of specimen preparation methods is given in Section 3.3.2. The typical sampling period was during Burn One, during Burn Two, during Burn Three, and during Burn four. A graphical timeline for the typical sampling period can be found in Figure 3.2. 1 2 3 4 1 2 3 1 2 1. Coal Only Sample Days = 2. Coal + Tires Sample Days = 3. Coal + Tires + Plastics Sample Days = 4. Coal + Tires + Broiler Litter Sample Days = Legend: - Coal only as fuel - Coal, tires, and broiler litter as fuel - Coal and tires as fuel - Collect material samples - Coal, tires, and plastics as fuel - Collect emissions samples Burn Period (Days) Post-Burn Period (Days)Fuel Type(s) Pre-Burn Period (Days) Figure 3.2: Sampling Timeline 10 2 103 3.2.1 Collection of Materials All of the materials used in the production process were sampled and tested for various properties. All but one of these materials can be divided into two categories. These categories are process inputs and process outputs. For a detailed description of the production of portland cement, see Section 2.2. Process input materials are those that are used to produce portland cement. The inputs at this specific cement plant were the raw materials, of which there were six, as well as the fuels. Five of the six raw materials were combined in strictly controlled proportions in order to produce a material known as kiln feed, also considered raw material seven. 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 were sampled and tested for various properties as described in the following sections. The process output materials are clinker, portland cement, and emissions. Each of these materials were sampled and tested for various properties. An emphasis was placed on the primary output, portland cement. Each of these process output materials were sampled and tested for various properties as described in the following sections. One final material that was collected and tested is cement kiln dust (CKD). CKD is primarily composed of fine particulate matter that does not combine with the other materials in the kiln to become clinker. For a complete discussion of CKD, see Section 2.3. What distinguishes CKD from the other materials is that it is both an output and an 104 input. It is a byproduct of the clinkering process, but it is recycled back into the kiln feed just before entering the kiln. As with the other materials, CKD was sampled and tested for various properties as described in Section 3.3.5. 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 a percent by weight (wt. %), or as parts per million (ppm). The former is the percentage of the total unit weight comprised by 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. 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 is 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. Table 3.1 shows the standard parameters that were tested for by the cement plant and by the external laboratory. Each of the parameters shown in Table 3.1 was determined by XRF, except for Na2Oeq, which is calculated from the concentrations of Na2O and K2O by the formula presented in ASTM 105 C 150. The approximate detection limits for the XRF used at the external laboratory are shown in Table 3.2. Table 3.1: Standard Chemical Parameters Standard Cement Plant Parameters (wt. %) (wt. %) (ppm) Al2O3 Al2O3 Arsenic (As) CaO CaO Barium (Ba) Fe2O3 Fe2O3 Cadmium (Cd) K2O K2O Chlorine (Cl) MgO MgO Cobalt (Co) Na2O Na2O Chromium (Cr) Na2Oeq P2O5 Copper (Cu) SiO2 SiO2 Mercury (Hg) SO3 SO3 Manganese (Mn) Moisture TiO2 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 Concrete was made from the portland cement collected during each of the burn periods. The specific tests associated with concrete are described in Section 3.3.9. Any other tests that were specific to only one material were discussed in the section pertaining to that material. 106 Table 3.2: Approximate Detection Limits for XRF used at the External Laboratory Parameter Lower Limit of Detection Al2O3 (wt. %) 0.01 CaO (wt. %) 0.01 Fe2O3 (wt. %) 0.01 K2O (wt. %) 0.01 MgO (wt. %) 0.01 Na2O (wt. %) 0.01 P2O5 (wt. %) 0.01 SiO2 (wt. %) 0.02 SO3 (wt. %) 0.01 TiO2 (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 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. 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), to be discussed in Section 3.3.3, which determines its chemical composition. 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. Figure 3.3: Diagram of the Cement Plant 1 2 3 4 Clinker Silo To Storage and Distribution Quarry (RM 3) RM 1 RM 2 RM 4 RM 5 Proportioning Equipment Roller Mill Homogenizing Silo CKD Collector Primary Crusher PGNAA Coal Mill Finish Mill Clinker Cooler Preheater/Precalciner Main Emissions Stack 13 5 Broiler LitterPlastics 10 11 Tires 9 6 RM 6 7 12 8 14 KEY: RM ? Raw Material Emissions Fuels CKD Raw Materials/Clinker/Cement Sample Pointi Rotary Kiln 10 8 109 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, or Raw Material Seven. After the kiln feed has been 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 is added to the raw materials, a sample was collected at Sample Point 12 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 3.6. 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. Figure 3.5: Kiln Feed Sampling Figure 3.6: Sampling of Clinker 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. Additionally, 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 14 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. Figure 3.7: Automated Plunger Removing Coal Samples 112 The broiler litter and plastics utilize an injection point just above the tires?, and are inserted using a conveyor and screw system as shown in Figure 3.10. The tires, plastics, and broiler litter were sampled at Sample Points Nine, Ten, and Eleven 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. The plastics and broiler litter 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 Figure 3.10: Plastics and Broiler Litter Kiln Injection System Conveyor Screw 114 Once the clinker has been 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 3.11. 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 115 3.3.2 Sample Preparation, Shipping, and Storage Once all of the samples were collected for a given sampling period, the samples had to be prepared for shipping and/or testing. All of the typical containers that were filled with samples were each emptied into two-gallon, heavy-duty, plastic bags, which were 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 following the same path. This method was used in order 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. 116 Approximately two kilograms of each sample were stored in a cool, dry place indefinitely. All of the specimens that were tested by the cement plant did not require preparation by staff from Auburn University. 3.3.3 Analyzing the Chemical Composition of Raw Materials There were seven raw materials that were tested in all. Each of the particular raw materials? source and name 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, 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, were 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 period. 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 117 sampling for raw material six was one discrete sample collected during the grinding 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 four 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 period. 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 118 were made into individual composite specimens to be tested by the external laboratory alone. Tires were sampled once during each burn period in which they were used. Sampling of the two 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, a proximate and an ultimate analysis were conducted on each sample. Table 3.3 shows a detailed list of the data collected in each of these analyses. In addition to the proximate and ultimate analysis, 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, or broiler litter. For the coal, the cement plant conducted the same tests as the external laboratory. Table 3.3: Proximate and Ultimate Analysis Details Proximate Analysis (wt. %) Ultimate Analysis (wt. %) Moisture Hydrogen Ash Carbon Volatile Matter Nitrogen Fixed Carbon Sulfur Oxygen Ash Moisture 119 3.3.5 Analyzing the Chemical Composition of Cement Kiln Dust The cement kiln dust (CKD) was sampled two times per 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 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, 120 which was created in accordance with Section 3.3.2, using each of the twelve discrete samples collected during that day. 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 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. 121 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 content was determined on each of the daily composites using a total organic carbon (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. The tests performed by Auburn University were done so on a single composite specimen prepared over each of the burn periods. Table 3.4, Table 3.5, and Table 3.6 show the physical properties of cement tested by Auburn University, the cement plant, and the cement plant?s specialty laboratory, respectively. These tables also show the specifications and units used for each test. 122 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 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 Vicat Final Set Min C 191 Drying Shrinkage Development % C 596 Table 3.5: Cement Physical Property Tests Performed by Cement Plant Property Units ASTM Specification Air in Mortar % C 185 Blaine Specific Surface Area m2/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 Vicat Final Set Min C 191 Table 3.6: Cement Physical Property Tests Performed by Cement Plant Specialty Laboratory Property Units ASTM Specification Heat of Hydration 7 days kJ/kg C 186 Heat of Hydration 28 days kJ/kg C 186 Particle Size Distribution N/A Laser Diffraction 123 3.3.9 Analyzing the Properties of Concrete For each of the burn periods, 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 the first 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 period using the 5- gallon 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. 124 Table 3.7: Mix A Proportions Water 273 lbs/yd3 4.38 ft3 Cement (Type I) 620 lbs/yd3 3.15 ft3 Coarse Aggregate (# 57 Crushed Limestone) 1,900 lbs/yd3 10.61 ft3 Fine Aggregate (Natural River Sand) 1,272 lbs/yd3 7.78 ft3 Air 4.0 % 1.08 ft3 Air-Entraining Admixture 1.2 oz/yd3 0.00 ft3 0.44 Total Volume 27.00 ft 3 Mixture Properties Water/Cement ratio: 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. Table 3.9 shows the tests conducted by both entities, as well as those conducted only by Auburn University. The specification associated with each test is also shown. 125 Table 3.8: Mix B Proportions Water 260 lbs/yd3 4.17 ft3 Cement (Type I) 705 lbs/yd3 3.59 ft3 Coarse Aggregate (#78 CrushedLimestone) 1,942 lbs/yd3 11.36 ft3 Fine Aggregate (Natural River Sand) 1,115 lbs/yd3 6.79 ft3 Air 4.0 % 1.08 ft3 Water-Reducing Admixture 14.1 oz/yd3 0.01 ft3 Air-Entraining Admixture 1.8 oz/yd3 0.00 ft3 0.37 Total Volume = 27.00 ft 3 Mixture Properties Water/Cement ratio: VolumesMaterials Item The typical concrete mix at Auburn University was made by preparing enough material, in the proportions shown in Table 3.7 or Table 3.8, to produce seven cubic feet 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. 126 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. The emissions that were monitored from the main stack were carbon monoxide (CO), nitrogen oxides (NOx), sulfur dioxide (SO2), and volatile organic compounds (VOC). 3.4 Conclusion The test procedure described in the previous sections was developed to provide the most thorough data possible regarding the effects of the alternative fuels on the 127 production process, as well as on the products themselves. All materials involved in the 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 variances 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. 128 Chapter 4 Presentation and Analysis of Data 4.1 Introduction This chapter presents the collected data along with an analysis and discussion of these results. The data pertaining to each material tested follow the same order utilized in Chapter Three. For the discussion of each material, there are three goals: presentation of data, analysis of data, and discussion of results. For each material, the results presented by the various testing agencies are discussed separately. Comparisons are made between testing agencies when it is determined to be necessary. The first task of this chapter is simply to present the data pertaining to each test or parameter for that material. When there are ten or more data points for a set of results, a complete set of summary statistics are given. 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. The latter statistic is given in the form of a P- value based on Anderson-Darling statistics. 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.3. The second task of this chapter is to provide an analysis of the data. In this section, graphical representations are presented showing the difference in means between 129 each of the burns relative to the primary burn, which is the coal plus tires burn (Burn Two). Burn Two was chosen as the burn to which all other burns are compared because the cement plant burns coal and tires during normal operation. In addition to the graphs, when there are more than ten data points, a table is shown that indicates whether or not any changes in means were statistically significant. A P-value is presented that serves as the indicator for statistical significance. The limiting P-value used for determination of statistical significance was selected to be 0.10. This was done because the sample sizes for all materials except emissions were considered to be small to very small. Any P- value above this limiting value will signify that the difference in means for that specific result is not statistically significant. The final task of this chapter is discussion of 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. Finally, this task compares the parameters that are significantly changed to effects reported in the literature review. Where applicable, 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 two alternative fuels. It was the goal of this study to produce portland cement using both recycled industrial plastics and broiler litter. The implementation of these alternative fuels is a complex endeavor for the cement plant. Because of this fact, the broiler litter test was not completed within the timeframe necessary for the results to be presented and discussed in this document. Therefore, only data pertaining to Burn One, Burn Two, and Burn Three 130 are presented. However, this study will continue, and the data associated with the broiler litter burn will be presented in future documentation related to this project. 4.2 Research Conditions Each of the test burn periods lasted a total of three days. Considerable time elapsed between each burn period, 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 were changed relative to each burn, in order to assure maximum production. Some of these aspects that were variable were the kiln feed rate, fuel feed rates, and production rates. Since these aspects of the production process are proprietary information, the ranges for each of these parameters are given, instead of the averages. Burn One utilized coal as the only fuel, and was conducted between 7 AM on April 18, 2006 and 7 AM on April 21, 2006. The kiln feed rate for Burn One was between 250 and 310 tons per hour. The total coal feed rate was between 18 and 20 tons per hour. Finally, the clinker production rate for Burn One was between 160 and 200 tons per hour. Burn Two utilized coal and tires as fuel, and was conducted between 7 AM on July 11, 2006 and 7 AM on July 14, 2006. The kiln feed rate during Burn Two was between 90 and 330 tons per hour. The total coal feed rate was between 10 and 20 tons per hour. The total tire feed rate was between 0.03 and 1.4 tons per hour. These rates correspond to between a 1 and 10 percent tire-to-fuel replacement rate on an energy 131 basis. The rate of tire replacement was controlled by the development of sulfur build-ups which limited airflow within the system. The clinker rates for this burn period were between 100 and 200 tons per hour. Burn Three utilized coal, tires, and recycled post-industrial plastics as the fuel, and was conducted between 7 AM on April 3, 2007 and 7 AM on April 6, 2007. The kiln feed rate during Burn Three was between 260 and 330 tons per hour. The total coal feed rate was between 10 and 20 tons per hour. The tire feed rate was between 0.3 and 4 tons per hour. This results in a tire-to-fuel replacement rate of 2 to 8 percent, on a heat replacement basis. Just as with Burn Two, this rate was controlled by the development of sulfur build-ups in the system. The feed rate for the plastics was between 2.5 and 3.5 tons per hour. This rate was found to be controlled by the low density of the plastics, and the ability of the equipment at the cement plant to handle it. Finally, the clinker rates for Burn Three were between 170 and 240 tons per hour. 4.3 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 collected or tested at the cement plant. 