PREFACE |
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xxiii | |
PREFACE TO THE FIRST EDITION |
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xxv | |
LIST OF ACRONYMS AND ABBREVIATIONS |
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xxvii | |
CHAPTER 0 HOW TO USE INDUSTRIAL ORGANIC CHEMICALS, SECOND EDITION |
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1 | (14) |
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0.1 Why this Book was Written and how it is Structured |
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1 | (2) |
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0.2 North American Industry Classification |
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3 | (1) |
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0.3 Units and Nomenclature |
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4 | (1) |
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4 | (11) |
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5 | (1) |
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6 | (3) |
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9 | (1) |
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9 | (2) |
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11 | (1) |
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0.4.6 CD-ROM and On-Line Databases |
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12 | (3) |
CHAPTER 1 THE CHEMICAL INDUSTRY |
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15 | (42) |
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15 | (5) |
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1.2 Size of the Chemical Industry |
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20 | (1) |
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1.3 Characteristics of the Chemical Industry |
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21 | (27) |
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21 | (7) |
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1.3.1.1 Realignment of Business Segments |
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26 | (2) |
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1.3.2 Participation in International Trade |
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28 | (1) |
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1.3.3 Competition from Developing Countries |
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29 | (3) |
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1.3.4 Capital Intensity and Economies of Scale |
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32 | (1) |
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1.3.5 Criticality and Pervasiveness |
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33 | (2) |
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1.3.6 Freedom of Market Entry |
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35 | (1) |
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1.3.7 Strong Health and Safety Regulation |
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36 | (5) |
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1.3.8 High Research and Development Expenditures |
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41 | (5) |
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46 | (2) |
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1.4 The Top Chemical Companies |
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48 | (2) |
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50 | (3) |
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53 | (4) |
CHAPTER 2 CHEMICALS FROM NATURAL GAS AND PETROLEUM |
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57 | (43) |
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2.1 Petroleum Distillation |
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61 | (6) |
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2.2 Petroleum Refining Reactions |
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67 | (25) |
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67 | (9) |
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2.2.1.1 Choice of Feedstock |
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70 | (1) |
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2.2.1.2 Economics of Steam Cracking |
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71 | (5) |
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2.2.1.3 Mechanism of Cracking |
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76 | (1) |
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76 | (3) |
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2.2.3 Catalytic Reforming |
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79 | (3) |
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82 | (2) |
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84 | (1) |
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2.2.6 Hydrotreating and Coking |
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84 | (2) |
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86 | (1) |
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87 | (1) |
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87 | (5) |
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2.2.9.1 Metathesis Outside the Refinery |
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89 | (1) |
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2.2.9.2 Mechanism of Metathesis |
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90 | (2) |
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2.3 The Refinery-A Perspective |
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92 | (4) |
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2.3.1 The Function of the Refinery and the Potential Petroleum Shortage |
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92 | (1) |
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2.3.2 Unleaded Gasoline and the Clean Air Act |
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93 | (3) |
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2.4 Separation of Natural Gas |
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96 | (1) |
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96 | (4) |
CHAPTER 3 CHEMICALS AND POLYMERS FROM ETHYLENE |
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100 | (67) |
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105 | (4) |
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3.1.1 Discovery of Low- and High-Density Polyethylenes |
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105 | (1) |
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3.1.2 Low-Density Polyethylene |
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106 | (1) |
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3.1.3 High-Density Polyethylene |
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107 | (1) |
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3.1.4 Linear Low-Density Polyethylene |
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108 | (1) |
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3.1.5 Very High Molecular Weight Polyethylene |
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109 | (1) |
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109 | (4) |
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3.2.1 Chlorosulfonated Polyethylene |
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109 | (1) |
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3.2.2 Ethylene-Vinyl Acetate |
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110 | (1) |
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111 | (1) |
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3.2.4 Copolymer from "Incompatible" Polymer Blends |
