Report No. 61A CHLORINE Supplement A by YEN CHEN YEN May 1074 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE I I MENLO PARK, CALIFORNIA
CONTENTS 1 2 3 INTRODUCTION... 1 SUMMARY... 3 INDUSTRY STATUS... 13 Production and Production Capacity... 13 The Problem of Chlorine-Alkali Balance... 26 4 COMPARISON OF PROCESSES... Comparison of Diaphragm and Mercury for Salt Electrolysis... Comparison of Three Processes Coproducing Chlorine and Soda Ash... Comparison of Processes for Production of Caustic Soda and Soda Ash... Comparison of Processes for Converting Hydrogen Chloride to Chlorine... 29 29 35 38 39 5 6 CHLORINE FROM SALT ELECTROLYSIS IN DIAPHRAGM CELLS Review of Processes................ Commercial Diaphragm Cells............ Chlorine from Salt Electrolysis in Diaphragm Cells Process Description............... Process Discussion............... Cost Estimate.................. Metal Anodes Versus Graphite Anodes........ Salt Electrolysis in Diaphragm Cells for Production Caustic Soda with Low Salt Content........ CHLORINE FROM SALT ELECTROLYSIS IN MERCURY CELLS... Review of Processes... Mercury Cells... The Mercury Pollution Problem... Characteristics of Modern Mercury Cells... Evaluation of a Process for Manufacturing Chlorine by Salt Electrolysis Using Mercury Cells... Process Description... Process Discussion... Cost Estimate... Metal Anodes Versus Graphite Anodes........... 43.... 60.... 65.... 65.... 78.... 79.... 86 of.... 43 86 91 91 91 99 112 114 114 130 131 138 vii
CONTENTS 7 CHLORINE FROM HYDROGEN CHLORIDE.......,...... 141 Preparation of Feed.................... 141 Review of Processes for Converting HCl to Chlorine.... 141 Chlorine from Hydrogen Chloride by Oxidation with Nitrogen................ 151 Process Description................... 151 Process Discussion......,............ 159 Cost Estimate...................... 159 Chlorine from Electrolysis of Hydrochloric Acid...,.. 166 Chlorine from Oxidation of Hydrogen Chloride Using a Heterogeneous Catalyst................. 166 8 CHLORINE AS A COPRODUCT OF SODIUM CARBONATE,,...... 175 Review of Processes.................... 175 Modified Solvay Process................. 175 Conventional Solvay Process.,............. 177 Combined Electrolysis/Solvay Process.......... 178 Evaluation of Modified Solvay Process (Dual Solvay Process...................... 181 Manufacture of Chlorine from Ammonium Chloride...... 188 Integration of Modified Solvay Process and Chlorine Production from Ammonium Chloride............. 198 Conversion of Conventional Solvay Process to Modified Solvay Process.................. 198 Chlorine from Electrolysis with Coproduction of Sodium Carbonate by Carbonation.............. 200 Chlorine from Salt Electrolysis Integrated with Solvay Process...................... 203 APPENDIX A DESIGN AND COST BASIS.............. 211 APPENDIX B POWER COST FOR ELECTROCHEMICAL INDUSTRIES.... 215 APPENDIX C STANDARDS AND REGULATIONS IN MERCURY EMISSION.. 221 CITED REFERENCES....................... 223 PATENT REFERENCES BY COMPANY................. 247 viii
ILLUSTRATIONS 4.1 Chlorine from Salt Electrolysis Comparison of Fixed Capital Investment for Diaphragm and Mercury.......... 30 4.2 4.3 4.4 4.5 4.6 4.7 4.8 5.1 5.2 6.1 6.2 7.1 7.2 8.1 8.2 Chlorine from Salt Electrolysis Comparison of Production Costs for Diaphragm Cell Process and Mercury at Different Capacities and Power Rates............... 31 Chlorine from Salt Electrolysis Effect of Unit Prices of Steam and Power on Relative Production Costs of Diaphragm and Mercury.................. 32 Chlorine from Salt Electrolysis Production Cost of Diaphragm and Mercury Using Brine as Raw Material........ 33 Comparison of Fixed Capital for Processes Producing Chlorine and Soda Ash.........,........ 36 Comparison of Production Costs for Processes Producing Chlorine and Soda Ash.................. 37 Capital Investment (Battery Limits plus Utilities) of Processes for Converting HCl to Chlorine....... 