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. 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 132 most cases. This was done because the major parameters were determined by both the cement plant and the external laboratory. Finally, specialty laboratory results (SLR) are those that were collected at the cement plant?s specialty laboratory. In all tables that present summary statistics, the abbreviation C.V. stands for coefficient of variation. It is calculated by dividing the standard deviation of the data set by the average, and is reported as a percentage. In addition, as the normality P-value decreases, the coefficient becomes less meaningful. 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. In the tables where a percent difference is given, this statistic is abbreviated as % Diff. This difference is relative to the results of the coal plus tires burn, from the testing agency in question. For instance, in any given table of results as presented by the cement plant, the percent difference is relative to the coal plus tires, as reported by the cement plant. If the data were reported by the external laboratory, the percent difference is relative to the coal plus tires burn, as reported by the external laboratory. Summary statistics will not include the coefficient of variation or the P-value relative to normality for data sets which contain less than ten data points. The same limit will be utilized for determining statistically significant differences relative to Burn Two. Even though statistical significance will not be reported for such small data sets, a graphical representation of percent difference between means relative to Burn Two will be given. These percent difference plots may show the results from different testing agencies. Once again, these differences are relative to the coal plus tires burn as reported by the testing agency in question. In the plots of percent difference for chemical 133 . compositions, the same set of major parameters will be 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 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. Table 4.1 shows the results of the chemical analysis conducted by the cement plant on Raw Materials One, Two, and Three. Table 4.2 shows the results of the chemical analyses conducted by the external laboratory on the same three raw materials. Table 4.3 and Table 4.4 show the chemical composition of Raw Materials Four, Five, and Six for the cement plant and the external laboratory, respectively. Table 4.1: CPR - Chemical Composition of Raw Materials One, Two, and Three Burn 1 Burn 2 Burn 3 Burn 1 Burn 2 Burn 3 Burn 1 Burn 2 Burn 3 Al 2 O 3 25.80 22.80 23.22 0.33 0.30 0.39 2.68 3.16 2.98 CaO 3.95 4.38 4.27 54.00 54.10 52.85 41.54 40.94 41.59 Fe 2 O 3 10.20 9.27 14.41 0.14 0.17 0.00 1.63 1.43 1.30 K 2 O 2.57 2.08 2.15 0.07 0.01 0.07 0.18 0.17 0.26 MgO 1.21 1.09 2.21 1.15 0.95 0.97 3.50 3.48 3.29 Na 2 O 0.38 0.40 0.42 0.00 0.00 0.03 0.01 0.07 0.10 SiO 2 43.70 44.90 43.03 0.96 0.85 2.04 14.00 14.35 13.77 SO 3 0.66 1.21 0.13 0.18 1.05 0.10 0.12 0.14 0.15 Moisture 9.07 19.81 34.60 5.80 1.80 3.00 NC NC NC LOI 9.07 11.63 7.10 43.18 42.47 43.20 NC NC NC Notes: NC - Not Collected Raw Material One Raw Material Two Raw Material Three Parameter (wt. %) 134 Table 4.2: ELR - Chemical Composition of Raw Materials One, Two, and Three Burn 1 Burn 2 Burn 3 Burn 1 Burn 2 Burn 3 Burn 1 Burn 2 Burn 3 Al 2 O 3 (wt. %) 24.76 24.07 26.87 0.19 0.07 0.87 3.23 5.32 8.09 CaO (wt. %) 2.95 2.74 3.20 50.49 54.92 91.85 43.00 36.02 43.79 Fe 2 O 3 (wt. %) 9.96 10.97 12.35 0.13 0.15 0.47 1.89 2.75 3.56 K 2 O (wt. %) 2.25 2.25 2.69 0.06 0.06 0.14 0.34 0.40 0.69 MgO (wt. %) 1.26 1.07 1.52 0.77 0.82 3.04 1.17 1.18 1.86 Na 2 O (wt. %) 0.53 0.55 0.60 0.00 0.03 0.47 0.00 0.08 0.11 P 2 O 5 (wt. %) 0.63 0.56 0.63 0.01 0.00 0.01 0.03 0.06 0.04 SiO 2 (wt. %) 43.44 43.09 50.21 0.51 0.49 2.86 15.92 22.11 41.12 SO 3 (wt. %) 0.30 0.15 0.09 0.12 0.15 0.20 0.29 0.25 0.12 TiO 2 (wt. %) 1.15 1.10 1.37 0.01 0.00 0.00 0.23 1.04 0.43 Moisture (wt. %) 17.71 23.67 22.26 2.54 0.02 2.93 4.53 0.34 6.51 LOI (wt. %) 12.77 13.44 11.99 47.72 43.32 42.91 33.93 30.78 27.56 As (ppm) 173 137 299 ND ND 6 7 18 23 Ba (ppm) 1867 1510 2000 68 88 300 316 293 300 Cd (ppm) ND ND NR ND ND NR ND ND NR Cl (ppm) 23 125 25 24 265 29 42 158 34 Co (ppm) 43 45 64 ND ND 12 26 ND 15 Cr (ppm) 139 135 203 ND ND 16 62 40 54 Cu (ppm) 269 200 219 ND ND 18 21 ND 46 Hg (ppm) 0.07 0.01 NR 0.01 0.03 NR 0.04 0.03 NR Mn (ppm) 280 302 1000 24 18 300 801 96 1200 Mo (ppm) ND ND 40 ND ND 12 ND ND 13 Ni (ppm) 112 114 122 ND ND 14 ND 21 16 Pb (ppm) 63 67 195 12 12 4 17 47 27 Sb (ppm) 20 ND NR 32 80 NR 82 30 NR Se (ppm) 3 3 NR 1 ND NR 1 ND NR Sr (ppm) 1432 1373 1800 172 225 400 240 259 400 V (ppm) 303 271 325 ND ND 17 49 103 74 Zn (ppm) 84 150 363 ND 24 26 27 90 52 Notes: ND - Not Detected NR - Not Reported Raw Material Three Property Raw Material One Raw Material Two Raw Material Three was not tested using XRF at the cement plant. This analysis was done using a Prompt Gamma Neutron Activation Analyzer (PGNAA). This is the reason for there not being results for moisture and loss on ignition for this raw material. 135 For a more thorough discussion of the chemical analysis of the raw materials, see Section 3.3.1. Table 4.3: CPR - Chemical Composition of Raw Materials Four, Five, and Six Burn 1 Burn 2 Burn 3 Burn 1 Burn 2 Burn 3 Burn 1 Burn 2 Burn 3 Al 2 O 3 4.22 6.28 7.60 1.79 0.76 1.14 0.87 1.87 2.62 CaO 28.90 35.10 38.10 0.87 2.16 1.66 36.80 29.10 32.57 Fe 2 O 3 34.70 25.00 14.50 1.72 1.45 1.63 0.45 0.30 0.25 K 2 O 0.19 0.02 0.05 0.32 0.16 0.28 0.11 0.19 0.25 MgO 8.80 10.40 12.90 0.08 0.19 0.19 1.05 1.40 3.15 Na 2 O 0.00 0.00 NR 0.03 0.00 NR 0.00 0.00 0.20 SiO 2 15.40 16.50 24.60 93.70 92.20 95.90 3.98 8.14 13.56 SO 3 1.27 0.60 0.41 0.38 1.12 0.21 44.40 41.67 34.95 Moisture 8.00 4.46 6.50 7.70 4.30 3.40 12.30 8.70 10.40 LOI 2.99 1.84 0.10 0.48 1.56 0.40 12.24 17.63 11.40 Notes: Parameter (wt. %) Raw Material Four Raw Material Five Raw Material Six NR - Not Reported 136 Table 4.4: ELR - Chemical Composition of Raw Materials Four, Five, and Six Burn 1 Burn 2 Burn 3 Burn 1 Burn 2 Burn 3 Burn 1 Burn 2 Burn 3 Al 2 O 3 (wt. %) 3.64 3.90 4.27 1.47 1.92 1.00 1.22 0.76 2.71 CaO (wt. %) 5.57 31.68 29.01 0.19 0.37 0.41 33.31 30.90 38.80 Fe 2 O 3 (wt. %) 52.83 40.25 34.03 0.91 1.17 0.59 0.74 0.25 0.50 K 2 O (wt. %) 0.79 0.03 0.20 0.43 0.25 0.17 0.13 0.16 0.26 MgO (wt. %) 1.66 11.95 12.16 0.30 0.19 0.18 1.50 0.62 2.78 Na 2 O (wt. %) 0.20 0.03 0.13 0.00 0.07 0.04 0.03 0.06 0.16 P 2 O 5 (wt. %) 0.56 0.61 0.47 0.01 0.03 0.00 0.03 0.01 0.03 SiO 2 (wt. %) 13.51 12.37 15.27 95.59 94.77 97.37 5.93 4.58 13.21 SO 3 (wt. %) 0.69 0.20 0.30 0.25 0.01 0.00 38.60 41.90 41.23 TiO 2 (wt. %) 0.16 0.26 0.25 0.43 0.28 0.20 0.05 0.02 0.10 Moisture (wt. %) 12.49 0.31 6.01 4.31 4.20 2.29 2.09 0.80 4.06 LOI (wt. %) 20.39 ND -1.30 0.45 0.93 0.35 18.44 20.74 18.06 As (ppm) 6 ND 4 ND 7 4 ND ND < 2 Ba (ppm) 308 ND 200 131 ND 200 73 ND 300 Cd (ppm) 6 3 NR ND ND NR ND ND NR Cl (ppm) 114 238 100 43 59 13 7 105 30 Co (ppm) 38 ND 4 ND ND 5 ND ND 7 Cr (ppm) 285 2672 3249 ND ND 9 ND ND 32 Cu (ppm) 5452 61 23303336ND< 10 Hg (ppm) 0.01 0.05 NR 0.01 0.01 NR 0.09 0.09 NR Mn (ppm) 7919 19571 38700 153 78 200 340 82 1200 Mo (ppm) 18 72 90 ND ND 23 ND ND 23 Ni (ppm) 192 11 75 ND 22 < 5 ND 9 5 Pb (ppm) 450 13 21 40 8 9 8 21 23 Sb (ppm) ND 36 NR ND ND NR ND ND NR Se (ppm) 2 2 NR ND 1 NR 1 ND NR Sr (ppm) 127 169 200 50 122 100 573 566 800 V (ppm) 97 687 604 ND ND 20 ND ND 18 Zn (ppm) 6464 134 198 80 13 2 ND ND 8 Notes: ND - Not Detected Raw Material Four Raw Material Five Raw Material Six NR - Not Reported Property 137 Table 4.5 shows the percent change in each parameter for Raw Materials One, Two, and Three, as reported by the cement plant. Table 4.6 shows the percent change for the same raw materials as reported by the external laboratory. Table 4.7 and Table 4.8 show the percent change for Raw Materials Four, Five, and Six, as reported by the cement plant and the external laboratory, respectively. The percent changes for each burn are relative to Burn Two. Wherever a result was not reported by the cement plant, or the result was zero for Burn Two, a value of not applicable (NA) was reported in these tables. Table 4.5: CPR - Percent Change in Raw Materials One, Two, and Three Burn 1 Burn 3 Burn 1 Burn 3 Burn 1 Burn 3 Al 2 O 3 13.2 1.8 10.0 30.0 -15.2 -5.8 CaO -9.8 -2.5 -0.2 -2.3 1.5 1.6 Fe 2 O 3 10.0 55.4 -17.6 NA 14.0 -9.3 K 2 O 23.6 3.4 600.0 600.0 5.9 54.9 MgO 11.0 102.8 21.1 2.1 0.6 -5.5 Na 2 O -5.0 5.0 NA NA -85.7 47.6 SiO 2 -2.7 -4.2 12.9 140.0 -2.4 -4.0 SO 3 -45.5 -89.3 -82.9 -90.5 -14.3 9.5 Moisture -54.2 74.7 222.2 66.7 NA NA LOI -22.0 -39.0 1.7 1.7 NA NA Notes: Raw Material One Raw Material Two Raw Material Three NA - Not Applicable Percent Change Relative to Burn Two Parameter 138 Table 4.6: ELR - Percent Change in Raw Materials One, Two, and Three Burn 1 Burn 3 Burn 1 Burn 3 Burn 1 Burn 3 Al 2 O 3 2.9 11.63 179.7 1167.58 -39.3 52.02 CaO 7.8 16.79 -8.1 67.25 19.4 21.56 Fe 2 O 3 -9.2 12.59 -13.7 204.35 -31.4 29.32 K 2 O -0.3 19.32 -2.3 133.12 -16.2 71.10 MgO 18.4 42.52 -6.8 269.10 -1.2 57.16 Na 2 O -4.2 8.12 -100.0 1726.10 -100.0 39.41 P 2 O 5 11.3 11.78 NA NA -43.5 -34.82 SiO 2 0.8 16.51 4.7 484.84 -28.0 85.98 SO 3 106.8 -38.94 -15.9 37.13 20.0 -51.11 TiO 2 4.4 24.41 NA NA -78.4 -58.78 Moisture -25.2 -5.95 16649.6 19221.40 1250.9 1841.39 LOI -5.0 -10.77 10.2 -0.94 10.2 -10.45 As 26.5 118.25 NA NA -62.3 24.93 Ba 23.6 32.41 -23.4 239.49 8.0 2.45 Cd NA NA NA NA NA NR Cl -81.6 -80.00 -90.9 -89.06 -73.4 -78.48 Co -5.3 41.94 NA NA NA NR Cr 3.0 50.07 NA NA 52.6 33.90 Cu 34.4 9.34 NA NA NA NR Hg 600.0 NA -66.7 NA 33.3 NR Mn -7.3 231.40 33.2 1565.14 730.2 1144.35 Mo NA NA NA NA NA NR Ni -1.1 7.40 NA NA NA -23.96 Pb -6.1 192.06 -2.3 -66.70 -63.4 -42.97 Sb NA NA -59.9 NA 176.2 NR Se 34.0 NA NA NA NA NR Sr 4.3 31.05 -23.4 77.95 -7.2 54.67 V 12.1 20.13 NA NA -51.8 -27.86 Zn -44.2 141.99 NA 8.23 -70.3 -42.41 Notes: Percent Difference Relative to Burn Two Property Raw Material ThreeRaw Material One Raw Material Two NA - Not Applicable 139 Table 4.7: CPR - Percent Change in Raw Materials Four, Five, and Six Burn 1 Burn 3 Burn 1 Burn 3 Burn 1 Burn 3 Al 2 O 3 -32.8 21.0 135.5 50.0 -53.5 40.2 CaO -17.7 8.5 -59.7 -23.1 26.5 11.9 Fe 2 O 3 38.8 -42.0 18.6 12.4 50.0 -16.7 K 2 O 850.0 150.0 100.0 75.0 -42.1 31.6 MgO -15.4 24.0 -57.9 0.0 -25.0 125.0 Na 2 O NA NA NA NA NA NA SiO 2 -6.7 49.1 1.6 4.0 -51.1 66.6 SO 3 110.6 -32.0 -66.1 -81.3 6.6 -16.1 Moisture 79.4 45.7 79.1 -20.9 41.4 19.5 LOI 62.5 -94.6 -69.2 -74.4 -30.6 -35.3 Notes: Parameter Percent Change Relative to Burn Two Raw Material Six NA - Not Applicable Raw Material Four Raw Material Five Although the percent change of each parameter is presented for the raw materials, no conclusions can be drawn based on these data alone. The proportions of each material that were combined to produce the kiln feed were 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 has been reported. 140 Table 4.8: ELR - Percent Change in Raw Materials Four, Five, and Six Burn 1 Burn 3 Burn 1 Burn 3 Burn 1 Burn 3 Al 2 O 3 -6.7 9.48 -23.3 -47.90 61.5 257.71 CaO -82.4 -8.44 -48.5 11.08 7.8 25.55 Fe 2 O 3 31.2 -15.46 -21.9 -49.60 192.0 97.99 K 2 O 2465.4 549.56 68.8 -32.83 -15.1 64.73 MgO -86.1 1.79 56.3 -5.17 140.6 345.91 Na 2 O 555.0 322.21 -100.0 -45.81 -46.9 153.43 P 2 O 5 -7.0 -22.38 -62.5 -100.00 324.7 280.14 SiO 2 9.3 23.47 0.9 2.74 29.6 188.60 SO 3 253.3 53.84 2263.7 -100.00 -7.9 -1.59 TiO 2 -37.8 -2.57 50.1 -29.76 218.5 533.57 Moisture 3866.9 1808.83 2.7 -45.44 162.0 408.92 LOI NA NA -51.4 -62.17 -11.1 -12.94 As NA NA NA -45.81 NA NA Ba NA NA NA NA NA NA Cd 91.0NANANANANA Cl -52.1 -57.98 -27.1 -77.97 -93.3 -71.43 Co NA NA NA NA NA NA Cr -89.3 21.61 NA NA NA NA Cu 2426.4 183.02 -23.6 11.76 NA NA Hg -80.0 NA 0.0 NA 0.0 NA Mn -59.5 97.74 96.2 156.29 314.5 1362.09 Mo -74.3 25.27 NA NA NA NA Ni 1604.5 564.32 NA NA NA -47.20 Pb 3269.4 57.39 378.4 6.68 -64.6 7.94 Sb NA NA NA NA NA NA Se -18. NANANANANA Sr -25.1 18.10 -59.2 -18.25 1.3 41.38 V -85.8 -12.03 NA NA NA NA Zn 4707.4 47.27 528.4 -84.20 NA NA Notes: Property NA - Not Applicable Raw Material Four Raw Material Five Raw Material Six Percent Difference Relative to Burn Two 141 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, consisted of ten, twelve, and seven data points for Burns One, Two, and Three, respectively. Table 4.9 shows the summary statistics for each of the burns. Although Burn Three did not consist of ten or more data points, it was determined to be necessary to report all summary statistics due to the critical nature of the kiln feed to the overall production process. Table 4.9: CPR - Chemical Composition of Kiln Feed Average (wt. %) C.V. (%) P-Value Average (wt. %) C.V. (%) P-Value Average (wt. %) C.V. (%) P-Value Al 2 O 3 3.11 2.4 0.561 3.23 2.6 1 0.092 3.01 2.1 0.386 CaO 43.95 0.5 0.642 43.04 0.8 0.166 43.74 0.6 1 0.078 Fe 2 O 3 2.03 3.9 0.526 2.01 3.2 0.965 1.90 4.0 0.356 K 2 O 0.33 2.9 1 0.005 0.29 5.3 1 <0.005 0.28 1.7 1 <0.005 MgO 1.92 2.4 0.954 2.51 6.6 1 0.064 2.07 2.9 0.440 Na 2 O 0.04 14.4 1 0.008 0.10 18.6 0.238 0.04 17.8 1 0.021 Na 2 O eq 0.26 4.2 0.241 0.29 5.3 0.336 0.23 3.9 1 0.091 SiO 2 13.67 1.1 0.960 14.38 1.7 0.181 13.66 1.4 0.156 SO 3 0.29 12.4 0.502 0.29 12.1 0.611 0.11 18.3 0.223 LOI 36.59 0.4 0.430 35.05 1.2 0.249 34.72 0.7 0.183 Notes: 1 Data Not Normally Distributed Parameter Burn One Burn Two Burn Three Table 4.10 shows the percent change in chemical parameters in the kiln feed based on the cement plant data. All parameters exhibited a statistically significant change relative to the kiln feed used in Burn Two, except for Fe 2 O 3 and SO 3 from Burn One and K 2 O from Burn Three. 142 Table 4.10: CPR - Percent Change in Mean for Kiln Feed Percent Difference P-Value Significant Percent Difference P-Value Significant Al 2 O 3 -3.7 0.002 Yes -6.8 0.000 Yes CaO 2.1 0.000 Yes 1.6 0.000 Yes Fe 2 O 3 1.0 0.476 No -5.5 0.003 Yes K 2 O 13.8 0.000 Yes -3.4 0.130 No MgO -23.5 0.000 Yes -17.5 0.000 Yes Na 2 O -60.0 0.000 Yes -60.0 0.000 Yes Na 2 O eq -10.3 0.000 Yes -20.7 0.000 Yes SiO 2 -4.9 0.000 Yes -5.0 0.000 Yes SO 3 0.0 0.983 No -62.1 0.000 Yes LOI 4.4 0.000 Yes -0.9 0.071 Yes Parameter Burn One Burn Three The kiln feed was analyzed by the external laboratory in the form of a single composite sample collected during each burn period. Table 4.11 shows the results of the XRF scan conducted by the external laboratory, along with the relative differences between the burns. Burn One showed a number of parameters that exhibited a percent change greater than ten percent relative to Burn Two. These parameters, in decreasing order of the absolute value of percent change are: Na 2 O, Moisture, SO 3 , P 2 O 5 , SiO 2 , TiO 2 , K 2 O, Fe 2 O 3 , and Al 2 O 3 . The results from Burn Three showed a very different trend than the same burn as reported by the cement plant. Each of the major param showed an increase of more than 15 percent relative to Burn Two. The only exceptions were Na eters 2 O, moisture, and LOI. The apparent complete change in chemical composition of the kiln feed for Burn Three was most likely purposefully done by the cement plant. 