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111 | (1) |
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3.2.5 Ethylene-Propylene Elastomers |
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111 | (1) |
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3.2.6 Ultra-Low-Density Polyethylene |
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112 | (1) |
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3.2.7 Photodegradable Copolymers |
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112 | (1) |
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113 | (6) |
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113 | (1) |
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3.3.2 Ziegler Oligomerization of Ethylene |
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114 | (1) |
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3.3.3 Other Ethylene Oligomerization Technologies |
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115 | (1) |
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3.3.4 The Shell Higher Olefins Process (SHOP) |
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116 | (3) |
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119 | (2) |
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121 | (3) |
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124 | (2) |
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126 | (6) |
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127 | (2) |
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3.7.2 Proposed Non-Ethylene Oxide Processes for Ethylene Glycol Production |
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129 | (3) |
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132 | (3) |
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135 | (2) |
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3.10 Major Chemicals from Ethylene-A Summary |
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137 | (2) |
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3.11 Lesser Volume Chemicals from Ethylene |
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139 | (1) |
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3.11.1 Hydroformylation-Propionaldehyde, Propionic Acid, and n-Propanol |
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140 | (1) |
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141 | (1) |
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3.11.3 Acetaldehyde Chemistry |
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142 | (4) |
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146 | (1) |
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3.11.5 Ethylenediamine and Related Compounds |
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147 | (2) |
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3.11.6 Ethylene Oxide and Ethylene Glycol Derivatives |
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149 | (1) |
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149 | (1) |
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3.11.6.2 Glycol Ethers and Esters |
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149 | (1) |
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3.11.6.3 Ethylene Carbonate |
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150 | (3) |
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3.11.6.4 Aminoethyl Alcohols (Ethanolamines) and Derivatives |
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153 | (1) |
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154 | (1) |
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155 | (1) |
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3.11.6.7 Ethylene Glycol Derivatives |
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156 | (2) |
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3.11.7 Vinyl Chloride and Ethylene Dichloride Derivatives |
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158 | (1) |
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3.11.8 Vinyl Fluoride and Vinylidene Fluoride |
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159 | (1) |
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3.11.9 Ethylene Dibromide |
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160 | (1) |
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3.11.10 Ethanol Derivatives |
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161 | (1) |
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3.11.11 Vinyl Esters and Ethers |
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162 | (1) |
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163 | (4) |
CHAPTER 4 CHEMICALS AND POLYMERS FROM PROPYLENE |
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167 | (56) |
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4.1 On-Purpose Propylene Production Technologies and Propane Dehydrogenation |
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168 | (1) |
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4.2 Propylene via Deep Catalytic Cracking |
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169 | (1) |
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4.3 Propylene via Olefin Metathesis |
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169 | (2) |
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4.4 Propylene via Selective C4C5 Cracking |
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171 | (1) |
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4.5 Main Polymers and Chemicals from Propylene |
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172 | (3) |
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4.5.1 Propylene Polymers and Copolymers |
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172 | (3) |
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175 | (1) |
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176 | (5) |
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181 | (3) |
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4.8.1 Uses of Acrylonitrile |
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183 | (1) |
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4.9 Cumene, Cumene Hydroperoxide, and Phenol |
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184 | (3) |
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4.10 Acetone and Isopropanol |
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187 | (1) |
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4.10.1 Methyl Methacrylate |
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188 | (5) |
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4.10.2 Methyl Isobutyl Ketone and other Acetone Derivatives |
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193 | (2) |
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195 | (3) |
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4.11.1 Propylene Oxide Applications |
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198 | (1) |
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4.11.2 Projected Propylene Oxide-Propylene Glycol Processes |
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199 | (1) |
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4.11.3 Other Novel Syntheses of Propylene Oxide |
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200 | (1) |
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4.11.3.1 Direct Oxidation |
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200 | (1) |
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4.11.3.2 Use of Peracids or Hydrogen Peroxide |
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201 | (1) |
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4.11.3.3 Electrochemical Processes |