40 Production Cost of Chlorine from Hydrogen Chloride... 41 Chlorine from Salt Electrolysis Diaphragm................. 69 Chlorine from Salt Electrolysis-Diaphragm Production Costs at Different Production Levels..... 85 Chlorine from Salt Electrolysis Mercury.................. 121 Chlorine from Salt Electrolysis-Mercury Production Costs at Different Production Levels..... 137 Chlorine from HCl by Oxidation with Nitrogen Oxides ascatalyst... 155 Chlorine from HCl by Oxidation with Nitrogen Oxides as Catalyst Production Costs at Different Production Levels..... 165 Crystallization of Ammonium Chloride.......... 182 Chlorine from Ammonium Chloride Production Costs at Different Production Levels..... 197 ix
2.1 2.2 3.1 3.2 3.3 3.4 3.5 5.1 5.2 5.3 5.4 5.5 5.6 5.7 5.8 5.9 5.10 5.11 5.12 Comparison of Costs of Processes for Making Chlorine from Salt... Comparison of Costs of Processes for Recovery of Chlorine from Hydrogen Chloride... Chlorine Producers in the United States... Chlorine Producers in Canada... Chlorine Producers in Europe Except Eastern Bloc... Chlorine Producers in Japan... Chlorine Producers in Other Countries... Met al Anodes Construction Features of Metal Anodes in Diaphragm Cells Bipolar Diaphragm Cells Diaphragm Cells with Graphite Anodes Diaphragms for Chlorine-Alkaline Cells Other Construction Features of Diaphragm Cells Operation of Diaphragm Cells Brine Purification Patent Summary... Caustic Soda Recovery and Purification Chlorine Purification, Drying, and Compression Patent Summary.... i... Recovery or Removal of Chlorine from a Dilute Chlorine Stream... Electrolysis of Dilute Brine or Seawater 5 6 14 17 18-22 24 44 47 49 50 57 54 55 56 57 58 59 60 Xi
5.13 5.14 5.15 5.16 5.17 5.18 5.19 5.20 6.1 6.2 6.3 6.4 6.5 6.6 6.7 Characteristics of Some Diaphragm Cells Available for License................. Chlorine from Salt Electrolysis--Diaphragm Important Operation Data................ Chlorine by Salt Electrolysis--Diaphragm Major Process Equipment and Utilities Summary..... Chlorine from Salt Electrolysis--Diaphragm Composition of Stream Flows.............. Chlorine from Salt Electrolysis--Diaphragm Waste Streams..................... Chlorine by Salt Electrolysis--Diaphragm Total Capital Investment................ Chlorine by Salt Electrolysis-Diaphragm Production Costs.................... Cost for Purification of Caustic Soda......... Metal Anodes in Mercury Cells Patent Summary..................... Graphite Electrodes for Mercury Cells Patent Summary..........,.......... Electrode Spacing of Mercury Cells Patent Summary..................... Base and Cover of Mercury Cell Patent Summary..................... Electrolyte Movement in Cells Patent Summary..................... Mercury Flow in Cells Patent Summary....,................ Other Features in Mercury Cells Patent Summary..................... 61 67 68. 73 77 81 83 88 92 93 94 95 95 96 97 xii
6.8 Additives to Mercury Cells Patent and Literature Summary............. 97 6.9 Denuding Vessel Patent Summary..................... 98 6.10 Mercury Purification Patent Summary..................... 98 6.11 6.12 6.13 6.14 6.15 6.16 6.17 6.18 6.19 6.20 6.21 6.22 6.23 6.24 6.25 Brine Treatment for Mercury Cells Patent Summary..................... 100 Special Mercury Cells Patent Summary..................... 101 Removal of Mercury from Gas Streams Patent and Literature Summary............. 103 Removal of Mercury from Caustic Soda Patent and Literature Summary............. 105 Removal of Mercury from Circulating Brine Patent and Literature Summary............. 106 Removal of Mercury from Sludges Patent and Literature Summary............. 107 Removal of Mercury from Aqueous Waste Effluent Patent and Literature Summary............. 108 Estimated Mercury Loss.......,......... 111 Some Hoechst-Uhde Mercury Cells............ 113 Chlorine from Salt Electrolysis-Mercury Important Operating Conditions............, 118 Chlorine from Salt Electrolysis--Mercury Major Process Equipment and Utilities Summary..... 119 Chlorine from Salt Electrolysis--Mercury Composition of Stream Flows.............. 125. Chlorine by Salt Electrolysis-Mercury Waste Streams..... ;............... 129 Chlorine from Salt Electrolysis--Mercury Total Capital Investment................ 133 Chlorine from Salt Electrolysis-Mercury Production Costs.................... 135 Xiii