143 Table 4.11: ELR - Chemical Composition of Kiln Feed 144 A Burn Two Value (wt. %) % Diff. Value (wt. %) Value (wt. %) % Diff. Al 2 O 3 3.04 10.5 2.75 4.91 78.5 CaO 44.17 9.8 40.23 65.27 62.2 Fe 2 O 3 2.15 12.0 1.92 3.01 56.8 K 2 O 0.32 10.3 0.29 0.50 72.4 MgO 1.90 -8.7 2.08 3.35 61.1 Na 2 O 0.01 -66.7 0.03 0.01 -66.7 P 2 O 5 0.05 25.0 0.04 0.07 75.0 SiO 2 13.37 -21.4 17.00 21.87 28.6 SO 3 0.35 45.8 0.24 0.34 41.7 TiO 2 0.17 -15.0 0.20 0.24 20.0 Moisture 0.06 -66.7 0.18 0.10 -44.4 LOI 34.44 -2.1 35.18 34.67 -1.4 Value (ppm) % Diff. Value (ppm) Value (ppm) % Diff. As 2 -83.3 12 18 50.0 Ba 191 -25.4 256 400 56.3 Cd ND NA ND NR NA Cl 111 46.1 76 63 -17.1 Co ND NA 20 14 -30.0 Cr 51 -15.0 60 86 43.3 Cu 42 NA ND 41 NA Hg 0 NA 0 NR NA Mn 664 110.1 316 1700 438.0 Mo ND NA ND 16 NA Ni ND NA 14 12 -14.3 Pb 23 155.6 9 < 4 NA Sb 32 -63.2 87 NR NA Se 0NAND Sr 260 13.5 229 500 118.3 V 39 -18.8 48 73 52.1 Zn 112 5.7 106 37 -65.1 Notes: ND - Not Detected NA - Not Applicable Parameter Burn One Burn Three 145 Figure 4.1 shows a plot of the percent difference for the primary parameters, as reported by both testing agencies. For each testing agency, the percent differences are relative to Burn Two as reported by that testing agency. The cement plant results show two parameters, MgO and Na 2 O, which showed a decrease of more than ten percent for Burn One and Burn Three. Additionally, K 2 O for Burn One also showed a change of more than ten percent. The greatest difference in kiln feed was in SO 3 for Burn Three. This parameter exhibited a decrease of more than 60 percent. Figure 4.1 shows just how dramatic the changes were between Burn Three and Burn Two for the results from the external laboratory. The results from the external laboratory for Burn One were much less dramatic. The only parameters between these burns that showed a large change were Na 2 O with a 70 percent decrease, and SO 3 with a 48 percent increase. The reasons for the changes in chemical composition of the kiln feed can be many. One primary explanation is that the cement plant changed the composition purposely in order to assist in the production process. For instance, a change in many different parameters may result in more efficient conversion from kiln feed to clinker. An additional explanation may be that a change in composition of the kiln feed may result in a significant change in emissions properties. Since the composition of the kiln feed is closely monitored and adjusted by the cement plant, modifications to blending of raw materials are made with a purpose. -80 -60 -40 -20 0 20 40 60 80 100 Percent Differen c e in Mean Relative to B urn Two CPR - Burn One CPR - Burn Three ELR - Burn One ELR - Burn Three Al 2 OSO 3 SiO 2 Na 2 OMgOK 2 OFe 2 O 3 CaO 146 Figure 4.1: Percent Changes in Mean for Kiln Feed Relative to Burn Two 147 4.3.3 Chemical Composition of Fuel Sources Pulverized coal is the primary fuel used to produce clinker from the kiln feed at the cement plant. A proximate, ultimate, and combustion analysis 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 discrete sample during each burn period. The results of these tests, along with the percent differences for Burn One and Burn Three relative to Burn Two are presented in Table 4.12. The parameters in the Burn One coal which showed the greatest increase relative to Burn Two were oxygen, Na 2 O, and SO 3 , which showed increases of 42, 26, and 13 percent, respectively. The parameters showing the greatest decrease between these two burns were sulfur and MgO, which showed decreases of 31 and 21 percent, respectively. Overall, the chemical composition of the coal used during Burn One, and the coal used during Burn Two were reasonably similar. Unfortunately, the coal source used by the cement plant was changed between Burn Two and Burn Three. This decision was made with production and economic issues in mind. The result of this new coal source can be seen in the percent differences between Burn Three and Burn Two, as shown in Table 4.12. The parameters showing the greatest change were sulfur and Fe 2 O 3 , which increased by 149 and 481 percent, respectively. Table 4.12: CPR - Chemical Analysis and Percent Difference for Coal Burn Two Value (wt. %) % Diff. Value (wt. %) Value(wt. %) % Diff. Ash 18.9 6.1 17.82 23.43 31.5 Fixed Carbon 50.17 -3.6 52.05 48.43 -7.0 Volatile Matter 30.93 2.7 30.13 28.14 -6.6 Carbon 69.06 -3.0 71.17 64.41 -9.5 Hydrogen 4.25 -2.1 4.34 4.01 -7.6 Nitrogen 1.51 4.1 1.45 1.31 -9.7 Oxygen 5.22 41.5 3.69 3.05 -17.3 Sulfur 1.06 -30.7 1.53 3.79 147.7 Al 2 O 3 24.67 5.2 23.45 15.43 -34.2 CaO 13.32 4.6 12.74 3.23 -74.6 Fe 2 O 3 5.83 -6.6 6.24 36.24 480.8 K 2 O 1.97 -8.8 2.16 1.94 -10.2 MgO 1.18 -20.8 1.49 1.04 -30.2 Na 2 O 0.39 25.8 0.31 0.36 16.1 SiO 2 42.89 -7.2 46.21 36.17 -21.7 SO 3 8.36 12.8 7.41 4.4 -40.6 12102 -3.2 12506 11255 -10.0 Notes: 1 Value is Reported as BTU/lb Pr oxim at e Analysis Heat Value 1 Ult i ma te A n alysis Burn One Burn Three Test Parameter S t a n d a rd Pa r a m ete rs The tests conducted by the cement plant were also conducted by the external laboratory. However, the specimens that were tested by the external laboratory were composites prepared from six discrete samples collected throughout each of the burn periods. For this reason, the results presented by the external laboratory more accurately reflect the chemical composition of the coal over the entire burn phase. The results from the proximate, ultimate, and combustion analysis conducted by the external laboratory 148 are shown in Table 4.13. These results showed that the ash content of Burn One showed the largest increase relative to Burn Two. Just as was reported by the cement plant, the oxygen composition between Burn One and Burn Two showed a large increase; in this case it was 26 percent. Hydrogen and moisture showed the largest decrease between Burns One and Two, with decreases of 27 and 11 percent. As was expected, the results between Burns Three and Two showed dramatic differences in just about all parameters. The largest increases were for ash and sulfur. The largest decreases were between hydrogen and fixed carbon. Table 4.13: ELR ? Proximate, Ultimate, and Combustion Analysis for Coal Burn Two Value (wt. %) % Diff. Value (wt. %) Value(wt. %) % Diff. Ash 22.45 34.1 16.74 24.54 46.6 Fixed Carbon 49.58 -9.5 54.81 47.68 -13.0 Volatile Matter 27.97 -1.7 28.45 27.78 -2.4 Carbon 67.61 -7.5 73.09 64.68 -11.5 Hydrogen 3.61 -22.5 4.66 3.93 -15.7 Nitrogen 1.1 -9.8 1.22 1.08 -11.5 Oxygen 3.95 25.8 3.14 4.11 30.9 Sulfur 1.28 11.3 1.15 1.66 44.3 11698 1 -7.3 12624 1 11369 1 -9.9 Notes: 1 Value is Reported as BTU/lb Pr oxim at e Ana lysis Burn Three Test Parameter Burn One Ul ti ma te An a l y s i s Heat Value 1 In addition to the results shown in Table 4.13, the standard external laboratory parameters for the coal, along with the differences relative to Burn Two, are shown in 149 150 Table 4.14. All of these results were determined by XRF. Two different sets of units were used to report these data. The primary parameters, those that showed a more prominent presence, are reported as a percent of the total weight, while the less prominent parameters were reported as parts per million (ppm). The parameters that showed a presence less than the detection limit of the XRF are reported as not detected (ND). The majority of the standard parameters shown in Table 4.14 were determined on the ash of the fuel. Select parameters could only be determined on the dry coal. In such cases, this is noted. The results presented in Table 4.14 show primary parameters for the coal from Burns One and Two to be reasonably similar. Na 2 O and P 2 O 5 were the only parameters that showed a change of more than ten percent. Of the less prominent parameters, the arsenic showed the greatest change between Burns One and Two. However, since the composition of the arsenic in Burn Two was only 80 ppm, it is difficult to determine whether this difference is practically significant. Cl, Cu, Mn, and Zn also showed large changes between Burns One and Two. Just as with the results already presented for the coal from Burn Three relative to the coal from Burn Two, Table 4.14 shows large differences in most parameters. Of the primary parameters, Fe 2 O 3 showed the greatest difference, with an increase of over 100 percent. The less prominent parameters mostly showed large changes as well, most notable were Mn and Mo, both of which showed an increase of more than 300 percent. Figure 4.2 presents the percent change in the primary parameters from both testing agencies. Fe 2 O 3 is not shown simply because of the large percent difference from the cement plant concerning Burn Two, relative to the other parameters. Table 4.14: ELR ? Standard Parameters for Coal Burn Two Value (wt. %) % Diff. Value (wt. %) Value (wt. %) % Diff. Al 2 O 3 25.07 -1.8 25.53 21.04 -17.6 CaO 7.52 -5.6 7.97 8.25 3.5 Fe 2 O 3 7.60 3.4 7.35 15.16 106.3 K 2 O 2.57 -3.4 2.66 2.49 -6.4 MgO 1.35 0.7 1.34 1.25 -6.7 Na 2 O 0.22 -47.6 0.42 0.36 -14.3 P 2 O 5 0.18 -10.0 0.20 0.23 15.0 SiO 2 47.39 3.0 46.01 43.44 -5.6 SO 3 6.95 -5.2 7.33 6.5 -11.3 TiO 2 1.12 -2.6 1.15 0.96 -16.5 Value (ppm) % Diff. Value (ppm) Value (ppm) % Diff. As 325 306.3 80 315 293.8 Ba 1273 17.5 1083 1300 20.0 Cd ND NA ND 5 1 NA Cl 125 1 -31.3 182 134 1 -26.4 Co ND NA 29 43 48.3 Cr 109 -14.2 127 116 -8.7 Cu 150 29.3 116 102 -12.1 Hg < 1 NA ND < 1 NA Mn 220 -38.0 355 1500 322.5 Mo ND NA 9 39 333.3 Ni 80 -19.2 99 92 -7.1 Pb 41 -12.8 47 45 -4.3 Sb ND NA ND NR NA Se ND NA 8 1 1 -87.7 Sr 487 -17.5 590 500 -15.3 V 225 0.0 225 214 -4.9 Zn 67 -49.6 133 197 48.1 ND - Not Detected NA - Not Applicable NR - Not Reported 1 Dry Basis Notes: Burn Three St andar d Par a m e t e r s Test Parameter Burn One 151 -80 -60 -40 -20 0 20 40 Percent Difference in Mea n Rela tiv e to B u rn Two CPR - Burn One CPR - Burn Three ELR - Burn One ELR - Burn Three Al 2 OSO 3 SiO 2 Na 2 OMgOK 2 OCaO 152 Figure 4.2: Percent Differences in Coal Relative to Burn Two 153 The second fuel that was used at the cement plant was whole tires. These tires are not tested for their chemical composition by the cement plant. They were however, sampled by Auburn University, and tested by the external laboratory. The samples were collected by removing approximately eight tires from the feed stream, reducing a section of each to one inch squares, and making a single composite specimen from the pieces. One composite sample, 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, are shown in Table 4.15. The percent difference between the tires used in Burn Three and the tires used in Burn Two are also shown. Overall, there was a relatively large difference in many of the parameters. Oxygen and moisture showed the greatest decreases, while nitrogen, sulfur, and heat content 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. Table 4.16 shows the standard external laboratory parameters for the tires. Every primary parameter except for Fe 2 O 3 showed a decrease. Of those which decreased, all but Al 2 O 3 and MgO showed decreases of more than 28 percent. Most of the less prominent parameters also showed substantial changes. Once again, these differences are most likely simply due to the variability in the actual tire feed stream. Table 4.15: ELR - Proximate, Ultimate, and Combustion Analysis for Tires Burn Two Value (wt. %) Value (wt. %) % Diff. Ash 13.72 14.56 6.1 Fixed Carbon 24.6 26.38 7.2 Moisture 1 0.14 0.07 -50.0 Volatile Matter 61.68 59.06 -4.2 Carbon 72.34 75.94 5.0 Hydrogen 7.05 6.53 -7.4 Nitrogen 0.36 0.52 44.4 Oxygen 4.98 0.46 -90.8 Sulfur 1.54 2.00 29.9 14467 14687 1.5 Notes: 1 As Received 2 Values Reported as BTU/lb Heat Value 2 Test Parameter Proximate An alysis Ultima te Analysis Burn Three 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. Figure 4.3 shows the percentage of the total fuel consumed that is tires. This percentage was calculated using the average heat value of the fuels (reported from each burn period) 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. The data reported in Figure 4.3 is a 30-minute rolling average, reported over each of the 72-hour burn periods in which tires were used. Where data were not reported by the cement plant, gaps in the plots are shown. The average tire replacement rate during Burn Two was 6.5 percent. The average replacement rate during Burn Three was 4.8 percent. The lower rate for Burn Period Three was due to the fact that a portion of the coal was also replaced by the plastics. 154 Table 4.16: ELR - Standard Parameters for Tires 155 50. Burn Two Value (wt. %) Value (wt. %) % Diff. Al 2 O 3 1.18 1.15 -2.5 CaO 2.36 1.68 -28.8 Fe 2 O 3 68.64 84.72 23.4 K 2 O 0.33 0.17 -48.5 MgO 0.35 0.33 -5.7 Na 2 O 0.31 0.19 -38.7 P 2 O 5 0.21 0.12 -42.9 SiO 2 16.87 4.91 -70.9 SO 3 2.64 0.51 -80.7 TiO 2 0.20 0.01 -95.0 Value (ppm) Value (ppm) % Diff. As (ppm) NR NR NA Ba (ppm) 300 300 0.0 Cd (ppm) 1 63- Cl (ppm) 1 405 NR NA Co (ppm) 616 536 -13.0 Cr (ppm) 118 178 50.8 Cu (ppm) 1398 900 -35.6 Hg (ppm) 1 0.4 0 NA Mn (ppm) 4100 5200 26.8 Mo (ppm) 28 23 -17.9 Ni (ppm) 367 239 -34.9 Pb (ppm) 11 13 18.2 Sb (ppm) NR NR NA Se (ppm) 1 < 1 < 1 NA Sr (ppm) 200 100 -50.0 V (ppm) 37 50 35.1 Zn (ppm) 54000 48400 -10.4 Notes: NR - Not Reported ND - Not Detected NA - Not Applicable 1 Dry Basis Stan d a rd Parameters Burn Three Test Parameter 0 3 6 9 12 15 18 21 24 27 0 8 16 24 32 40 48 56 64 72 Time (hrs) Alt. Fuel to T o ta l Fuel Replacement Ra te (%) Burn Two - Tires (Avg. = 6.5) Burn Three - Tires (Avg. = 4.8) Burn Three - Plastics (Avg. = 16.9) 156 Figure 4.3: Alternative Fuel to Total Fuel Substitution Rate by Heat Equivalency Basis The plastics used in Burn Three were 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 4.17. Table 4.18 shows the summary statistics which apply to the standard external laboratory parameters for the plastics. Perhaps the most interesting result was the extremely high concentration of CaO in the plastics, which composed 92 percent of the total weight. Table 4.17: ELR ? Proximate, Ultimate, and Combustions Analysis of Plastics for Burn Three 157 Test Parameter Average C.V. (%) P-Value 2 Ash (wt. %) 8.75 40.8 1 0.013 Fixed Carbon (wt. %) 2.95 43.9 1 0.026 Moisture (wt. %) 0.32 40.5 1 0.026 Volatile Matter (wt. %) 88.30 2.7 1 <0.005 Carbon (wt. %) 64.23 13.1 1 <0.005 Hydrogen (wt. %) 8.06 18.4 1 <0.005 Nitrogen (wt. %) 1.27 31.6 0.888 Oxygen (wt. %) 17.46 49.3 1 <0.005 Sulfur (wt. %) 0.22 185.6 1 <0.005 12754 7.9 0.313 Notes: 1 Not Normally Distributed 3 As Received 2 Based on Anderson-Darling Statistics 4 Value is as BTU/lb Proximate Analysis Ul ti mate An alysis Heat Value 4 Table 4.18: ELR - Standard Parameters of Plastics for Burn Three Test Parameter Average (wt. %) C.V. (%) P-Value 2 Al 2 O 3 0.48 59.8 1 <0.005 CaO 92.00 2.0 1 0.034 Fe 2 O 3 0.54 25.8 1 0.041 K 2 O 0.13 40.4 1 <0.005 MgO 1.75 4.2 0.727 Na 2 O 0.17 91.9 1 <0.005 P 2 O 5 0.14 41.3 0.429 SiO 2 2.12 34.6 1 <0.005 SO 3 0.41 30.5 0.116 TiO 2 1.77 46.8 0.177 Parameter Average (ppm) C.V. (%) P-Value 2 As 62 62.7 1 0.067 Ba 4100 47.1 0.518 Cd 7 3 9.3 1 <0.005 Cl 54 3 25.8 1 <0.005 Co 142 27.8 0.113 Cr 356 33.0 0.504 Cu 369 28.4 0.279 Hg <0.001 3 NA NA Mn 300 20.9 1 <0.005 Mo 6 172.3 0.144 Ni 50 165.2 1 <0.005 Pb 628 59.6 1 0.009 Sb NR NA NA Se < 1 3 NA NA Sr 600 8.8 1 <0.005 V 66 83.8 1 <0.005 Zn 283 50.0 0.275 Notes: NR - Not Reported 1 Not Normally Distributed NA - Not Applicable 2 Based on Anderson-Darling Statistics 3 Dry Basis St andar d Par a m e t e r s 158 159 Figure 4.3 shows the replacement rate of the plastics relative to the total amount of fuels consumed. 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 12,812 BTU/lb for the plastics, and 11,897 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 84.3 kg/m 3 . Table 4.19 shows the chemical composition of all of the fuels. 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 4.19 shows the heat value for each of the fuels. The tires used during Burn Three had the highest heat value, followed by the tires from Burn Two. The plastics had a higher heat value than any of the coal samples. Many differences between the fuels are shown in Table 4.19. The tires and the plastics contained very little Al 2 O 3 , but each of the coal samples was approximately 25 percent Al 2 O 3 . The plastics were over 90 percent CaO, whereas the coal and tires contained less than 10 percent. The Fe 2 O 3 was much higher in the tires than in the coal 160 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 4.19: ELR ? Chemical Composition of all Fuels Burn One Coal Coal Tires Coal Tires Plastics Al 2 O 3 (wt. %) 25.08 25.54 1.18 21.04 1.15 0.48 CaO (wt. %) 7.53 7.97 2.36 8.25 1.68 92.00 Fe 2 O 3 (wt. %) 7.61 7.35 68.64 15.16 84.72 0.54 K 2 O (wt. %) 2.58 2.67 0.33 2.49 0.17 0.13 MgO (wt. %) 1.35 1.34 0.35 1.25 0.33 1.75 Na 2 O (wt. %) 0.22 0.43 0.31 0.36 0.19 0.17 P 2 O 5 (wt. %) 0.18 0.20 0.21 0.23 0.12 0.14 SiO 2 (wt. %) 47.39 46.01 16.87 43.44 4.91 2.12 SO 3 (wt. %) 6.95 7.33 2.64 6.5 0.51 0.41 TiO 2 (wt. %) 1.12 1.15 0.20 0.96 0.01 1.77 As (ppm) 325 80 NR 316 NR 62 Ba (ppm) 1274 1083 300 1300 300 4100 Cd (ppm) 1 NDND6537 Cl (ppm) 1 125 182 405 134 NR 54 Co (ppm) ND 30 616 44 536 142 Cr (ppm) 109 127 118 117 178 356 Cu (ppm) 150 116 1398 103 900 369 Hg (ppm) 1 0ND0000 Mn (ppm) 221 355 4100 1500 5200 300 Mo (ppm) ND 9 28 39 23 6 Ni (ppm) 81 100 367 92 239 50 Pb (ppm) 42 48 11 45 13 628 Sb (ppm) ND ND NR NR NR NR Se (ppm) 1 ND 8 < 1 1 < 1 < 1 Sr (ppm) 487 591 200 500 100 600 V (ppm) 226 225 37 214 50 66 Zn (ppm) 68 133 0 197 0 283 11698 12624 14467 11369 16754 12754 Notes: ND - Not Detected NR - Not Reported 1 Dry Basis Burn Two Burn Three S t a n d ard Parameters Heat Value (BTU/lb) Test Parameter 161 4.3.4 Chemical Composition of Cement Kiln Dust The cement plant collected two cement kiln dust samples every day during each of the burn periods. Each of these samples was tested once for the standard cement plant parameters, except for moisture and loss on ignition. Table 4.20 shows the results of these tests, along with the percent differences of Burns One and Three relative to Burn Two. Table 4.20: CPR ? Chemical Analysis and Percent Difference for CKD Burn Two Value (wt. %) % Diff. Value (wt. %) Value (wt. %) % Diff. Al 2 O 3 3.69 -7.5 3.99 3.65 -8.5 CaO 47.54 6.4 44.69 47.63 6.6 Fe 2 O 3 1.81 -10.0 2.01 1.73 -13.9 K 2 O 0.48 14.3 0.42 0.38 -9.5 MgO 1.65 0.0 1.65 1.80 9.1 Na 2 O 0.07 -12.5 0.08 0.05 -37.5 SiO 2 11.68 -3.0 12.04 11.56 -4.0 SO 3 1.13 18.9 0.95 0.84 -11.6 S t an dard Parameters Parameter Burn One Burn Three Test The six cement kiln dust samples that were collected at the cement plant were also tested by the external laboratory. Once again, there were not enough data points to present a complete set of summary statistics. The averages and percent differences from the external laboratory are presented in Table 4.21. From this table one can see that many of the parameters showed a change of more than ten percent for Burns One and Three relative to Burn Two. 162 Table 4.21: ELR - Chemical Composition of Cement Kiln Dust 163 A Burn Two Value (wt. %) % Diff. Value (wt. %) Value (wt. %) % Diff. Al 2 O 3 3.76 1.3 3.71 5.11 37.7 CaO 56.32 20.4 46.77 72.01 54.0 Fe 2 O 3 2.00 -4.3 2.09 2.57 23.0 K 2 