Report No. 63 SULFUR DIOXIDE REMOVAL FROM STACK GASES by EARL D. OLIVER July 1970 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA
CONTENTS 1 INTRODUCTION.......,................. 2 SUMMARY........................... 3 INDUSTRY STATUS... History... Plants... Pilot Plants... Promotional Agreements... Potential Recovery... Potential Markets... Outlook....... 4 GENERAL CONSIDERATIONS... Power Generation and Gas Composition... Recovery Process Power Requirements... Process Materials Costs... Design Criteria... Attractiveness Criteria... 5 REMOVAL OF FLY ASH... Design Requirements... Wet Scrubbers... Cyclone Separators... Electrostatic Precipitators... Combinations of Cyclone Separators and Electrostatic Precipitators... Cost Estimates... Capital Costs... Production Costs... 6 ADDITIVE INJECTION PROCESS... Introduction... Chemistry... Review of Processes... Process Description... Process Discussion... Cost Estimates... Capital Costs... Production Costs... 1 3 21 21 22 22 28 28 29 32 35 35 44 46 46 48 53 53 57 58 61 64 64 64 70 75 75 76 78 81 86 93 93 94 V
CONTENTS 7 CEMENT SULFURIC ACID PROCESSES... 92 Introduction... 99 Chemistry... 101 Review of Commercial Processes... 103 Process Description... 107 Process Discussion... 112 Cost Estimates... 114 Capital Costs Production Cost;... 8 ALKALIZED ALUMINA PROCESS... 121 114 114 Introduction... :... 121 Chemistry... 121 Review of Processes... 123 Process Description... 123 Process Discussion... 127 Cost Estimates... 131 Capital Costs... 131 Production Costs... 134 9 CATALYTIC OXIDATION PROCESSES................ 135 Introduction... 135 Chemistry... 135 Review of Processes... 137 Process Description... 140 Process Discussion... 144 Cost Estimates... 146 Capital Costs... 146 Production Costs... 146 10 CARBON ADSORPTION PROCESSES... 153 Introduction... 153 Chemistry... 153 Review of Processes... 155 Process Description... 160 Process Discussion... 166 Cost Estimates... 167 Capital Costs... 167 Production Costs... 167 vi
CONTENTS 11 12 13 ALKALI SULFITE ABSORPTION PROCESSES... 171 Chemistry... 171 Review of Processes... 174 Process Description... 177 Process Discussion... 182 Cost Estimates... 187 Capital Costs... 187 Production Costs... 192 Sodium Sulfite System... 198 MODIFIED CHAMBER PROCESS... 205 Introduction... 205 Chemistry... 205 Review of Processes... 207 Process Description... 208 Process Discussion... 214 Cost Estimates... 217 Capital Costs... 217 Production Costs... 218 OTHER PROCESSES... 223 Introduction... 223 Dry Metal Oxides and Hydroxides... 223 Aqueous Scrubbing... 229 Irorganic Liquid Processes... 243 Organic Liquid Processes... 243 Inorganic Solids Other Than Oxides... 247 Organic Solid Processes... 247 Direct Reduction Processes... 247 Physical Methods of Separation... 251 APPENDIX A DESIGN AND COST BASIS... APPENDIX B PHYSICAL DATA... APPENDIX C RAW MATERIAL AND PRODUCT SPECIFICATIONS... APPENDIX D SAFETY AND HANDLING... CITED REFERENCES... PATENT REFERENCES BY COMPANY... 253 257 259 261 263 299 vii