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202 | (2) |
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4.11.3.4 Biotechnological Approaches |
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204 | (1) |
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4.12 n-Butyraldehyde and Isobutyraldehyde |
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205 | (2) |
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4.12.1 Uses for Butyraldehyde and Isobutyraldehyde |
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207 | (1) |
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4.12.2 Other Oxo Products |
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208 | (1) |
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4.13 Major Chemicals from Propylene-A Perspective |
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209 | (2) |
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4.14 Lesser Volume Chemicals from Propylene |
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211 | (1) |
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4.14.1 Allyl Chloride and Epichlorohydrin |
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211 | (3) |
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214 | (1) |
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215 | (1) |
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216 | (2) |
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4.14.5 Acrylonitrile Derivatives |
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218 | (1) |
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218 | (5) |
CHAPTER 5 CHEMICALS AND POLYMERS FROM THE C4 STREAM |
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223 | (32) |
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5.1 Chemicals and Polymers from Butadiene |
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226 | (16) |
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5.1.1 Acrylonitrile-Butadiene-Styrene Resins (ABS) |
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230 | (1) |
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5.1.2 Hexamethylenediamine |
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231 | (5) |
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5.1.3 Lesser Volume Chemicals from Butadiene |
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236 | (7) |
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236 | (1) |
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5.1.3.2 Dimerization and Trimerization |
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237 | (2) |
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5.1.3.3 Diels-Alder Reactions |
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239 | (1) |
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240 | (1) |
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241 | (1) |
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5.1.3.6 trans-1,4-Hexadiene |
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241 | (1) |
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5.1.3.7 Dimethyl-2,6-naphthalene Dicarboxylate |
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241 | (1) |
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5.1.3.8 Butadiene Monoepoxide |
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241 | (1) |
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5.2 Chemicals and Polymers from Isobutene |
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242 | (6) |
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5.2.1 Methyl tert-butyl Ether |
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243 | (1) |
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244 | (1) |
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5.2.3 Polyisobutenes and Isobutene Oligomers and Polymers |
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244 | (1) |
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245 | (1) |
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5.2.5 Methyl Methacrylate |
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245 | (1) |
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5.2.6 Lesser Volume Chemicals from Isobutene |
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245 | (3) |
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5.3 Chemicals and Polymers from 1- and 2-Butenes |
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248 | (1) |
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5.4 Chemicals from η-Butane |
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249 | (2) |
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249 | (1) |
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249 | (2) |
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251 | (4) |
CHAPTER 6 CHEMICALS AND POLYMERS FROM THE C5 STREAM |
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255 | (12) |
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6.1 Separation of the C5 Stream |
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256 | (3) |
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259 | (4) |
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6.3 Cyclopentadiene and Dicyclopentadiene |
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263 | (2) |
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6.4 Pentene-1 and Piperylene |
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265 | (1) |
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266 | (1) |
CHAPTER 7 CHEMICALS AND POLYMERS FROM BENZENE |
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267 | (45) |
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269 | (16) |
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275 | (1) |
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276 | (5) |
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277 | (1) |
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7.1.2.2 Polvcarbonate Resins |
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277 | (3) |
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7.1.2.3 Lesser Volume Uses for Bisphenol A |
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280 | (1) |
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281 | (2) |
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283 | (1) |
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7.1.5 Chlorinated Phenols |
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283 | (1) |
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7.1.6 2,6-Xylenol and Cresols |
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284 | (1) |
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7.1.7 Aniline from Phenol |
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284 | (1) |
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285 | (9) |
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285 | (5) |
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7.2.1.1 Nylons from Adipic Acid |
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289 | (1) |
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290 | (4) |
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294 | (2) |
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7.3.1 4,4'-Diphenylmethane Diisocyanate (MDI) |
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296 | (3) |
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299 | (2) |
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301 | (1) |
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301 | (1) |
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302 | (6) |
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308 | (1) |