O 0.42 -25.0 0.56 0.46 -17.9 MgO 1.89 23.5 1.53 2.54 66.0 Na 2 O 0.01 0.0 0.01 0.08 700.0 P 2 O 5 0.05 25.0 0.04 0.06 50.0 SiO 2 11.32 2.3 11.07 15.70 41.8 SO 3 1.43 14.4 1.25 1.01 -19.2 TiO 2 0.21 0.0 0.21 0.25 19.0 Moisture 0.06 -72.7 0.22 0.13 -40.9 LOI 22.54 -30.7 32.54 33.25 2.2 Value (ppm) % Diff. Value (ppm) Value (ppm) % Diff. As 3 -83.3 18 29 61.1 Ba 278 -10.0 309 333 7.8 Cd ND NA ND NR NA Cl 482 716.9 59 131 122.0 Co 14 -12.5 16 13 -18.8 Cr 32 -27.3 44 54 22.7 Cu 49 226.7 15 47 213.3 Hg 0.02 NA < 0.01 NR NA Mn 315 87.5 168 883 425.6 Mo ND NA ND 16 NA Ni 11 -21.4 14 14 0.0 Pb 20 11.1 18 22 22.2 Sb 55 -5.2 58 NR NA Se 1-0.02 NRN Sr 320 9.2 293 533 81.9 V 54 10.2 49 64 30.6 Zn 91 -9.0 100 38 -62.0 Notes: NA - Not Applicable Parameter Burn One Burn Three ND - Not Detected 164 Some of the less prominent parameters are also a concern in the cement kiln dust. From Table 4.21 one can see that the Arsenic (As), which is a toxic element, was higher for both of the burns that used tires. It showed the greatest concentration in the burn that utilized both tires and plastics. It is also interesting to note that the chlorine (Cl) was over 700 percent higher in Burn One than in Burn Two, and about 600 percent higher than Burn Three. Cu and Mn also showed a large change in both Burns One and Three. Figure 4.4 shows a graphical representation of the percent differences in values from both the cement plant and the external laboratory, for the primary parameters. The result for Na 2 O is not shown, because of the difference between Burns Three and Two from the external laboratory relative to the rest of the percent differences. The primary point to notice is that the result from the external laboratory concerning Burn Three showed relatively large changes in all of the parameters. CaO and MgO showed an increase for all burns from both laboratories. The rest of the parameters do not consistently show the same relative change in the data obtained from both testing laboratories. -40 -20 0 20 40 60 80 Percent Difference in Mea n Rela tiv e to B u rn Two CPR - Burn One CPR - Burn Three ELR - Burn One ELR - Burn Three Al 2 OSO 3 SiO 2 Fe 2 O 3 MgOK 2 OCaO Figure 4.4: Percent Change in Means of CKD Relative to Burn Two 165 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. There were twelve samples collected per day by the cement plant. Each of these samples was tested for chemical composition. The results shown in Table 4.22 are the summary statistics from at least 36 discrete samples collected for each burn at the cement plant. Table 4.22: CPR - Summary Statistics of Chemical Composition of Clinker 166 Fe 2 O 3 3.41 6.6 1 0.012 3.35 4.7 0.289 3.56 6.1 1 <0.005 K 2 O 0.56 4.1 1 0.022 0.48 3.8 0.118 0.46 4.6 1 0.077 MgO 2.93 2.3 0.453 3.48 5.4 1 <0.005 3.25 3.3 0.589 Na 2 O 0.07 6.8 1 <0.005 0.10 9.6 1 <0.005 0.07 5.8 1 <0.005 Na 2 O eq 0.44 3.7 1 0.022 0.41 3.7 1 0.069 0.37 4.4 1 0.053 SiO 2 21.38 0.9 0.391 21.23 0.9 0.869 21.31 1.2 1 <0.005 SO 3 0.84 12.1 0.323 0.66 12.1 0.117 0.91 21.1 1 <0.005 Free CaO 1.10 37.1 0.605 1.06 38.8 1 <0.005 1.24 41.0 0.374 C 3 A 8.28 6.8 1 0.043 7.78 4.9 0.416 7.61 5.4 1 0.021 C 4 AF 10.37 6.7 1 0.009 10.21 4.7 0.206 10.86 6.2 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 C 2 S 14.90 16.6 0.742 13.91 13.2 0.602 14.96 16.4 1 0.007 Notes: 1 Data Not Normally Distributed 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 5.07 2.0 0.840 5.14 2.0 1 <0.005 CaO 64.96 0.4 0.116 64.48 0.2 0.908 64.55 0.6 1 0.039 Parameter Burn One Burn Two Burn Three Table 4.23 shows the percent difference of the means for Burns One and Three relative to the mean of Burn Two. 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. In most cases, there was a statistically significant difference between means. This does not mean they are practically significant, however. The parameters that did not show a statistically significant difference were Free CaO, C 4 AF, and C 3 S for Burn One, along with CaO and SiO 2 for Burn Three. One point worth noting is that the P-value for most of the Bogue compounds are above 0.03. This indicates that all of these compounds showed at least some statistical similarity. Selected differences presented in Table 4.23 are shown graphically in Figure 4.5. Table 4.23: CPR ? Percent Differences and Statistical Significance for Clinker Percent Difference P-Value Significant Percent Difference P-Value Significant Al 2 O 3 4.54 0.000 Yes 1.38 0.005 Yes CaO 0.74 0.000 Yes 0.11 0.310 No Fe 2 O 3 1.79 0.241 No 6.27 0.000 Yes K 2 O 16.67 0.000 Yes -4.17 0.000 Yes MgO -15.80 0.000 Yes -6.61 0.000 Yes Na 2 O -30.00 0.000 Yes -30.00 0.000 Yes Na 2 O eq 7.32 0.000 Yes -9.76 0.000 Yes SiO 2 0.71 0.001 Yes 0.38 0.135 No SO 3 27.27 0.000 Yes 37.88 0.000 Yes Free CaO 3.77 0.647 No 16.98 0.000 Yes C 3 A 6.43 0.000 Yes -2.19 0.086 Yes C 4 AF 1.57 0.253 No 6.37 0.000 Yes C 3 S -1.21 0.166 No -1.75 0.031 Yes C 2 S 7.12 0.055 Yes 7.55 0.042 Yes Parameter Burn One Burn Three 167 168 Based on the cement plant results, a few parameters showed large changes. There was a 27 percent and a 37 percent increase in SO 3 for Burns One and Three, respectively. Burn One showed a 26 percent decrease in Na 2 O, and Burn Three showed a 30 percent decrease in the same parameter. Other parameters from Burn One that showed changes greater than ten percent were K 2 O and MgO, which showed an increase of 16 percent and a decrease of 15.8 percent, respectively. Many of these notable changes in chemical composition are discussed with reference to the chemical changes present in the cement. From the discrete clinker samples collected at the cement plant, a single composite sample was prepared for each day during each burn period. Each of these composite samples was tested in duplicate for chemical composition by the external laboratory. Table 4.24 shows these results, along with the percent differences between burn periods. Of the less prominent parameters, both Cu and Ni showed an increase of more than 100 percent for Burn One. Mn exhibited the largest change during Burn Three, where it showed and increase of more than 200 percent. From Figure 4.5 it can be seen that the SO 3 showed an increase of at least 37 percent in each burn. Another large change was the Na 2 O. It showed a decrease of 70 percent for Burn One and an increase of over 100 percent for Burn Three. However, because the overall concentration of Na 2 O is so small, a small change in concentration results in a large percent change. K 2 O and MgO also showed a change of over ten percent for Burn Period One. The most significant result shown in Figure 4.5 is the percent change in Al 2 O 3 , CaO, Fe 2 O 3 , and SiO 2 . Each showed very little change between either of the burns from both the cement plant and the external laboratory. These results are significant because 169 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. After comparing the results from Table 4.19 and Table 4.24, it is very difficult to conclude that the chemical composition of the fuels directly impacts the chemical composition of the clinker. In fact, it appears as though the effect that the fuels directly have on the composition of the clinker is minimal with respect to the many other aspects of the production process that are designed to produce clinker with a consistent chemical composition. Perhaps the most important thing to conclude is that the four primary parameters of the clinker, Al 2 O 3 , CaO, Fe 2 O 3 , and SiO 2 , each showed no practically significant change, regardless of the fuel that was used. Table 4.24: ELR - Chemical Composition of Clinker Burn Two Value % Diff. Value Value % Diff. Al 2 O 3 5.26 4.57 5.03 4.96 -1.4 CaO 65.15 1.37 64.27 64.71 0.7 Fe 2 O 3 3.34 2.45 3.26 3.32 1.8 K 2 O 0.59 15.69 0.51 0.42 -17.6 MgO 2.88 -18.41 3.53 3.40 -3.7 Na 2 O 0.01 -75.00 0.04 0.10 150.0 P 2 O 5 0.08 33.33 0.06 0.07 16.7 SiO 2 21.23 -2.93 21.87 21.50 -1.7 SO 3 0.96 37.14 0.70 0.98 40.0 TiO 2 0.30 15.38 0.26 0.26 0.0 Moisture 0.01 -50.00 0.02 0.00 NA LOI 0.15 -60.53 0.38 0.13 -65.8 Value (ppm) % Diff. Value (ppm) Value (ppm) % Diff. As 8 -61.90 21 36 71.4 Ba 365 79.80 203 367 80.8 Cd ND NA 3 NR NA Cl 238 -43.87 424 177 -58.3 Co 15 NA ND 12 NA Cr 72 -7.69 78 90 15.4 Cu 65 160.00 25 28 12.0 Hg 0.00 NA 0.00 NR NA Mn 958 81.78 527 1683 219.4 Mo 11 NA ND 19 NA Ni 43 152.94 17 15 -11.8 Pb 36 9.09 33 12 -63.6 Sb 57 16.33 49 NR NA Se 0 NA 2 NR NA Sr 402 1.52 396 500 26.3 V 64 -1.54 65 66 1.5 Zn 134 -28.34 187 68 -63.6 Notes: NA - Not Applicable Parameter Burn One Burn Three ND - Not Detected 170 -100 -50 0 50 100 150 200 Percent Differen c e in Mean Relative to B urn Two CPR - Burn One CPR - Burn Three ELR - Burn One ELR - Burn Three Al 2 O 3 SO 3 SiO 2 Na 2 OMgOK 2 OFe 2 O 3 CaO 171 Figure 4.5: Percent Change in Chemical Composition Means for Clinker The final result concerning the chemical composition of clinker is the Rietveld analysis. This test determines the Bogue compounds of the material, and does so more accurately than the formulae used in ASTM C 150. Table 4.25 shows these results, along with the percent difference relative to Burn Two. The results for Burn Three were not available at the time of preparation of this document. Table 4.25: SLR - Rietveld Analysis of Clinker 172 Burn Two Value (wt. %) % Diff. Value (wt. %) Value (wt. %) % Diff. Alite 68.23 9.1 62.52 CIP NA Belite 13.17 -29.0 18.54 CIP NA Ferrite 10.23 -3.8 10.63 CIP NA Aluminate 5.17 20.8 4.28 CIP NA Notes: Burn One Burn Three Parameter CIP - Collection in Progress NR - Not Reported NA - Not Applicable 4.3.6 Chemical Composition of 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. The tests at the cement plant were conducted on eight discrete specimens each day during all three burn periods. The complete set of summary statistics, based on the results collected by the cement plant, is shown in Table 4.26. Table 4.26: CPR - Summary Statistics for Cement Chemical Composition 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 CaO 63.49 0.5 0.843 62.56 0.7 1 0.008 62.79 0.8 1 0.009 Fe 2 O 3 3.10 3.2 1 0.056 3.02 3.0 0.297 3.21 3.8 1 <0.005 K 2 O 0.52 1.9 1 <0.005 0.44 3.4 1 0.023 0.44 2.5 1 0.021 MgO 2.87 2.9 1 <0.005 3.27 5.5 1 <0.005 3.21 1.8 1 0.095 Na 2 O 0.09 7.8 1 <0.005 0.11 12.0 1 <0.005 0.08 8.0 1 <0.005 Na 2 O eq 0.43 1.6 <0.005 0.41 2.9 1 <0.005 0.37 2.1 1 <0.005 SiO 2 20.56 0.5 0.646 19.96 1.4 0.810 20.59 1.0 1 0.049 SO 3 2.61 6.2 1 0.075 2.63 7.5 0.751 2.68 8.8 0.126 Free CaO 0.94 23.3 1 <0.005 0.99 21.5 0.751 1.39 19.6 0.183 LOI 1.03 17.4 0.859 1.22 13.1 0.270 1.25 18.0 0.347 C 3 A 7.94 3.3 0.118 7.23 3.3 1 0.030 7.43 4.7 0.413 C 4 AF 9.45 3.2 1 0.016 9.20 3.0 0.109 9.79 3.8 1 <0.005 C 3 S 56.75 4.7 0.738 59.76 5.6 0.623 54.26 4.0 0.330 C 2 S 16.15 13.5 0.380 12.15 26.2 0.281 18.10 10.4 0.732 Blaine SSA 377 2 2.9 1 <0.005 380 2 3.0 0.376 369 2 5.9 0.927 Notes: 2 Units are m 2 /kg 1 Data Not Normally Distributed Parameter Burn One Burn Two Burn Three Table 4.27 shows the percent difference relative to Burn Two between all of the parameters tested for at the cement plant. Almost every parameter showed a statistically significant change relative to Burn Two. From Burn One, the only parameters that did not show a statistically significant change relative to Burn Two were SO 3 and Blaine specific surface area. Burn Three and Burn Two showed more similarities than Burn One and Burn Two. CaO, K 2 O, MgO, SO 3 , LOI, and Blaine specific surface area (SSA) all showed no statistically significant difference. One thing to consider, however, is that just because many parameters showed a statistically significant difference, does not mean that 173 these same parameters have shown a practically significant difference. 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. Table 4.27: CPR ? Chemical Composition Percent Difference in Mean for Cement Percent Difference P-Value Significant Percent Difference P-Value Significant Al 2 O 3 6.87 0.000 Yes 4.08 0.000 Yes CaO 1.49 0.000 Yes 0.37 0.158 No Fe 2 O 3 2.65 0.003 Yes 6.29 0.000 Yes K 2 O 18.18 0.000 Yes 0.00 0.231 No MgO -12.23 0.000 Yes -1.83 0.123 No Na 2 O -18.18 0.000 Yes -27.27 0.000 Yes Na 2 O eq 4.88 0.000 Yes -9.76 0.000 Yes SiO 2 3.01 0.000 Yes 3.16 0.000 Yes SO 3 -0.76 0.787 No 1.90 0.531 No Free CaO -5.05 0.000 Yes 40.40 0.000 Yes LOI -15.57 0.000 Yes 2.46 0.698 No C 3 A 9.82 0.000 Yes 2.77 0.046 Yes C 4 AF 2.72 0.005 Yes 6.41 0.000 Yes C 3 S -5.04 0.000 Yes -9.20 0.000 Yes C 2 S 32.92 0.000 Yes 48.97 0.000 Yes Blaine SSA -0.98 0.271 No -3.19 0.103 No Parameter Burn One Burn Three 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 174 175 (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 Burn Two, are shown in Table 4.28. Of the less prominent parameters, Ba, Cu, and Mn showed an increase of approximately 100 percent for Burn One. As and Cl showed a decrease of more than 50 percent in Burn One. Ba and Mn each showed an increase of over 100 percent in Burn Three. Cl, Cu, and Zn showed decreases of approximately 50 percent or more in Burn Three. Figure 4.6 graphically shows the major parameters for both testing agencies. Al 2 O 3 , CaO, Fe 2 O 3 , and SiO 2 , are the primary compounds in the cement, and have the greatest impact on the physical properties of cement, and on the properties of concrete. Figure 4.6 shows that there was very little change in concentration of each of these parameters. Just as with the clinker, these results suggest that, regardless of the fuel that is being burned, the cement plant is capable of maintaining consistent concentrations in Al 2 O 3 , CaO, Fe 2 O 3 , and SiO 2 . Figure 4.6 shows that K 2 O, MgO, and Na 2 O each showed appreciable differences in at least one burn. These parameters make up a small portion of the cement, therefore, a small change in concentration shows a large percent difference. Also, once again, just because the difference is appreciable, does not necessarily mean that it is practically significant. Additionally, each of these compounds are less important to the properties of cement and concrete than Al 2 O 3 , CaO, Fe 2 O 3 , and SiO 2 . Just as with the clinker, when the data shown in Table 4.19 is compared with the results shown for the cement, it not possible to conclude that the chemical composition of the fuels has any effect on the chemical composition of the cement. This is to be 176 expected based on the results from the clinker, because the only chemical difference between the clinker and cement is the addition of a relatively small amount of Raw Material 6. Table 4.28: ELR - Chemical Composition of Cement 177 A Burn Two Value (wt. %) % Diff. Value (wt. %) Value (wt. %) % Diff. Al 2 O 3 5.04 4.8 4.81 4.93 2.5 CaO 63.99 1.5 63.05 63.18 0.2 Fe 2 O 3 3.20 4.6 3.06 3.11 1.6 K 2 O 0.49 4.3 0.47 0.40 -14.9 MgO 2.89 -14.5 3.38 3.47 2.7 Na 2 O 0.01 -85.7 0.07 0.12 71.4 P 2 O 5 0.08 33.3 0.06 0.06 0.0 SiO 2 20.53 -2.5 21.05 21.51 2.2 SO 3 2.78 -4.1 2.90 2.71 -6.6 TiO 2 0.26 8.3 0.24 0.26 8.3 Moisture 0.28 -41.7 0.48 0.39 -18.8 LOI 0.69 -17.9 0.84 0.91 8.3 C 3 S 58.06 12.5 51.62 48.39 -6.3 C 2 S 15.06 -29.7 21.42 25.16 17.5 C 3 A 7.96 5.2 7.57 7.80 3.0 C 4 AF 9.74 4.4 9.33 9.46 1.4 TOC ND NA ND 0.05 NA Value (ppm) % Diff. Value (ppm) Value (ppm) % Diff. As (ppm) 8 -55.6 18 27 50.0 Ba (ppm) 321 134.3 137 300 119.0 Cd (ppm) ND NA ND NR NA Cl (ppm) 80 -85.2 541 57 -89.5 Co (ppm) 14 NA ND 13 NA Cr (ppm) 82 3.8 79 92 16.5 Cu (ppm) 64 106.5 31 14 -54.8 Hg (ppm) 0.00 NA 0.00 NR NA Mn (ppm) 958 91.2 501 1600 219.4 Mo (ppm) 8NAND 2 NA Ni (ppm) ND NA ND 12 NA Pb (ppm) 33 -10.8 37 27 -27.0 Sb (ppm) 51 -19.0 63 NR NA Se (ppm) 10.0 1 NRN Sr (ppm) 409 2.0 401 500 24.7 V (ppm) 62 19.2 52 69 32.7 Zn (ppm) 126 -30.8 182 62 -65.9 Notes: ND - Not Detected NR - Not Reported NA - Not Applicable Parameter Burn One Burn Three -100 -80 -60 -40 -20 0 20 40 60 80 Percent Differen c e in Mean Relative to B urn Two CPR - Burn One CPR - Burn Three ELR - Burn One ELR - Burn Three Al 2 OSO 3 SiO 2 Na 2 OMgOK 2 OFe 2 O 3 CaO 178 Figure 4.6: Percent Difference in Chemical Composition Means for Cement The final chemical composition of cement that was determined was the Bogue compounds by Rietveld Analysis. This test was conducted by the cement plant specialty laboratory. The results of this test are shown in Table 4.29. Along with the results, the percent differences relative to Burn Two are also shown. The results for Burn Three had not been received by the time of the completion of this document. Table 4.29: SLR - Rietveld Analysis on Cement 179 Burn Two Value (wt. %) % Diff. Value (wt. %) Value (wt. %) % Diff. Alite 65.11 12.4 57.94 CIP NA Belite 17.12 -6.6 18.33 CIP NA Ferrite 6.36 -37.9 10.24 CIP NA Aluminate 5.67 35.2 4.20 CIP NA Notes: CIP - Collection in Progress NR - Not Reported NA - Not Applicable Parameter Burn One Burn Three 4.3.7 Physical Properties of Cement The physical properties of the cement were determined by personnel at the cement plant and at Auburn University. Both testing entities conducted the same tests; the one exception was that Auburn determined the drying shrinkage development of paste prisms. The results of the physical properties conducted by the cement plant are shown in Table 4.30. Table 4.31 shows the results from the physical property tests conducted by Auburn University. 