7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8 7.9 7.10 7.11 7.12 Concentrated Hydrochloric Acid from a Dilute HCl Gas Stream or Dilute Acid Patent Summary..................... 142 Anhydrous Hydrogen Chloride from a Solution or a Dilute HCl Gas Stream Patent Summary..................... 143 Chlorine from HCl Electrolysis Patent Summary..................... 145 Chlorine from Oxidation of HCl Using Heterogeneous Catalyst Patent Summary..................... 147 Chlorine from Oxidation with Nitric Acid or Nitrogen Oxides in Homogeneous Phase Patent Summary..................... 149 Other Processes for Converting Hydrogen Chloride to Chlorine.................. 151 Chlorine from HCl by Oxidation with Nitrogen Reaction Conditions.................. 153 Chlorine from HCl by Oxidation with Nitrogen Major Process Equipment and Utilities Summary..... 154 Chlorine from HCl by Oxidation with Nitrogen Composition of Stream Flows.............. 157 Chlorine from HCl by Oxidation with Nitrogen Waste Streams..................... 158 Chlorine 'from HCl by Oxidation with Nitrogen Total Capital Investment................ 161 Chlorine from HCl by Oxidation with Nitrogen Production Costs.................... 163 7.13 Chlorine from Electrolysis of Hydrochloric Acid Total Capital Investment................ 167 xiv
7. 14 7.15 7.16 8.1 8.2 8.3 8.4 8.5 8.6 8.7 X.8 8.9 8.10 8.11 8.12 Chlorine from Electrolysis of Hydrochloric Acid Production Costs.................... 169 Chlorine from Hydrogen Chloride Oxidation Using a Heterogeneous Catalyst Total Capital Investment................ 173 Chlorine from Hydrogen Chloride Oxidation Using a Heterogeneous Catalyst Production Costs.................... I 7;: Chlorine from Ammonium Chloride Patent Summary..................... 176 Electrolysis of Ammonium Chloride Patent Summary ;.................... 177 Processes Useful in the Disposal of Waste from Solvay Soda Production Patent and Literature Summary............. 179 Sodium Carbonate by Electrolysis or from Caustic Soda Patent Summary..................... 1 X1) Modified Solvay Process Using Solid Salt Total Capital Investment................ 183 Modified Solvay Process Using Solid Salt Production Costs.....,.............. Chlorine from Ammonium Chloride Using Air Total Capital Investment................ Chlorine from Ammonium Chloride Using Air Production Costs.................... 191 Chlorine from Ammonium Chloride Using Oxygen Total Capital Investment................ 193 Chlorine from Ammonium Chloride Using Oxygen Production Costs.................... 195 Capital Expenditure and Change of Production for Conversion of an Existing Soda Plant from Conventional Solvay Process to Modified Process........... 399 Payout in Converting Conventional Solvay Soda Process to Modified Solvay Process............... 200 1x5 1X9 xv
8.13 Chlorine and Soda Ash by Electrolysis and Carbonation Total Capital Investment................ 201 8.14 Chlorine and Soda Ash by Electrolysis and Carbonation Production Costs.................... 205 8.15 Chlorine by Salt Electrolysis Integrated with the Solvay Process for Making Soda Ash Capital Investment................... 208 8.16 Chlorine by Salt Electrolysis Integrated with the Solvay Process for Making Soda Ash Production Costs.................... 209 xvi