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309 | (3) |
CHAPTER 8 CHEMICALS AND POLYMERS FROM TOLUENE |
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312 | (8) |
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8.1 Hydrodealkylation and Disproportionation |
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313 | (1) |
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314 | (1) |
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8.3 Dinitrotoluene and Toluene Diisocyanate |
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314 | (2) |
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8.4 Lesser Volume Chemicals from Toluene |
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316 | (2) |
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318 | (2) |
CHAPTER 9 CHEMICALS AND POLYMERS FROM XYLENES |
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320 | (18) |
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9.1 o-Xylene and Phthalic Anhydride |
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322 | (1) |
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9.1.1 Uses of Phthalic Anhydride |
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323 | (4) |
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9.2 m-Xylene and Isophthalic Acid |
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327 | (2) |
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9.2.1 Uses of Isophthalic Acid |
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328 | (1) |
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9.3 p-Xylene and Terephthalic Acid-Dimethyl Terephthalate |
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329 | (6) |
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9.3.1 Oxidation of p-Xylene |
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329 | (2) |
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9.3.2 Alternate Sources for Terephthalic Acid |
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331 | (1) |
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9.3.3 Poly(ethylene terephthalate) |
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332 | (2) |
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9.3.4 Lower Volume Polymers from Terephthalic Acid |
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334 | (1) |
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9.4 Major Chemicals from Xylenes: A Summary |
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335 | (1) |
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336 | (2) |
CHAPTER 10 CHEMICALS FROM METHANE |
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338 | (1) |
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338 | (3) |
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10.2 Halogenated Methanes |
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341 | (1) |
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342 | (1) |
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343 | (1) |
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343 | (1) |
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10.2.4 Tetrachloromethane and Carbon Disulfide |
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344 | (3) |
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347 | (1) |
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347 | (2) |
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349 | (3) |
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10.3.2 Lesser Uses for Acetylene |
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352 | (1) |
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353 | (1) |
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10.4.1 Steam Reforming of Methane |
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354 | (1) |
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10.4.2 Variants of Steam Reforming |
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355 | (1) |
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10.4.3 Partial Oxidation of Hydrocarbons |
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356 | (1) |
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357 | (1) |
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357 | (1) |
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10.5 Chemicals from Synthesis Gas |
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358 | (1) |
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10.5.1 Ammonia and Its Derivatives |
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358 | (2) |
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10.5.1.1 Urea and Melamine Resins |
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360 | (2) |
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362 | (2) |
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364 | (1) |
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365 | (3) |
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10.5.2.3 Acetic Anhydride |
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368 | (2) |
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10.5.2.4 Methanol to Gasoline |
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370 | (1) |
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10.5.2.5 Methanol to Olefins |
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371 | (2) |
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10.5.2.6 Lower Volume and Proposed Uses for Methanol |
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373 | (2) |
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10.5.2.7 C1-Based Development Processes |
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375 | (2) |
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10.6 Carbon Monoxide Chemistry |
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377 | (1) |
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10.6.1 Proposed Chemistry Based on Carbon Monoxide |
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378 | (4) |
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382 | (1) |
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10.7.1 Sasol GTL Technology |
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382 | (1) |
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10.7.2 Shell Middle Distillate Synthesis |
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383 | (1) |
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10.7.3 Other GTL Technologies |
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383 | (1) |
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384 | (3) |
CHAPTER 11 CHEMICALS FROM ALKANES |
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387 | (1) |
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11.1 Functionalization of Methane |
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388 | (1) |
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11.1.1 Methane to Methanol-Formaldehyde |
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388 | (1) |
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11.1.2 Dimerization of Methane |
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389 | (1) |
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11.1.3 Aromatization of Methane |
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390 | (1) |
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11.2 Functionalization of C2-C4 Alkanes |
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391 | (1) |
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11.2.1 Oxidation of C2-C4 Alkanes |
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391 | (2) |
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11.2.2 Dehydrogenation of C2-C4 Alkanes |