180 A graphical representation of selected results can be seen in Figure 4.7. Just as with the chemical composition plots of this nature, the percent differences for each of the testing agencies are relative to Burn Two data as determined by that testing agency. Some of the percent differences are not shown in Figure 4.7. Notably, the compressive strength and drying shrinkage results were plotted on their own, and are discussed later in this section. Figure 4.7 shows that a major change was seen in the autoclave expansion. Burn Three showed an 83 percent increase, and Burn One showed a 40 percent decrease relative to Burn Two as reported by the cement plant. Auburn University reported an increase of 67 and 33 percent for Burn One and Three respectively, for the same property. Another interesting result to note from Figure 4.7 is that Burn Three showed an acceleration in setting times, both initial and final, in the Gillmore and Vicat setting test, at both testing agencies. This result may suggest that the cement produced during Burn Three has a tendency to set more quickly than the cement produced during Burns One and Two. The setting time results for Burn One relative to Burn Two do not show results that allow for any conclusive results to be made. However, six of the eight results did show a dramatic retardation in setting times. The final property that showed large changes for Burns One and Three, relative to Burn Two, is the air content in mortar, as shown in Table 4.30. This test was only conducted by the cement plant. Both burns showed an increase in air content relative to Burn Two. 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 cement, and is not practically significant to this study. Table 4.30: CPR - Physical Properties and Percent Change for Cement Burn Value % Diff. Value Value % Diff. Air in Mortar (%) 6.7 15.5 5.8 6.6 13.8 Blaine Specific Surface Area (m 2 /kg) 366 -3.9 381 374 -1.8 Autoclave Expansion (% Exp.) 0.06 -40.0 0.10 0.18 80.0 Cube Flow (%) 125.7 2.2 123.0 122.5 -0.4 Compressive Strength (MPa) 1 day 15.3 -0.6 15.4 13.6 -11.7 3 days 24.3 -2.8 25.0 22.2 -11.2 7 days 31.9 -2.1 32.6 30.7 -5.8 28 days 42.7 -3.0 44.0 42.8 -2.7 Normal Consistency (%) 25.6 -0.4 25.7 25.9 0.8 Gillmore Initial Set (Min.) 105 -8.7 115 98 -15.2 Gillmore Final Set (Min.) 275 3.0 267 263 -1.5 Vicat Initial Set (Min.) 80 9.6 73 62 -15.1 Vicat Final Set (Min.) 180 -23.4 235 225 -4.3 Property Burn One Burn Three 181 Table 4.31: AUR - Physical Properties and Percent Change for Cement Burn Value % Diff. Value Value % Diff. Autoclave Expansion (% Exp.) 0.05 66.7 0.03 0.04 33.3 Cube Flow (%) 91 -7.1 98 111 13.3 Compressive Strength (MPa) 1 day 9.30 -15.5 11.0 11.5 4.5 3 days 17.2 -25.5 23.1 17.1 -26.0 7 days 25.8 -13.4 29.8 24.8 -16.8 28 days 35.1 -11.1 39.5 38.8 -1.8 Normal Consistency (%) 25.4 -3.1 26.2 26.2 0.0 Gillmore Initial Set (Min.) 150 108.3 72 72 0.0 Gillmore Final Set (Min.) 238 64.1 145 105 -27.6 Vicat Initial Set (Min.) 106 53.6 69 66 -4.3 Vicat Final Set (Min.) 236 72.3 137 115 -16.1 Drying Shrinkage (%) 7 days -0.042 -17.6 -0.051 -0.045 -11.8 14 days -0.068 -5.6 -0.072 -0.069 -4.2 21 days -0.079 -4.8 -0.083 -0.081 -2.4 28 days -0.087 -7.4 -0.094 -0.089 -5.3 Property Burn One Burn Three 182 -60 -40 -20 0 20 40 60 80 100 120 Percent Change Relati ve to Burn Two CPR - Burn One CPR - Burn Three AUR - Burn One AUR - Burn Three Autoclave Exp. Gill. Initial Set Gill. Final Set Vicat Initial Set Vicat Final Set 183 Figure 4.7: Percent Difference in Physical Properties of Cement 184 The results from both the cement plant and Auburn University for mortar cube compressive strengths are presented graphically in Figure 4.8. The most notable aspect of these results is that the numbers presented by the cement plant are all higher than those presented by Auburn. 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. Based on those criteria, none of the results presented by the cement plant are significantly different between burns. However, the results presented by Auburn University show that the compressive strength of the three- and seven-day cubes for Burn Two are significantly stronger than those of either of the other burns. These results will be compared with the compressive strength results associated with concrete in Section 4.3.8. The final test of the physical properties of cement, which was conducted only at Auburn University, was drying shrinkage of paste prisms. The results of this test are shown graphically in Figure 4.9. The ages associated with these results are cement ages. The specimens were cured for three days prior to exposure to drying conditions. These results are presented with a shrinkage value reported as a positive percentage of the original length. From Figure 4.9 one can see that the trend of the results is reasonably definitive, although not too different. At all ages, Burn One showed the least shrinkage, and Burn Two showed the most shrinkage, while Burn Three was consistently in the middle. These results will be compared with the drying shrinkage results exhibited by concrete in Section 4.3.8. 0 5 10 15 20 25 30 35 40 45 50 0 7 14 21 28 35 Age (days) C o mpressive Strength (MP a ) CPR - Burn One CPR - Burn Two CPR - Burn Three AUR - Burn One AUR - Burn Two AUR - Burn Three 185 Figure 4.8: Compressive Strength Development of Mortar Cubes from Both Testing Agencies 0.000 0.010 0.020 0.030 0.040 0.050 0.060 0.070 0.080 0.090 0.100 0 7 14 21 28 35 Drying Age (days) Dr y i ng Shri n ka g e (%) Burn One Burn Two Burn Three 0 Figure 4.9: AUR - Drying Shrinkage Development of Mortar Prisms 186 Another physical property of the cement is the heat of hydration. This is the amount of heat generated by the cement as the hydration process progresses. This test was conducted by the specialty laboratory, and the results can be seen in Table 4.32. This table also shows the difference between Burns One and Two. The results for Burn Three had not been received by Auburn personnel at the time of the completion of this document. The heat of hydration data are very similar between Burns One and Two. Table 4.32: SLR - Heat of Hydration of Cement 187 Burn Two Value (kJ/kg) % Diff. Value (kJ/kg) Value (kJ/kg) % Diff. 7 days 359 -2.2 367 CIP NA 28 days 395 -0.4 397 CIP NA Notes: CIP - Collection in Progress NA - Not Applicable Age Burn One Burn Three The final physical property of cement that was determined 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, this result may help to explain some of the differences in some of the physical properties of the cement and concrete. The results of this test are shown in Figure 4.10. From this result, one can see that the particle distribution of Burn One was somewhat finer that of Burn Two. 0 10 20 30 40 50 60 70 80 90 100 1 10 100 1000 Laser Particle Size Distribution, ?m Percent Pa ssing Burn One Burn Two Figure 4.10: SLR - Particle Size Distribution of Cement 188 189 4.3.8 Properties of Concrete Concrete was produced using the cement collected during each of the burn phases. There were two different concrete mixtures that were produced relative to each burn phase. The results for each type of mixture are discussed individually due to the fact that proportions of the mixtures were different, and cannot be compared with one another. The first mixture, Mix A, was a conventional mixture with a water-to-cement ratio of 0.44, and utilized only an air-entraining admixture. This mixture was made at Auburn University and at the concrete laboratory of the cement plant. Table 4.33 shows the concrete property results of Mix A. Burn Three does not show any results from the laboratory of the cement plant because this mixture had not been produced by the completion of this document. Additionally, setting time and splitting tensile strength data were not determined by the cement plant. The percent difference for each concrete property reported in Table 4.33 is calculated relative to the concrete mixture produced at Auburn University using cement from Burn Two. These differences for all properties except for compressive strength and splitting tensile strength are shown in Figure 4.11. It is obvious from this figure that the most dramatic change was in the slump. The results concerning slump from the cement plant showed a decrease of 64 and 71 percent for Burns One and Two, respectively. This difference can most likely be attributed to differences in laboratory practices and/or conditions between the cement plant and Auburn University. Therefore, it is not a 190 property attributable to the cement used, and is only significant relative to the strengths of the concrete. It is important to note that the 91-day permeability results are similar, especially after considering that the within-test repeatability for ASTM C 1202 is on the order of 1000 Coulombs. From this data it may thus be concluded that the concrete made from each of these cements should have similar permeability. Table 4.33: AUR and CPR - Concrete Mix A Results AUR % Diff. CPR % Diff. AUR CPR % Diff. AUR % Diff. Total Air Content (%) 4.0 -5.9 3.6 -15.3 4.25 3.2 -24.71 4.0 -5.9 Slump (mm) 100 11.1 30 -66.7 90 30 -66.67 90 0.0 Unit Weight (kg/m 3 ) 2394 -1.8 2450 0.5 2439 2448 0.37 2464 1.0 Initial Set (Min.) 211 -3.2 218 0.0 218 247 13.30 216 -0.9 Final Set (Min.) 298 9.2 322 17.9 273 NC NA 266 -2.6 Compressive Strength (MPa) 1 day 12.3 -11.5 15.8 13.7 13.9 15.1 8.63 14.0 0.7 3 days 22.7 9.7 23.3 12.6 20.7 21.9 5.80 23.1 11.6 7 days 25.2 -11.3 33.3 17.3 28.4 32.8 15.49 28.5 0.4 28 days 35.0 -5.7 43.3 16.7 37.1 42.2 13.75 39.0 5.1 91 days 41.6 0.5 48.2 16.4 41.4 49.6 19.81 CIP NA Splitting Tensile Strength (MPa) 1 day 1.7 -15.0 NC NA 2.0 NC NA 1.7 -15.0 3 days 2.4 4.3 NC NA 2.3 NC NA 2.3 0.0 7 days 2.6 -7.1 NC NA 2.8 NC NA 2.8 0.0 28 days 3.2 -3.0 NC NA 3.3 NC NA 3.5 6.1 91 days 3.7 -7.5 NC NA 4.0 NC NA CIP NA Permeability @ 91 days (Coulombs) 2650 -9.6 2530 -13.7 2930 2660 -9.22 CIP NA Notes: CIP - Collection in Progress NC - Not Collected NA - Not Applicable Property Burn One Burn Two Burn Three 191 -80 -70 -60 -50 -40 -30 -20 -10 0 10 20 30 Percent Difference Relati ve to AUR for Burn Two AUR - Burn One AUR - Burn Three CPR - Burn One CPR - Burn Two Total Air PermeabilityFinal SetInitial Unit Wgt.Slump Figure 4.11: Percent Difference in Mix A Concrete Results Relative to AUR Burn Two 192 193 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 results of Mix A are shown in Table 4.33. These results are plotted relative to one another in Figure 4.12. The most noticeable difference in compressive strength is that both of the mixtures conducted by the cement plant produced higher compressive strengths. This result was also shown in the compressive strength of mortar cubes. The fact that the slumps of the cement plant mixtures were considerably lower than that for those produced at Auburn University indicates that the fresh concrete had a lower consistency at the time of placement. This may indicate that less free mixing water was available; these concretes were thus made with a slightly lower water-to-cement ratio. This result is most likely the primary reason for the difference in strengths between the two testing entities. However, the value that is more meaningful is the relative difference between the concrete strengths for each burn. The results from the cement plant show very little difference at all ages between the concrete from Burns One and Two. The compressive strength results reported by Auburn University show a meaningful difference at ages of seven and 28 days. The acceptable range of results, as specified by ASTM C 39, for a single operator, is 7 percent. Based on this criteria, Burn One showed a significant change relative to Burn Two at 1, 3, and 7 days. However, because two results decreased, and one increased, these results are inconclusive. Burn Three showed a significant increase over Burn Two only at a concrete age of 3 days. 194 Because the results at other ages were so similar, these results are once again inconclusive. There was a significant difference between Burns One and Three at concrete ages of 1, 7, and 28 days. This may suggest that the concrete produced from Burn Two cement is significantly stronger than that produced from Burn One cement. These results will be compared with those of Mix B in the following sections. Results from splitting tensile strength tests of concrete produced from portland cement from Burns One, Two, and Three can be seen in Figure 4.13. According to ASTM C 496, the acceptable range of results within a single laboratory is 14 percent. Based on this criteria, there were no significant changes in splitting tensile strength between any of the burns. The greatest difference occurred at a concrete age of one day, and was only one percent above the acceptable range of results. This suggests that there were no significant changes in splitting tensile strength for Mix A. 0 10 20 30 40 50 60 0 7 14 21 28 35 42 49 56 63 70 77 84 91 98 Concrete Age (days) Co mpressiv e Streng th (M Pa) AUR - Burn One AUR - Burn Two AUR - Burn Three CPR - Burn One CPR - Burn Two 195 Figure 4.12: Compressive Strength for Mix A Concrete 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 0 7 14 21 28 35 42 49 56 63 70 77 84 91 98 Concrete Age (days) Splitting Tensile Streng t h (MPa) AUR - Burn One AUR - Burn Two AUR - Burn Three 196 Figure 4.13: AUR - Splitting Tensile Strength for Mix A Concrete The drying shrinkage development of concrete Mix A is shown in Table 4.34. The results are presented with shrinkage values reported as positive numbers. All values are given as a percent length change relative to the original length. In addition to the length change value, the percent difference of Burns One and Three relative to Burn Two are also presented. The concrete was exposed to drying conditions after seven days of saturated curing after concrete placement. Due to the timing of the burn, shrinkage results for the concrete from Burn Three are only reported up to a concrete age of 28 days. Table 4.34: Drying Shrinkage Development of Mix A Concrete 197 Burn Two Length Chage (%) % Diff Length Chage (%) Length Chage (%) % Diff 4 0.009 -50.0 0.018 0.008 -55.6 7 0.018 -33.3 0.027 0.011 -59.3 14 0.028 -17.6 0.034 0.020 -41.2 28 0.029 -17.1 0.035 0.029 -17.1 56 0.038 5.6 0.036 CIP NA 112 0.045 2.3 0.044 CIP NA 224 0.049 4.3 0.047 CIP NA 448 CIP NA CIP CIP NA Notes: CIP - Collection in Process NA - Not Applicable Drying Age (days) Burn One Burn Three The results in Table 4.34 are presented graphically in Figure 4.14, 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. 198 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 determination of the heat of hydration produced under semi-adiabatic conditions. The results of this test for concrete Mix A can be seen in Figure 4.15. 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 based on temperature. The equivalent age is shown on a logarithmic scale. As one can see from Figure 4.15, there was essentially no difference in degree of hydration between the three burns. The concrete from Burn Three reached a slightly higher degree of hydration at an equivalent age of 10,000 hours, but the difference is still very small. Based on this result, there was very little difference in hydration progression between the three burns. 