ILLUSTRATIONS 4.1 4.2 5.1 5.2 5.3 5.4 6.1 6.2 6.3 7.1 8.1 8.2 9.1 9.2 10.1 11.1 11.2 11.3 11.4 11.5 11.6 12.1 12.2 Comparison of Plant Size and Heat Rate... Stack Gas Rates... Proposed Revision to ASME Model Ordinance for Permissible Fly-Ash Emissions... Purchase Cost of Dry Centrifugal Collectors in 1968... Purchase Cost of High-Voltage Electrostatic Precipitators in1968... Installed Capital Cost of Electrostatic Precipitator Systems Excluding Disposal...... Turbulent Contact Absorber... Dust Removal...... Alkalized Alumina Process... Solids Entraining Device... Cat-Ox Process... Cat-Ox Process Effect of Variables... Reinluft Process... Condensed System MsSaOs-MsSO,-Ha0...... Phase Diagram... Battery Limits Plus Utilities Cost... Effect of Operating Level and Plant Capacity on Production Cost... Cost of Acid Making Section of a Sulfuric Acid Plant...... Effect of Operating Level and Plant Capacity on Production Cost... ix 39 40 56 65 66 71 83 90 91 109 125 128 141 151 163 173 179 185 191 197 202 211 222
TABLES 2.1 3.1 3.2 3.3 3.4 4.1 4.2 5.1 5.2 6.1 6.2 6.3 6.4 6.5 6.6 6.7 7.1 7.2 7.3 7.4 7.5 7.6 7.7 Summary of Evaluations for 800 Megawatt Power Plant... 7 Commercial Stack Gas Treating Plants... 23 Prototype and Semi-Works Stack Gas Treating Plants... 25 Stack Gas Treating Processes in Pilot Plant Stage... 27 Data on Sulfur Products... 30 Summary of Capital Charges... 49 Calculation of Levelized Charges... 50 Air Cleaning Equipment Installed Cost Based on 1,000 Megawatt Unit... 68 Electrostatic Precipitator Production Costs... 74 Additive Injection Processes... 79 Studies of Sulfur Dioxide Sorption by Limestone... 80 Major Process Equipment and Utilities Summary... 83 Stream Flows... 85 Total Capital Investment... 95 Operating Costs... 96 Credits... 97 Cement Sulfuric Acid Plants in Operation at End of 1968.. 100 Analysis of Portland Cements... 102 Typical Composition Limits of U.S. Coal Ash... 104 Chlorine Content of Selected U.S. Coals... 104 es for License... 105 Major Process Equipment and Utilities Summary... 109 Stream Flows... 111 xi
TABLES 7.8 7.9 Total Capital Investment........,........ 116 Production Costs..................... 117 7.10 7.11 8.1 9.1 9.2 9.3 9.4 9.5 10.1 10.2 10.3 10.4 10.5 11.1 11.2 11.3 11.4 Licenser's Estimate of Total Capital Investment...... 118 Licenser's Estimate of Production Costs.......... 119 Alkalized Alumina Processes............... 124 Catalytic Oxidation Processes............... 138 Cat-Ox Process Major Process Equipment and Utilities Summary.,..... 141 Cat-Ox Process Stream Flows....................... 143 Monsanto Cat-Ox Process Total Capital Investment................. 149 Monsanto Cat-Ox Process Production Costs..................... 150 Carbon Adsorption Processes................ 156 Reinluft Process Major Process Equipment and Utilities Summary.,..... 163 Reinluft Process Stream Flows....................... 165 Reinluft Process Total Capital Investment................. 168 Reinluft Process Production Costs..................... 169 Wellman-Lord Alkali Sulfite Processes........... 175 Major Process Equipment and Utilities Summary....... 179 Stream Flows....................... 181 Total Capital Investment................. 190 xii
TABLES 11.5 11.6 11.7 12.1 12.2 12.3 12.4 13.1 13.2 13.3 13.4 13.5 13.6 13.7 Production Costs... 195 Wellman-Lord Sodium Sulfite Process Total Capital Investment... 203 Wellman-Lord Sodium Sulfite Process Production Costs... 204 Major Process Equipment and Utilities Summary... 211 Stream Flows... 213 Total Capital Investment... 220 Production Costs... 221 Dry Metal Oxide Processes... 225 Aqueous Scrubbing Processes... 231 Inorganic Liquid Processes... 244 Organic Liquid Processes... 245 Processes Using Solids Other Than Oxides... 248 Organic Solid Processes... 249 Direct Reduction Processes... 250 xiii