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393 | (1) |
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11.2.3 Aromatization of C2-C4 Alkanes |
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394 | (1) |
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394 | (1) |
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395 | (4) |
CHAPTER 12 CHEMICALS FROM COAL |
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399 | (1) |
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12.1 Chemicals from Coke Oven Distillate |
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400 | (4) |
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12.2 The Fischer-Tropsch Reaction |
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404 | (2) |
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406 | (1) |
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12.4 Substitute Natural Gas (SNG) |
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407 | (1) |
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12.5 Synthesis Gas Technology |
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407 | (1) |
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408 | (1) |
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12.7 Coal and the Environment |
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409 | (1) |
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409 | (2) |
CHAPTER 13 FATS AND OILS |
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411 | (5) |
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416 | (3) |
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13.2 Fatty Nitrogen Compounds |
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419 | (2) |
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421 | (2) |
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13.4 Aminoamides and Imidazolines |
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423 | (1) |
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13.5 Azelaic, Pelargonic, and Petroselinic Acids |
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423 | (1) |
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424 | (2) |
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426 | (1) |
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426 | (2) |
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428 | (1) |
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13.10 Alcoholysis of Fats and Oils |
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428 | (1) |
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429 | (1) |
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13.11 The Future of Fat and Oil Chemistry |
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430 | (1) |
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13.11.1 Non-Caloric Fat-Like Substances |
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430 | (1) |
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13.11.2 Alkyl Polyglycosides |
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430 | (1) |
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13.11.3 Fatty Acid-Based Fuels and Lubricants |
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431 | (1) |
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432 | (3) |
CHAPTER 14 CARBOHYDRATES |
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435 | (24) |
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435 | (7) |
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442 | (1) |
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443 | (3) |
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446 | (3) |
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449 | (1) |
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14.5 Fermentation and Biotechnology |
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450 | (3) |
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453 | (1) |
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454 | (1) |
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14.5.3 Proteins by Recombinant DNA Technology |
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455 | (1) |
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14.5.4 A Fermentation Scenario |
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455 | (1) |
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14.5.5 Can Ethanol Be Justified as a Fuel? |
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456 | (1) |
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457 | (2) |
CHAPTER 15 HOW POLYMERS ARE MADE |
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459 | (5) |
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464 | (1) |
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465 | (4) |
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15.3 Step- and Chain-Growth Polymerizations |
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469 | (2) |
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15.3.1 Free Radical Polymerization |
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471 | (2) |
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473 | (2) |
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475 | (2) |
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477 | (1) |
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15.3.5 Polymerization Procedures |
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478 | (2) |
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15.3.6 Ionic Polymerization |
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480 | (6) |
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486 | (1) |
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486 | (3) |
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489 | (1) |
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15.3.10 Metal Complex Catalysts |
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489 | (4) |
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15.3.11 Metal Oxide Catalysts |
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493 | (1) |
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15.3.12 Metallocene and Other Single-Site Catalysts |
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494 | (4) |
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15.3.12.1 Single-Site Nonmetallocene Catalysts |
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498 | (1) |
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15.3.12.2 Late Transition Metal Catalysts |
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498 | (2) |
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15.3.12.3 Commercial Prospects |
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500 | (1) |
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15.4 Examples of Step Polymerization |
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501 | (1) |
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15.4.1 Phenoplasts and Aminoplasts |
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501 | (2) |
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503 | (3) |
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506 | (2) |
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15.4.4 Dendritic and Hyperbranched Polymers |
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508 | (4) |
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512 | (1) |
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512 | (4) |
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15.5.2 Glass Transition Temperature, Crystalline Melting Point, and Softening Temperature |
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516 | (1) |