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0 50 100 150 200 250 Drying Time (days) Dry i ng Shrinka ge (Percent Length Chang e ) Burn One Burn Two Burn Three 0 199 Figure 4.14: AUR - Drying Shrinkage Development for Mix A 0.0 0.2 0.4 0.6 0.8 1.0 1 10 100 1,000 10,000 Concrete Equivalent Age (hours) Degree of Hydration Burn One Burn Two Burn Three Figure 4.15: AUR - Semi Adiabatic Degree of Hydration Development for Mix A 200 201 The second mixture, Mix B, was a high-strength mixture with a water-to-cement ratio of 0.37. This mixture utilized both an air-entraining admixture and a water-reducing admixture. Mix B was only prepared by personnel at Auburn University. The results of tests on Mix B are shown in Table 4.35. Once again Burn Two was considered the baseline, and therefore is used as the reference for the percent differences. These changes, for all properties except compressive strength and splitting tensile strength, are presented graphically in Figure 4.16. Mix B showed an increase in total air content for both Burns One and Three. In fact, Burn One showed a 50 percent increase in this property over Burn Two, and these differences are also slightly reflected in the unit weight. The unit weight showed a maximum change of 2.2 percent, which occurred in Burn One. The slumps from Burns One and Three were both 152 millimeters. This was a decrease of approximately eight percent relative to Burn Two. The final property was setting time, which showed a similar change in both initial and final times for the Coal Only burn. This burn showed an increase in initial setting time of 33 percent, and an increase in final setting time of 39 percent. Burn Three showed an acceleration in initial set, which is the same result that was seen in mortar setting times and in Mix A. The final set time for Burn Three showed practically no change. Table 4.35: AUR - Concrete Results for Mix B Burn Two Value % Diff. Value Value % Diff. Total Air Content (%) 6.0 50.0 4.0 5.0 25.0 Slump (mm) 150 -6.3 160 150 -6.3 Unit Weight (kg/m 3 ) 2374 -2.2 2427 2413 -0.6 Initial Set (Min.) 318 33.1 239 229 -4.2 Final Set (Min.) 405 39.7 290 291 0.3 Compressive Strength (MPa) 1 day 20.8 -19.7 25.9 22.3 -13.9 3 days 31.9 -11.6 36.1 33.1 -8.3 7 days 37.7 -5.7 40.0 38.0 -5.0 28 days 44.3 -10.9 49.7 51.0 2.6 91 days 51.5 -12.9 59 CIP NA Splitting Tensile Strength (MPa) 1 day 2.5 -16.7 3.0 2.7 -10.0 3 days 3.3 -10.8 3.7 3.4 -8.1 7 days 3.7 -5.1 3.9 3.5 -10.3 28 days 4.1 -4.7 4.3 4.0 -7.0 91 days 4.3 -12.2 4.9 CIP NA Permeability @ 91 days (Coulombs) 2650 3.9 2550 CIP NA Notes: CIP - Collection in Process NA - Not Applicable Property Burn One Burn Three 202 -10 0 10 20 30 40 50 60 Percent Difference Relati ve to AUR fo r B u rn Two AUR - Burn One AUR - Burn Three Total Air PermeabilityFinal SetInitial Set Unit Wgt. Slump Figure 4.16: AUR - Percent Difference in Concrete Properties for Mix B 203 204 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 Burn One was significantly weaker than the concrete made from Burns Two and Three at all ages except for seven days. Based on this result, it is fairly conclusive that Burn One produced concrete with significantly 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. A graphical presentation of the splitting tensile strength of Mix B, conducted by Auburn University, can be seen in Figure 4.18. Just as with the splitting tensile strength results presented in Mix A, Burn One produced lower strengths than Burn Two, but at no ages did this difference surpass the acceptable range of results provided by ASTM C 496. Based on these results, there is no significant change in splitting tensile strength for Mix B. 0 10 20 30 40 50 60 70 0 10203040506070809010 Concrete Age (days) C o mpressive Strength (MP a ) AUR - Burn One AUR - Burn Two AUR - Burn Three 205 Figure 4.17: AUR - Compressive Strength for Mix B Concrete 0.0 1.0 2.0 3.0 4.0 5.0 6.0 0 10203040506070809010 Concrete Age (days) Splitting T e nsile Strength (MPa ) AUR - Burn One AUR - Burn Two AUR - Burn Three Figure 4.18: AUR - Splitting Tensile Strength for Mix B Concrete 206 The results of the drying shrinkage development test conducted at Auburn University on Mix B concrete can be seen in Table 4.36. Just as with the Mix A results, shrinkage values are reported as a positive percentage length change. Due to the timing of the burn phases, many of the long term results are yet to be collected. Table 4.36: AUR - Drying Shrinkage Development of Mix B Concrete 207 4 0.013 18.2 0.011 0.016 45.5 7 0.019 -5.0 0.020 0.018 -10.0 14 0.032 28.0 0.025 0.023 -8.0 28 0.037 23.3 0.030 0.036 NA 56 0.043 10.3 0.039 CIP NA 112 0.051 NA CIP CIP NA 224 CIP NA CIP CIP NA 448 CIP NA CIP CIP NA Notes: CIP - Collection in Process NA - Not Applicable Burn Two Length Chage (%) % Diff Length Chage (%) Length Chage (%) % Diff Drying Age (days) Burn One Burn Three 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 appears as though the drying shrinkage properties of the concrete were not significantly altered. Figure 4.20 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 Burns Two and Three are basically the same. Burn One, however, experienced lower hydration between equivalent ages of 10 and 1,000 hours. This result could explain the slightly lower compressive strengths for Burn One at one and three days. 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0 2040608010120 Drying Time (days) Dry i ng Shrinka ge (Percent Length Chang e ) Burn One Burn Two Burn Three 0 208 Figure 4.19: AUR - Drying Shrinkage Development for Mix B Concrete 0.0 0.2 0.4 0.6 0.8 1.0 1 10 100 1,000 10,000 Concrete Equivalent Age (hours) D e gr ee of H y d r at i o n Burn One Burn Two Burn Three Figure 4.20: AUR - Semi Adiabatic Degree of Hydration Development for Mix B 209 210 4.3.9 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 4.37 shows the summary statistics for these data. 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 now presented in terms of tons per ton of clinker produced. Figure 4.21 through Figure 4.24 show the time-history plot of each of the emissions relative to time. In addition, the average for each emission is given in the key. Table 4.37: CPR - Summary Statistics for Emissions Burn One Burn Two Burn Three Average (10 -3 ) 0.82 1.21 1.05 Coefficient of Variation (%) 8.3 8.0 9.4 P-Value 1 0.064 2 0.015 2 0.035 2 Average (10 -6 ) 0.40 11.24 0.41 Coefficient of Variation (%) 218.9 145.6 163.7 P-Value 1 <0.005 2 <0.005 2 <0.005 2 Average (10 -5 ) 2.31 3.42 2.61 Coefficient of Variation (%) 64.5 35.8 22.4 P-Value 1 <0.005 2 0.008 2 0.023 2 Average (10 -4 ) 7.68 5.41 5.67 Coefficient of Variation (%) 9.9 10.8 22.0 P-Value 1 0.060 2 0.214 0.375 1 Based on Anderson-Darling Statistics 2 Not Normally Distributed Notes: NO x ( t o ns/t on c linke r ) SO 2 ( t o ns/t on c linke r ) VO C ( t o ns/t on c linke r ) CO ( t o ns/t on c linke r ) 211 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 0 8 16 24 32 40 48 56 64 72 NO x E m issio ns (to ns/ton clinker x 10 -3 ) 212 Burn One (Avg. = 0.82) Burn Two (Avg. = 1.21) Burn Three (Avg. = 1.05) 0 Time (hrs) Figure 4.21: CPR - Time History Plot of NO x Emissions 0 0 0 1 10 100 1000 0 8 16 24 32 40 48 56 64 72 Burn One (Avg. = 0.40) Burn Two (Avg. = 11.24) Burn Three (Avg. = 0.41) SO 2 Emissions (ton s /ton clinker x 10 -6 ) 213 0.1 0.01 0.001 Time (hrs) Figure 4.22: CPR - Time History Plot of SO 2 Emissions 0 1 2 3 4 5 6 7 8 0 8 16 24 32 40 48 56 64 72 Time (hrs) VO C Emissions (tons/t o n clinker x 1 0 -5 ) Burn One (Avg. = 2.31) Burn Two (Avg. = 3.42) Burn Three (Avg. = 2.61) 214 Figure 4.23: CPR - Time History Plot of VOC Emissions 0 2 4 6 8 10 12 0 8 16 24 32 40 48 56 64 72 Time (hrs) CO E m issio ns (to ns/ton clinker x 10 -4 ) Burn One (Avg. = 7.68) Burn Two (Avg. = 5.41) Burn Three (Avg. = 5.67) Figure 4.24: CPR - Time History Plot of CO Emissions 215 Table 4.38 shows the percent differences between Burns One and Three relative to Burn Two. It also shows whether these results were statistically different, along with the corresponding P-values. Figure 4.25 shows these results graphically. The most striking difference is the one that applies to the SO 2 data. This SO 2 emissions data showed almost a 100 percent decrease for both Burns One and Three. After discussion with personnel at the cement plant, the consensus was that there was some type of anomaly with this emission during Burn Two. Although differences did occur in most of the other emissions, the cement plant personnel could offer no plausible explanation for these high SO 2 readings for Burn Two. The results shown in Figure 4.25 indicate that the NO x and VOC were reduced in Burns One and Three relative to Burn Two, whereas the CO emissions were increased. It is important to notice that the average CO levels were the lowest when alternative fuels were used. 216 Burn One Burn Three Percent Difference -32.4 -13.1 Statistically Different Yes Yes P-Value 0.000 0.000 Percent Difference -96.4 -96.4 Statistically Different Yes Yes P-Value 0.000 0.000 Percent Difference -32.5 -23.8 Statistically Different Yes Yes P-Value 0.000 0.000 Percent Difference 41.8 4.8 Statistically Different Yes No P-Value 0.000 0.115 CO NO x SO 2 VOC Table 4.38: CPR - Percent Difference and Significance of Emissions -120 -100 -80 -60 -40 -20 0 20 40 60 Change in Mea n Relativ e to Co al + Tires (%) Burn One Burn Three NO x COVOC SO 2 217 Figure 4.25: CPR - Percent Change in Means of Emissions Relative to Burn Two 218 4.4 Conclusion The production of portland cement utilizes many complex materials, facilities, and processes. The nature of the production process results in countless 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 implementation 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 build-ups inside 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 rate of the plastics was also limited by the equipment used. In this case, the injection system was limited in the quantity of the low-density plastic fuels that were being used. In spite of the limitations associated with these fuels, the results shown in Section 4.3.3 showed some positive results as well. The most prominent of these was the energy content of the alternative fuels. The heat value of each of the fuels was determined to be as follows: 1. Coal: 11,157 to 12,476 BTU/lb, 2. Tires: 14,467 to 14,687 BTU/lb, and 219 e these 3. Plastics: 11,327 to 14,446 BTU/lb. These results indicate that the tires and plastics have good combustion properties as they produce more heat per pound than the coal. These combustion properties, along with the costs associated with acquisition, mean that the cement plant will continue to use these fuels for the foreseeable 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 burn periods. 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. 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 by burning each of the fuels used in this study. These are significant results, becaus 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 impact the physical properties of the cement, and concrete 220 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 significant change between burn periods. 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 significantly affected by the cement from which it was made. Another property of 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 seen between each of the burns. This shows conclusively that each of the cements used in this study were significantly similar in their drying shrinkage properties. 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. 221 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 showed an increase relative to Burn Two in all cases but one. However, because of the one inconsistent result, no definitive conclusion could be drawn. The setting times for cement and concrete showed some significant changes. In the Gillmore and Vicat setting tests of cement pastes, the cement of Burn Three showed significant acceleration relative to that of Burns One and Two. The concrete made from Burn Three did not show a similar acceleration for either Mix A or Mix B. The setting time of Mix B concrete showed significant retardation for cement from Burn One. Again, however, this result was not corroborated by either the cement paste results or the Mix A results. Perhaps the most prominent result was the compressive strength of Burn One. In the mortar cube test, as well as both concrete mixtures, Burn One showed a trend in that it consistently produced the lowest compressive strengths. At various ages, Burn One was, at best, significantly similar to the other results, but in many cases, it was significantly weaker. 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 with the chemical composition of the cement, it is difficult to say that the fuels used were directly responsible for any changes that may 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 burn periods. The following list summarizes the emissions collected for each burn based on the averages: 222 1. NO x (Burn Two) > NO x (Burn Three) > NO x (Burn One), 2. SO 2 (Burn Two) > SO 2 (Burn Three) > SO 2 (Burn One), 3. VOC (Burn Two) > VOC (Burn Three) > VOC (Burn One), and 4. CO (Burn One) > CO (Burn Three) > CO (Burn Two). Based on these results, Burn Two showed the highest emissions for NO x , SO 2 , and VOC. This could possibly be attributed to the higher rate of tire use during Burn Two relative to Burn Three, and the lack of tire use in Burn One. However, CO, the primary greenhouse gas emitted by the cement plant, was the highest when only coal was used. Unfortunately, the variable nature of the cement production process makes it very difficult to conclusively say that the use of alternative fuels has a significant effect on cement and concrete properties, or on emissions characteristics. Although there were changes in some of these properties between burn periods, further research is necessary to determine whether these changes are a direct result of the use of alternative fuels. 223 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 is both profitable for the portland cement industry, and beneficial to the environment. 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, recycled industrial plastics, and broiler litter were examined as viable alternatives to traditional fuels. Tires have been used in the cement industry for many 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 224 makes use of the heat generated through the 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. The use of broiler litter as fuel in a cement plant releases some of the pressure that the environment may feel from land application. In this study, a full-scale, operational cement plant was used as the test venue. During normal production, the aforementioned alternative fuels were burned in four different test periods. Each of these test periods was called a burn period, and each utilized different combinations of these fuels. The first burn period that was conducted used only coal. The second burn period utilized coal and whole tires. Based on previous research conducted by the cement plant, standard operation at this specific facility uses this combination of fuels. For this reason, the coal plus tires burn was considered the baseline in this study. The third burn period utilized coal, tires, and plastics. The final burn period implemented coal, tires, and broiler litter. Due to the timing of the last burn period, the results had not been collected and are not reported in this document. These results will be presented in future work. Within each burn period, 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 burn periods. Due 225 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 out of the cement from each burn, and various concrete properties were tested. These physical properties of cement and concrete were then compared between burn periods in order to determine if the fuels had any impact. Finally, the emissions released by the cement plant were monitored during each burn period. These emissions were then compared between burn periods 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 the cement plant to maintain productive operation. 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 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 equipment to move the low-density material into the kiln. Despite these limiting factors, both of these fuels showed potential, in that they both had higher energy content than the coal. The average energy content for the coal was approximately 11,700 BTU/lb. The average energy content of the tires was approximately 14,500 BTU/lb. The average energy content of the plastics was approximately 12,800 BTU/lb. Based on the energy 226 content, as well as the cost of acquisition relative to the coal, the cement plant will continue to burn these fuels in the foreseeable future. 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 a significant difference between each of the burn periods 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 chemical composition of the clinker and cement were directly affected by the fuels that were used. The most significant results concerning chemical composition of clinker and cement were that the concentrations of Al2O3, CaO, Fe2O3, and SiO2 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 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 is used to produce. Many of the physical properties of cement that were tested did not show a significant difference between burn periods. Autoclave expansion and drying shrinkage of paste prisms were the most prominent results that showed no practically significant change. From these 227 results, it appeared as though the susceptibility to length change under various conditions was not altered between the burn periods. 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 setting times of as much as 27 percent relative to the cement produced using coal plus tires. The majority of the results did not show a significant difference in setting times between the cement produced during the other burn periods. The final result that showed a significant change was the mortar cube compressive strength. The cement produced using coal plus tires showed a trend of higher strengths than the other two burns, at all ages. This result was most significant at mortar ages of three and seven days, and was as much as 26 percent. The difference in compressive strength of mortar from the coal only burn and the coal, tires, and plastics burn was not significant. Although differences were found in the physical properties of cement between the burn periods, it was not possible to conclude that they were a direct result of the fuels that were used. The fourth objective of this study was to determine if the utilization of alternative fuels directly impacted the properties of concrete made from this portland cement. Two different concrete mixtures were made from the cement produced during each burn period. 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 results from both concrete mixtures showed no significant change in permeability between any of the burn periods. Additionally, the drying shrinkage development of both concrete mixtures did not show any significant changes between each burn period. This result agreed with that 228 for the drying shrinkage development of paste prisms. The splitting tensile strength of both concrete mixtures also showed no significant change between burn periods. A few results showed significant changes at certain ages, but no significant trends were shown. Some concrete properties did show significant trends, one of which was the setting time. In one of the concrete mixtures produced from the cement using coal only, a significant retardation in setting time occurred. This retardation was as much as 40 percent relative to the Coal plus Tires burn period, and the Coal, Tires, and Plastics burn period. However, this result was not corroborated in the other concrete mix. Besides this result, there were no significant changes in concrete setting time. The compressive strength of concrete cylinders is the primary property used to indicate the performance of concrete. This property did show a significant trend for the concrete made using the Coal Only cement. The concrete produced from this cement was significantly weaker, at most ages, than the concrete made from the cement produced during the Coal plus Tires burn. The difference in compressive strength between these two burns was as much as 20 percent. The concrete made from this cement was also significantly weaker, at many ages, than the concrete made from the cement produced by using Coal, Tires, and Plastics. The difference in these concretes was as much as 14 percent. Based on these results, the concrete made from the cement that was produced using Coal Only was significantly weaker than concrete made from either of the other burn periods. The final objective of this study was to determine if the utilization of alternative fuels directly impacted the 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 relative changes in the means of each emission were as follows: 229 1. NOx (Coal plus Tires) > NOx (Coal, Tires, and Plastics) > NOx (Coal), 2. SO2 (Coal plus Tires) > SO2 (Coal, Tires, and Plastics) > SO2 (Coal), 3. VOC (Coal plus Tires) > VOC (Coal, Tires, and Plastics) > VOC (Coal), 4. CO (Coal) > CO (Coal, Tires, and Plastics) > CO (Coal plus Tires). However, the variable nature of the production process once again minimized the ability of the researcher to say conclusively that the fuels used were directly responsible for any changes that were seen in the emissions. 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 satisfying those 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. These obstacles resulted in a number of delays in the timing of the burn periods. Now that the facilities are in place to handle these alternative fuels, it would be beneficial to conduct a number of burn periods using similar fuels within close proximity (time wise) to one another. Due to the delays experienced in this study, the burn periods were too far apart. These extended breaks between burn periods required 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 burn periods. 230 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 burn period 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 burn periods. Other parameters of the production process, which were not monitored by this project, were also likely altered between burn periods. Once again, these changes that were made rendered it impossible to determine if the chemical composition of the fuels had any effect on the chemical composition of the clinker and/or cement. 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. The emphasis of this project was the effect that alternative fuels had on everything from the production process 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. 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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 2 Raw Material Two 3 Raw Material Three 3 4 Raw Material Four 5 Raw Material Five Standard Cement Plant Parameters (Table A.10) 1 1 / burn Discrete During Each Burn Period Cement Plant Yes 6 Raw Material One 7 Raw Material Two 8 Raw Material Three 3 9 Raw Material Four 10 Raw Material Five Standard External Lab Parameters (Table A.12) 1 / burn Discrete During Each Burn Period External Lab No 11 Kiln Feed (Raw Material Seven) Standard Cement Plant Parameters (Table A.10) 2 2 / day Discrete Standard Sampling Period (Figure A.1) Cement Plant Yes 12 Kiln Feed (Raw Material Seven) Standard External Lab Parameters (Table A.12) 2 / day 3-Day Composites Standard Sampling Period (Figure A.1) External Lab No 13 Raw Material Six Standard Cement Plant Parameters (Table A.10) 1 1 / burn Discrete During Each Grinding Period Cement Plant Yes 14 Raw Material Six Standard External Lab Parameters (Table A.12) 1 / burn 3-Day Composites During Each Grinding Period External Lab No Notes: 1 Na 2Oeq is not collected 2 Moisture is not collected 3 Moisture and LOI is not collected 23 9 Table A.2a: 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.11) Cement Plant Yes 2 Pulverized Coal Ultimate Analysis (Table A.11) Cement Plant Yes 3 Pulverized Coal Standard Cement Plant Parameters (Table A.10) 1 Cement Plant Yes 4 Pulverized Coal Combustion Analysis (Table A.11) 2 / day 3-Day Composites Standard Sampling Period (Figure A.1) Cement Plant Yes 5 Pulverized Coal Proximate Analysis (Table A.11) External Lab No 6 Pulverized Coal Ultimate Analysis (Table A.11) External Lab No 7 Pulverized Coal Standard External Lab Parameters (Table A.12) 2 External Lab No 8 Pulverized Coal Combustion Analysis (Table A.11) 2 / day 3-Day Composites Standard Sampling Period (Figure A.1) External Lab No Notes: 1 Moisture, LOI, and Na 2Oeq is not collected 2 Moisture is not collected 24 0 Table A.2b: 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.11) External Lab No 2 Tires Ultimate Analysis (Table A.11) External Lab No 3 Tires Standard External Lab Parameters (Table A.12) 1 External Lab No 4 Tires Combustion Analysis (Table A.11) 1 / burn One Composite Sample Prepared from 8 Discrete Radial Section Samples Removed from Random Tires During Each Burn Period 2 External Lab No 5 Plastics Proximate Analysis. (Table A.11) External Lab No 6 Plastics Ultimate Analysis (Table A.11) External Lab No 7 Plastics Standard External Lab Parameters (Table A.12) 1 External Lab No 8 Plastics Combustion Analysis (Table A.11) 8 / day Discrete (Every Fourth Sample Analyzed in Duplicate) During Plastics Burn Period External Lab No 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 24 1 Table A.2c: 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.11) External Lab No 10 Broiler Litter Ultimate Analysis (Table A.11) External Lab No 11 Broiler Litter Standard External Lab Parameters (Table A.12) 1 External Lab No 12 Broiler Litter Combustion Analysis (Table A.11) 8 / day Discrete (Every Fourth Sample Analyzed in Duplicate) During Broiler Litter Burn Period External Lab No Notes: 1 To be determined for both the fuel and the fuel?s ash after combustion242 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.10) 1 2 / day Discrete Standard Sampling Period (Figure A.1) Cement Plant Yes 2 Standard External Lab Parameters (Table A.12) 2 / day Discrete Standard Sampling Period (Figure A.1) External Lab No Notes: 1 Na 2Oeq, Moisture, and LOI are not collected 24 3 Table A.4: 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.10) 1 XRF 12 / day Discrete Cement Plant Yes 2 Additional Chemical Composition: Free CaO ASTM C 114 12 / day Discrete Standard Sampling Period (Figure A.1) Cement Plant Yes 3 Clinker Phase Composition: C3S, C2S, C3A, C4AF ASTM C 150 N/A N/A N/A Cement Plant Yes 4 Clinker Phase Composition: C3S, C2S, C3A, C4AF Rietveld Analysis Cement Plant Specialty Lab No 5 Trace Element Content of Clinker: Standard External Lab Parameters (Table A.12) XRF 12 / day 1-Day Composites Standard Sampling Period (Figure A.1) External Lab No Notes: 1 Moisture and LOI are not collected 24 4 Table A.5: 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.10) 1 XRF 8 / day Discrete 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 3S, C2S, C3A, C4AF ASTM C 150 N/A N/A Cement Plant Yes 4 Clinker Phase Composition: C 3S, C2S, C3A, C4AF Rietveld Analysis 8 / day 1-Day Composites Cement Plant Specialty Lab No 5 Chemical Composition: Standard Cement Plant Parameters (Table A.10) 2 XRF 8 / day 1-Day Composites Cement Plant Yes 6 Trace Element Content of Cement: Standard External Lab Parameters (Table A.12) XRF 8 / day 1-Day Composites External Lab No 7 Additional Chemical Analysis: Total organic carbon (TOC) TOC Analyzer 8 / day 1-Day Composites Standard Sampling Period (Figure A.1) External Lab No Notes: 1 Moisture is not collected. 2 Moisture is not collected. FCaO is collected 24 5 Table A.6: 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 (m2/kg) ASTM C 185 ASTM C 204 8 / day 1-Day Composites Standard Sampling Period (Figure A.1) 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 (Figure A.1) 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 (Figure A.1) 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 (Figure A.1) Auburn University No Notes: 1 Auburn University will conduct these tests on one three-day composite sample during each burn period 24 6 Table A.7: 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 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 and 365 8 / day Single Composite Over Entire Burn Phase Notes: 1 Test will not be conducted by the cement plant Two standard concrete mixtures will be 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) 24 7 Table A.8: Analyzing Emissions Item # Material Analyzed Test Spec. Sampling Frequency Specimen Preparation Method Data Collection Period Tested by Routine? 1 Main Stack Emissions CO NOx SO2 VOC CEMS Continuous Real - Time Standard Emissions Sampling Frequency (Figure A.1) Cement Plant Yes 24 8 Table A.9: 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 24 9 Table A.10: Standard Cement Plant Parameters Parameter Analysis Technique Al2O3 CaO Fe2O3 K2O MgO Na2O Na2Oeq SiO2 SO3 ASTM C 114 and XRF Loss On Ignition Moisture ASTM C 114 Table A.11: Fuel Test Parameters Table A.12: 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 Al2O3 CaO Fe2O3 K2O MgO Na2O P2O5 SiO2 SO3 TiO2 As Ba Cd Cl Co Cr Cu Hg Mn Mo Ni Pb Sb Se Sr V Zn ASTM C 114 and XRF Loss On Ignition Moisture ASTM C 114 25 0 Table A.13: Abbreviations Abbreviation Definition % NC % Normal Consistency AEA Air entraining agent ASTM American Society for Testing and Materials C2S Dicalcium silicate C3A Tricalcium aluminate C3S Tricalcium silicate C4AF 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 25 1 1 2 3 4 1 2 3 1 2 1. Coal Only Sample Days = 2. Coal + Tires Sample Days = 3. Coal + Tires + Plastics Sample Days = 4. Coal + Tires + Broiler Litter Sample Days = Legend: - Coal only as fuel - Coal, tires, and broiler litter as fuel - Coal and tires as fuel - Collect material samples - Coal, tires, and plastics as fuel - Collect emissions samples Burn Period (Days) Post-Burn Period (Days)Fuel Type(s) Pre-Burn Period (Days) Figure A.1: Standard Sampling Period Timeline 25 2 253 Appendix B.1 Raw Data for Coal Only Burn Period B.1.1. GENERAL COMMENTS ? The raw data from the Coal Only Burn Period are presented in this appendix. ? The burn period 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 Al2O3 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 Fe2O3 10.20 0.14 NR 34.70 1.72 0.45 K2O 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 Na2O 0.38 0.00 0.01 0.00 0.03 0.00 SiO2 43.70 0.96 14.00 15.40 93.70 3.98 SO3 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 25 4 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 Al2O3 (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 Fe2O3 (wt. %) 9.96 0.13 1.89 52.83 0.91 0.74 K2O (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 Na2O (wt. %) 0.53 0.00 0.00 0.20 0.00 0.03 P2O5 (wt. %) 0.63 0.01 0.03 0.56 0.01 0.03 SiO2 (wt. %) 43.44 0.51 15.92 13.51 95.59 5.93 SO3 (wt. %) 0.30 0.12 0.29 0.69 0.25 38.60 TiO2 (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) 3 1 1 2 ND 1 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 25 5 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 Al2O3 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 Fe2O3 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 K2O 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 Na2O 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 Na2Oeq 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 SiO2 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 SO3 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-Value14/18/2006 4/19/2006 4/20/2006Property (wt. %) 25 6 257 Table B.1.4: ELR - Chemical Composition of Kiln Feed Property 3-Day Composite Al2O3 (wt. %) 3.05 CaO (wt. %) 44.18 Fe2O3 (wt. %) 2.15 K2O (wt. %) 0.33 MgO (wt. %) 1.90 Na2O (wt. %) 0.01 P2O5 (wt. %) 0.05 SiO2 (wt. %) 13.38 SO3 (wt. %) 0.35 TiO2 (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 258 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 Al2O3 24.67 CaO 13.32 Fe2O3 5.83 K2O 1.97 MgO 1.18 Na2O 0.39 SiO2 42.89 SO3 8.36 12102 Notes: 1 Value is Reported as BTU/lb Ul tim ate An aly sis Sta nd ar d P ar am ete rs Heat Value 1 Pr ox im ate An aly sis 259 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 ox im ate An aly sis Ul tim ate An aly sis Heat Value 1 260 Table B.1.7: ELR - Standard Parameters of Coal Property 3-Day Composite Al2O3 (wt. %) 25.08 CaO (wt. %) 7.53 Fe2O3 (wt. %) 7.61 K2O (wt. %) 2.58 MgO (wt. %) 1.35 Na2O (wt. %) 0.22 P2O5 (wt. %) 0.18 SiO2 (wt. %) 47.39 SO3 (wt. %) 6.95 TiO2 (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 Al2O3 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 Fe2O3 1.73 1.81 1.92 1.48 1.89 2.08 1.82 K2O 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 Na2O 0.08 0.07 0.07 0.06 0.06 0.08 0.07 SiO2 10.06 11 12.42 9.58 12.83 14.2 11.68 SO3 2.74 1.21 0.42 1.48 0.34 0.59 1.13 4/19/20064/18/2006 4/20/2006Property (wt. %) Average 26 1 262 Table B.1.9: ELR - Chemical Composition of CKD 8:00 AM 7:00 PM 7:00 AM 7:00 PM 7:00 AM 7:00 PM Al2O3 (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 Fe2O3 (wt. %) 1.97 2.03 1.96 2.27 1.93 1.88 2.01 K2O (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 Na2O (wt. %) 0.00 0.02 0.02 0.02 0.00 0.00 0.01 P2O5 (wt. %) 0.05 0.06 0.08 0.07 0.05 0.05 0.06 SiO2 (wt. %) 10.64 10.02 11.87 13.94 11.37 10.10 11.32 SO3 (wt. %) 1.54 2.59 0.53 0.77 0.85 2.32 1.43 TiO2 (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) 4 2 6 ND 3 ND 3.70 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 27 10 36 14 28 20.41 Sb (ppm) 57 52 58 47 44 72 55.10 Se (ppm) 2 2 1 ND 1 2 1.31 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 Al2O3 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 Fe2O3 3.53 3.42 3.53 3.42 3.61 3.74 3.75 3.80 K2O 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 Na2O 0.08 0.07 0.08 0.07 0.08 0.08 0.07 0.07 Na2Oeq 0.47 0.48 0.44 0.45 0.46 0.46 0.44 0.43 SiO2 21.47 21.60 21.70 21.60 21.53 21.53 21.62 21.65 SO3 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 C3A 8.20 7.90 8.00 8.10 8.00 7.50 7.90 7.80 C4AF 10.70 10.40 10.70 10.40 11.00 11.40 11.40 11.60 C3S 59.70 59.90 58.60 59.90 58.50 59.40 57.30 57.00 C2S 16.50 16.80 18.00 16.80 17.60 16.90 18.70 19.00 Property (wt. %) 4/18/2006 26 3 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 Al2O3 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 Fe2O3 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 K2O 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 Na2O 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 Na2Oeq 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 SiO2 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 SO3 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 C3A 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 C4AF 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 C3S 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 C2S 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 26 4 Table B.1.12: CPR - Chemical Composition of Clinker for 4/20/06 and 4/21/06 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 Al2O3 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 Fe2O3 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 K2O 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 Na2O 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 Na2Oeq 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 SiO2 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 SO3 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 C3A 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 C4AF 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 C3S 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 C2S 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-Value14/20/2006 4/21/2006Property (wt. %) Average 26 5 266 Table 13: ELR - Chemical Composition of Clinker Comp. 1 Comp. 2 Comp. 1 Comp. 2 Comp. 1 Comp. 2 Al2O3 (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 Fe2O3 (wt. %) 3.55 3.51 3.27 3.16 3.26 3.29 3.34 K2O (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 Na2O (wt. %) 0.05 0.02 0.00 0.01 0.00 0.01 0.01 P2O5 (wt. %) 0.09 0.09 0.08 0.08 0.08 0.08 0.08 SiO2 (wt. %) 21.95 21.64 20.84 20.68 21.53 20.77 21.24 SO3 (wt. %) 