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15.5.3 Molecular Cohesion |
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517 | (1) |
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15.5.4 Stress-Strain Diagrams |
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518 | (2) |
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520 | (1) |
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521 | (6) |
CHAPTER 16 INDUSTRIAL CATALYSIS |
|
527 | (1) |
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|
528 | (1) |
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16.1.1 Reaction Velocity and Selectivity |
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|
529 | (2) |
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16.1.2 Recovery of Unchanged Catalyst |
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|
531 | (1) |
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16.1.3 Catalyst Deactivation |
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|
532 | (1) |
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16.1.4 Access to Nonequilibrium Products |
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|
532 | (1) |
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16.2 Homogeneous and Heterogeneous Catalysis |
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|
533 | (1) |
|
16.2.1 Reactors for Heterogeneous Catalysts |
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|
534 | (1) |
|
16.2.2 "Immobilization" of Homogeneous Catalysts |
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|
535 | (1) |
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|
536 | (3) |
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16.4 Catalysis by Acids and Bases |
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|
539 | (4) |
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16.5 Dual Function Catalysis |
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|
543 | (1) |
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16.6 Catalysis by Metals, Semiconductors, and Insulators |
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|
544 | (1) |
|
16.6.1 Catalysts for Automobile Emission Control |
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|
545 | (1) |
|
16.7 Coordination Catalysis |
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|
546 | (1) |
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16.7.1 Catalysts for Stereoregular Compounds |
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|
547 | (2) |
|
16.7.2 Asymmetric Synthesis |
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|
549 | (1) |
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|
550 | (2) |
|
16.8.1 Catalytic Antibodies |
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|
552 | (1) |
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16.9 Shape-Selective Catalysts |
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|
553 | (3) |
|
16.10 Phase-Transfer and Fluorous Biphase Catalysis |
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|
556 | (2) |
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16.11 Catalysts of the Future |
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|
558 | (1) |
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|
558 | (1) |
|
16.11.2 Higher Selectivities |
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|
559 | (1) |
|
16.11.3 Catalysts with Greater Activity |
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|
559 | (1) |
|
16.11.4 Pollution Problems |
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|
560 | (1) |
|
16.11.5 Catalysts for New Reactions |
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|
560 | (1) |
|
16.11.6 Catalysts that Mimic Natural Catalysts |
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|
560 | (1) |
|
16.11.7 Catalyst Discovery via High Throughput Experimentation |
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|
561 | (1) |
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|
562 | (5) |
CHAPTER 17 SUSTAINABILITY AND GREEN CHEMISTRY |
|
567 | (2) |
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|
569 | (1) |
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|
570 | (1) |
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|
570 | (1) |
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|
571 | (1) |
|
17.1.3.1 Photovoltaic Cells |
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|
571 | (1) |
|
17.1.3.2 Artificial Photosynthesis |
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|
572 | (2) |
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|
574 | (1) |
|
17.1.5 The Hydrogen Economy |
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|
575 | (1) |
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|
576 | (4) |
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|
580 | (1) |
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|
581 | (4) |
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|
585 | (2) |
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|
587 | (1) |
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|
587 | (1) |
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17.2.3.2 Nonpesticide Lipophiles |
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|
588 | (1) |
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|
589 | (1) |
|
17.2.4.1 Sulfur Dioxide and Particulates |
|
|
589 | (1) |
|
17.2.4.2 Automobile Exhaust Emissions |
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|
590 | (3) |
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|
593 | (1) |
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|
594 | (1) |
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17.2.6.1 Waste Prevention |
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|
595 | (1) |
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|
595 | (1) |
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17.2.6.3 Combustion-Incineration |
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|
596 | (2) |
|
17.2.6.4 Sanitary Landfill |
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|
598 | (1) |
|
17.2.7 Petrochemical Industry Wastes |
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|
599 | (1) |
|
17.2.8 Other Environmental Problems |
|
|
600 | (1) |
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|
601 | (1) |
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17.3.1 The Decline in Acetylene Chemistry |
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|
602 | (1) |
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|
603 | (1) |
|
17.3.3 Replacement of Phosgene |
|
|
603 | (1) |
|
17.3.4 Monomethylation by Dimethyl Carbonate |
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|
604 | (1) |
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17.3.5 Liquid and Supercritical Carbon Dioxide and Water |
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|
605 | (2) |
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|
607 | (1) |
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|
608 | (1) |
|
17.3.8 Paired Electrosynthesis |
|
|
608 | (1) |
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17.3.9 Sertraline Synthesis |
|
|
609 | (2) |
|
17.3.10 Catalytic Dehydrogenation of Diethanolamine |
|
|
611 | (1) |
|
17.3.11 Genetic Manipulation |
|
|
611 | (1) |
|
17.3.12 Polyhydroxyalkanoates |
|
|
612 | (1) |
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|
613 | (1) |
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|
614 | (6) |
APPENDIX 1 A NOTE ON COST CALCULATIONS |
|
620 | (4) |
APPENDIX 2 UNITS AND CONVERSION FACTORS |
|
624 | (2) |
APPENDIX 3 SPECIAL UNITS IN THE CHEMICAL INDUSTRY |
|
626 | (3) |
INDEX |
|
629 | |