0.89 0.85 1.01 1.19 0.91 0.95 0.97 TiO2 (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) 10 8 9 9 7 9 8.65 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) 1 1 1 1 1 1 1.00 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 Average4/18/2006 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 Al2O3 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 Fe2O3 2.88 2.97 3.17 3.2 3.24 3.26 3.25 3.3 3.09 3.07 K2O 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 Na2O 0.11 0.1 0.09 0.09 0.1 0.09 0.09 0.09 0.1 0.1 Na2Oeq 0.45 0.44 0.43 0.43 0.44 0.43 0.43 0.43 0.44 0.45 SiO2 20.64 20.72 20.66 20.65 20.75 20.58 20.64 20.69 20.47 20.68 SO3 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 C3A 7.4 7.4 7.7 7.7 7.7 8.2 8.2 8.1 8.2 7.9 C4AF 8.8 9 9.6 9.7 9.9 9.9 9.9 10 9.4 9.3 C3S 61.2 58.8 53.6 54.6 53.9 52.9 52.3 53.6 57.2 56.8 C2S 13 15 18.8 18 18.9 19.1 19.7 18.9 15.5 16.5 Blaine SSA (m2/kg) 387 387 400 402 372 391 379 370 366 368 Notes: NC - Not Collected Property (wt. %) 4/18/2006 4/19/2006 26 7 Table B.1.15: CPR - Chemical Composition of Cement for 4/20/06 and 4/21/06 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 Al2O3 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 Fe2O3 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 K2O 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 Na2O 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 Na2Oeq 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 SiO2 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 SO3 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 C3A 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 C4AF 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 C3S 58 58 57 56.7 56.4 54.9 56.1 59 60.5 59.7 60.6 56.75 4.7 0.738 C2S 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 (m2/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-Value1C. V. (%)4/20/2006 4/21/2006 26 8 269 Table B.1.16: ELR - Chemical Composition of Cement Property 4/18/2006 4/19/2006 4/20/2006 Average Al2O3 (wt. %) 5.12 5.04 4.99 5.05 CaO (wt. %) 63.64 64.02 64.34 64.00 Fe2O3 (wt. %) 3.26 3.21 3.13 3.20 K2O (wt. %) 0.45 0.53 0.49 0.49 MgO (wt. %) 2.92 2.88 2.87 2.89 Na2O (wt. %) 0.05 0.00 0.00 0.02 P2O5 (wt. %) 0.08 0.08 0.08 0.08 SiO2 (wt. %) 20.56 20.62 20.42 20.53 SO3 (wt. %) 2.96 2.65 2.73 2.78 TiO2 (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 C3S (wt. %) -- -- -- 58.07 C2S (wt. %) -- -- -- 15.06 C3A (wt. %) -- -- -- 7.96 C4AF (wt. %) -- -- -- 9.74 TOC (wt. %) < 0.1 <0.1 <0.1 NA As (ppm) 9 6 9 8.00 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) 1 2 1 1.33 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 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 (m2/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 27 0 271 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 272 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 3.6 Slump (mm) 100 150 30 Unit Weight (kg/m3) 2393.7 2373.9 2449.8 Setting Time (Min.) Initial Set Final Set 211 298 318 405 218 322 Compressive Strength (MPa) 1 day 3 days 7 days 28 days 91 days 12.3 22.7 25.2 35.0 41.6 20.8 31.9 37.7 44.3 51.5 15.8 23.3 33.3 43.3 48.2 Splitting Tensile Strength (MPa) 1 day 3 days 7 days 28 days 91 days 1.7 2.4 2.6 3.2 3.7 2.5 3.3 3.7 4.1 4.3 NC NC NC NC NC Drying Shrinkage Development (% Length Change) 7 days 28 days 448 days -0.018 -0.029 CIP -0.019 -0.037 CIP NC NC NC Rapid Chloride Ion Penetration Test Electrical Conductance (Coulombs) 91 days 365 days 2651 CIP 2650 CIP 2528 CIP Notes: CIP - Collection in Progress NC - Not Collected Property AUR 273 B.1.11. EMISSIONS Table B.1.20: CPR - Emissions Time NOx(tons/ton clinker) SO2(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-04 274 Table B.1.21: CPR - Emission (Continued) Time NOx(tons/ton clinker) SO2(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-Value1 0.064 <0.006 <0.005 0.007 Notes: 1 Based on Anderson Darling Normality Test NC - Not Collected 275 Appendix B.2 Raw Data for Coal Plus Tires Burn Period B.2.1. GENERAL COMMENTS ? The raw data from the Coal plus Tires Burn Period are presented in this appendix. ? The burn period 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 276 Table B.2.2: ELR - Chemical Composition of Raw Materials al One Raw Material Two Raw Material Three Raw Material Four Raw Materi ND - Not Detected Property Raw Materi al 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: 277 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 7/11/2006 7/12/2006 7/13/2006 Average C. V. (%) Normality P-Value 1 Property (wt. %) 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 278 Table 4: ELR - Chemical Composition of Kiln Feed 279 ND - Not Detected 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: B.2.5. CHEMICAL COMPOSITION OF FUELS Table B.2.5: CPR - Chemical Composition of Coal 280 Notes: 1 Value is Reported as BTU/lb Heat Value 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 Ul ti mate An alysis St andar d Par a m e t e r s 1 P r oximate Analysis Table B.2.6: 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 1 281 Table B.2.7: 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 282 Table B.2.8: ELR - Proximate, Ultimate, and Combustion Analysis of Tires 283 Value is Reported as BTU/lb 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 Ul ti mate An alysis Heat Value 2 P r oximate Analysis Table B.2.9: ELR - Standard Parameters for Tires 284 NR - Not Reported 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 B.2.6. CHEMICAL COMPOSITION OF CEMENT KILN DUST (CKD) Table 10: 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. %) 285 Table 11: ELR - Chemical Composition of Cement Kiln Dust 286 ND - Not Detected 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 7/12/2006 7/13/2006 AverageProperty B.2.7. CHEMICAL COMPOSITION OF CLINKER Table B.2.12: 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 287 Table B.2.13: 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 7/13/2006 Property (wt. %) Average 7/14/2006 C. V. (%) Normality P-Value 1 Table B.2.14: 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 288 B.2.8. CHEMICAL COMPOSITION OF CEMENT Table B.2.15: CPR - Chemical Composition of Cement for 7/11/06 and 7/12/06 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 7/12/2006 Property (wt. %) 7/11/2006 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 289 Table B.2.16: 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 7/13/2006 7/14/2006 Property (wt. %) Average Normality P-Value 1 C. V. (%) 2 Data not normally distributed 290 Table B.2.17: 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 291 B.2.9. PHYSICAL PROPERTIES OF CEMENT Table B.2.18: CPR - Physical Properties of Cement 292 Vicat Final Set (Min) 210 240 255 235 Notes: % Exp. - % Expansion 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 Table B.2.19: 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 B.2.10. PROPERTIES OF CONCRETE Table B.2.20: Concrete Properties CPR Mix w/c=0.44 Mix w/c=0.37 Mix w/c=0.44 Total Air Content (%) 4.25 4.00 3.20 Slump (mm) 90.0 160 30 Unit Weight (kg/m 3 ) 2439 2427 2448.0 Setting Time (Min) Initial Set Final Set 218 273 239 290 247 NC Compressive Strength (MPa) 1 day 3 days 7 days 28 days 91 days 13.9 20.7 28.4 37.1 41.4 25.9 36.1 40.0 49.7 59.1 15.1 21.9 32.9 42.3 49,6 Splitting Tensile Strength (MPa) 1 day 3 days 7 days 28 days 91 days 2.0 2.3 2.8 3.3 4.0 3.0 3.7 3.9 4.3 4.9 NC NC NC NC NC Drying Shrinkage Development (% Length Change) 7 days 28 days 448 days -0.028 -0.035 CIP -0.021 -0.031 CIP NC NC NC Rapid Chloride Ion Penetration Test Electrical Conductance (Coulombs) 91 days 365 days 2930 CIP 2550 CIP 2660 CIP Notes: CIP - Collection in Progress NC - Not Collected AUR - Auburn University Result CPR - Cement Plant Result Property AUR 293 B.2.11. EMISSIONS Table B.2.21: 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-04 294 Table B.2.22: 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 295 296 Appendix B.3 Raw Data for Coal, Tires, and Plastics Burn Period B.3.1. GENERAL COMMENTS ? The raw data from the Coal, Tires, and Plastics Burn Period are presented in this appendix. ? 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 Table B.3.1: 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 Al2O3 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 Fe2O3 14.41 0.00 1.30 14.50 1.63 0.25 K2O 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 Na2O 0.42 0.03 0.10 NR NR 0.20 SiO2 43.03 2.04 13.77 24.60 95.90 13.56 SO3 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 29 7 Table B.3.2: 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 Al2O3 (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 Fe2O3 (wt. %) 12.35 0.47 3.56 34.03 0.59 0.50 K2O (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 Na2O (wt. %) 0.60 0.47 0.11 0.13 0.04 0.16 P2O5 (wt. %) 0.63 0.01 0.04 0.47 0.00 0.03 SiO2 (wt. %) 50.21 2.86 41.12 15.27 97.37 13.21 SO3 (wt. %) 0.09 0.20 0.12 0.30 0.00 41.23 TiO2 (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: ND - Not Detected 29 8 B.3.4. CHEMICAL COMPOSITION OF KILN FEED Table B.3.3: CPR - Chemical Composition of Kiln Feed 4:52 AM 1:54 PM 1:32 AM 1:40 PM 1:40 AM 1:46 PM 1:43 AM Al2O3 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 Fe2O3 1.96 1.84 1.77 1.98 1.96 1.91 1.9 1.90 4.0 0.356 K2O 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 Na2O 0.05 0.04 0.05 0.05 0.03 0.05 0.04 0.04 17.8 2 0.021 Na2Oeq 0.24 0.22 0.24 0.24 0.22 0.23 0.23 0.23 3.9 2 0.091 SiO2 13.83 13.88 13.83 13.74 13.47 13.52 13.41 13.67 1.4 0.156 SO3 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-Value1Property (wt. %) 4/3/2007 4/4/2007 4/5/2007 Average 29 9 300 Table B.3.4: ELR - Chemical Composition of Kiln Feed Property 3-Day Composite Al2O3 (wt. %) 4.91 CaO (wt. %) 65.27 Fe2O3 (wt. %) 3.01 K2O (wt. %) 0.50 MgO (wt. %) 3.35 Na2O (wt. %) 0.02 P2O5 (wt. %) 0.07 SiO2 (wt. %) 21.87 SO3 (wt. %) 0.34 TiO2 (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: NR - Not Reported 301 B.3.5. CHEMICAL COMPOSITION OF FUELS Table B.3.5: CPR - Chemical Composition of Coal 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 Al2O3 15.43 CaO 3.23 Fe2O3 36.24 K2O 1.94 MgO 1.04 Na2O 0.36 SiO2 36.17 SO3 4.40 11255 Notes: 1 Value is Reported as BTU/lb Heat Value 1 Pr ox im ate An aly sis Ul tim ate An aly sis Sta nd ar d P ar am ete rs 302 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 Pr ox im ate An aly sis Ul tim ate An aly sis Heat Value 1 303 Table B.3.7: ELR - Standard Parameters of Coal Property 3-Day Composite Al2O3 (wt. %) 21.04 CaO (wt. %) 8.25 Fe2O3 (wt. %) 15.16 K2O (wt. %) 2.49 MgO (wt. %) 1.25 Na2O (wt. %) 0.36 P2O5 (wt. %) 0.23 SiO2 (wt. %) 43.44 SO3 (wt. %) 6.50 TiO2 (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: ND - Not Detected 304 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 tim ate An aly sis Heat Value 2 Pr ox im ate An aly sis 305 Table B.3.9: ELR - Standard Parameters of Tires Property 3-Day Composite Al2O3 (wt. %) 1.15 CaO (wt. %) 1.68 Fe2O3 (wt. %) 84.72 K2O (wt. %) 0.17 MgO (wt. %) 0.33 Na2O (wt. %) 0.19 P2O5 (wt. %) 0.12 SiO2 (wt. %) 4.91 SO3 (wt. %) 0.51 TiO2 (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: NR - Not Reported 306 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 tim ate An aly sis Heat Value 2 Pr ox im ate An aly sis 307 Table B.3.11: ELR - Standard Parameters of Plastics Property 3-Day Composite Al2O3 (wt. %) 0.48 CaO (wt. %) 92.00 Fe2O3 (wt. %) 0.54 K2O (wt. %) 0.13 MgO (wt. %) 1.75 Na2O (wt. %) 0.17 P2O5 (wt. %) 0.14 SiO2 (wt. %) 2.12 SO3 (wt. %) 0.41 TiO2 (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 NR - Not Reported 308 Table B.3.12: AUR - Density of Plastics Sample # Density (kg/m3) 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 Al2O3 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 Fe2O3 1.93 1.93 1.76 1.55 1.56 1.68 1.75 1.74 K2O 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 Na2O 0.03 0.07 0.07 0.05 0.06 0.05 0.03 0.05 SiO2 12.4 13.43 14.15 9.67 9.34 10.61 11.37 11.57 SO3 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 30 9 310 Table B.3.14: ELR - Chemical Composition of Cement Kiln Dust 8:24 AM 7:38 PM 7:56 AM 7:39 PM 9:32 AM 1:47 AM Al2O3 (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 Fe2O3 (wt. %) 2.88 2.95 2.47 2.23 2.41 2.51 2.58 K2O (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 Na2O (wt. %) 0.11 0.08 0.08 0.06 0.06 0.09 0.08 P2O5 (wt. %) 0.11 0.08 0.06 0.04 0.04 0.06 0.07 SiO2 (wt. %) 19.66 17.53 14.52 12.34 14.27 15.92 15.71 SO3 (wt. %) 0.62 1.10 1.43 1.26 1.05 0.61 1.01 TiO2 (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 ND - Not Detected 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 Al2O3 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 Fe2O3 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 K2O 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 Na2O 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 Na2Oeq 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 SiO2 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 SO3 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 C3A 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 C4AF 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 C3S 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 C2S 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 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 Al2O3 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 Fe2O3 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 K2O 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 Na2O 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 Na2Oeq 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 SiO2 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 SO3 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 C3A 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 C4AF 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 C3S 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 C2S 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-Value1Average 4/5/2007 4/6/2007Property (wt. %) C. V. (%)311 312 Table B.3.17: ELR - Chemical Composition of Clinker Comp. 1 Comp. 2 Comp. 1 Comp. 2 Comp. 1 Comp. 2 Al2O3 (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 Fe2O3 (wt. %) 3.21 3.23 3.26 3.24 3.51 3.51 3.33 K2O (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 Na2O (wt. %) 0.19 0.10 0.09 0.07 0.09 0.07 0.10 P2O5 (wt. %) 0.08 0.07 0.07 0.07 0.07 0.08 0.07 SiO2 (wt. %) 21.46 21.71 21.90 21.76 21.08 21.14 21.51 SO3 (wt. %) 1.11 0.87 0.97 0.87 1.05 1.02 0.98 TiO2 (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 14 28 16 19 Ni (ppm) 18 10 21 8 26 9 15 Pb (ppm) 4 6 19 < 4 14 19 12 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 B.3.8. CHEMICAL COMPOSITION OF CEMENT Table B.3.18: CPR - Chemical Composition of Cement 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 Al2O3 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 Fe2O3 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 K2O 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 Na2O 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 Na2Oeq 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 SiO2 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 SO3 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 C3A 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 C4AF 10 10 9.8 10 10 10 10 9.6 9.2 9 10.1 9.79 3.8 <0.005 C3S 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 C2S 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 (m2/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 normally distributed NC - Not Collected Property (wt. %) Average Normality P-Value1C. V. (%)4/9/2007 4/10/2007 31 3 314 Table B.3.19: ELR - Chemical Composition of Cement Property 4/9/2007 4/9/2007 4/10/2007 Average Al2O3 (wt. %) 4.86 4.86 5.07 4.93 CaO (wt. %) 63.24 63.54 62.76 63.18 Fe2O3 (wt. %) 2.94 3.24 3.15 3.11 K2O (wt. %) 0.43 0.40 0.39 0.41 MgO (wt. %) 3.40 3.46 3.56 3.47 Na2O (wt. %) 0.11 0.07 0.20 0.13 P2O5 (wt. %) 0.07 0.06 0.06 0.06 SiO2 (wt. %) 21.60 21.17 21.77 21.51 SO3 (wt. %) 2.88 2.71 2.55 2.71 TiO2 (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 C3S (wt. %) -- -- -- 48.40 C2S (wt. %) -- -- -- 25.17 C3A (wt. %) -- -- -- 7.80 C4AF (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) < 1 1 3 2 Ni (ppm) 10 14 12 12 Pb (ppm) 8 42 30 27 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 NR - Not Reported 315 B.3.9. PHYSICAL PROPERTIES OF CEMENT Table B.3.20: CPR - Physical Properties of Cement Property 4/9/2007 4/10/2007 Average Air in Mortar (%) 6.4 6.8 6.6 Blaine Specific Surface Area (m2/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 Vicat Final Set (Min) 240 210 225 Notes: % Exp. - % 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 316 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/m3) 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 317 B.3.11. EMISSIONS Table B.3.23: CPR - Emissions Time NOx(tons/ton clinker) SO2(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 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-04 318 Table B.3.24: CPR - Emissions Time NOx(tons/ton clinker) SO2(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-Value1 0.035 <0.005 0.023 0.375 Notes: 1 Based on Anderson Darling Normality Test NC - Not Collected