Report No. 15A VINYL ACETATE Supplement A by YEN-CHEN YEN June 1972. A private report by the PROCESS ECONOMICS PROGRAM I STANFORD RESEARCH INSTITUTE MENLO I PARK, CALIFORNIA
CONTENTS 1 INTRODUCTION......,.................. 1 2 SUMMARY... 3 General Aspects... 3 Technical Aspects... 9 3 INDUSTRY STATUS...................,... 15 4 VINYL ACETATE FROM ETHYLENE BY VAPOR PROCESSES... 21 Chemistry... 21 Review of Processes... 24 Catalyst... 33 Reactants... 34 Reactor 34 Processes Without... 34 Recovery of Vinyl Acetate... 1'.. 35 Vinyl Acetate from Ethylene and... 37 Process Description... 37 Process Discussion... 47 Cost Estimates... 51 Vinyl Acetate from Ethylene Feed and Acetic Acid Formed in Process... 57 Process Description... 57 Process Discussion... 64 Cost Estimates... 64 Vinyl Acetate from Ethylene Feed and Acetic Acid Formed in Process from Acetaldehyde Feed... 69 Comparison of Variations of Ethylene Vapor Process... 69 5 VINYL ACETATE FROM ETHYLENE BY LIQUID PROCESSES... 71 Chemistry... 71 Review of Processes... 75 Catalyst... 75 Vinyl Acetate/Acetaldehyde Ratio... 86 One-Stage or Two-Stage... 86 Reaction Product in Gas or Liquid... 88 Reactors... 89 Separation and Purification of Vinyl Acetate... Recovery of Spent Catalyst, Removal of Precipitates and 89 High-Boiling Impurities... 90 V
CONTENTS 5 (continued) Vinyl Acetate from Ethylene by Single-Stage Liquid Process,. 93 Process Description,.,.,....,,,..,...,. 93 Process Discussion...................,. 107 Cost Estimates....,....,,............ 108 Modification--Using a Catalyst System Containing No Halide. 116 Modification--Without Acetaldehyde Production....... 116 Modification--Another Way To Recover Catalyst,..,.,. 117... 124 Process Description.................... 124 Process Discussion....,................ 132 Cost Estimates.,..................... 134 6 VINYL ACETATE FROM ETHANE... 141 Process Description... 141 Process Discussion... 150 Cost Estimates... 151 7 VINYL ACETATE FROM ACETYLENE BY VAPOR PROCESS,...,.., 155 Chemistry...............,.......... 155 Review of Processes.................. 155 Evaluation of the Process.,....,........... 159 8 VINYL ACETATE BY OTHER PROCESSES... 163 Acetaldehyde Process... 163 Vinyl Acetate from Vinyl Chloride... 163 Vinyl Acetate from Ethyl Acetate... 163 Vinyl Acetate from Ethylene by Oxidation by Peracetic Acid with a Selenic Oxide Catalyst... 164 9 MANUFACTURE OF OTHER VINYL ESTERS.....,..,..... 165 Acetylene Process...................... 165 Ethylene Process.................,...., 169 Transvinylation....,.................. 170 Vinyl Propionate from Acetylene by Vapor Process.....,. 170 Vinyl Ester of Versatic 63 Acid from Acetylene by Liquid Process.........,.............. 177 Vi
CONTENTS APPENDIX A DESIGN AND COST BASIS... 185 APPENDIX B PHYSICAL DATA... 189 APPENDIX C SPECIFICATIONS... 191 REFERENCES... 193 PATENT REFERENCES BY COMPANY... 221 Vii
ILLUSTRATIONS 4.1 4.2 4.3 4.4 5.1 5.2 5.3 5.4 5.5 6.1 7.1 9.1 B.1...................,.. 43 Acetic Acid Feed Production Costs at Different Production Levels. 56 : Hydrolysis Section..... 61 Production Costs at Different Production Levels..,... 68 Vinyl Acetate from Ethylene by Single-Stage Liquid Process. 99 Vinyl Acetate from Ethylene by Single-Stage Liquid Process Production Costs at Different Production Levels...... 115 Vinyl Acetate from Ethylene by Single-Stage Liquid Process: Alternative Way To Regenerate Catalyst and To Remove High Boiling Impurities..,.................. 121.. 129 Production Costs at Different Production Levels,..,.. 139 Vinyl Acetate from Ethane....,............ 147 Vinyl Acetate from Acetylene in Vapor Phase Production Costs at Different Production Levels,..... 162 Vinyl Ester of Versatic Acid from Acetylene..,.,... 179 Relative Volatilities Between Components of the System Acetic Acid-Vinyl Acetate-Acetaldehyde.........., 190 IX
TABLES 2.1 2.2 2.3 3.1 3.2 3.3 3.4 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 Manufacture of Vinyl Acetate Summary of Cost Estimates................. 5 Vapor Process for Vinyl Acetate from Ethylene and Summary of Cost Estimates for Variations in Design..,. 8 Manufacture of Other Vinyl Esters. Summary of Cost Estimates..........,...... 10 Vinyl Acetate Producers in the United States....... 16 Vinyl Acetate Producers in Japan............. 16 Vinyl Acetate Producers in Europe.,.......,... 18 Vinyl Acetate Producers in Regions Other than the United States, Europe, and Japan,.....,...... 19 Vinyl Acetate from Ethylene by Vapor Processes Patent Summary...................... 25 Recovery and Purification of Vinyl Acetate Patent Summary...................... 36 Major Process Equipment and Utilities Summary.,..... 42 Stream Flow....................... 45 Changes in Major Process Equipment for 10% COs in Recycle Gas........................ 50 Changes in Major Process Equipment for 30% COa in Recycle Gas........................ 50 Total Capital Investment................. 53 Production Costs..................... 55 Xi
TABLES 4.9 4.10 4.11 4.12 5.1 5.2 5.3 5.4 5.5 Major Process Equipment and Utilities Summary.,.,.., 59 Stream Flows........,............., 63 Total Capital Investment..........,..,... 65 Production Costs.....,..,...,,.,.,... 67 Vinyl Acetate from Ethylene by Single-Stage Liquid Processes with Redox Salts Patent Summary..,..,........,....... 77 es with Redox Salts Patent Summary...................,.. 83 Vinyl Acetate from Ethylene Oxidation with Oxygen by Liquid Processes Without Redox Salts Patent Summary.,,....,,......,,,,.,. 87 Vinyl Acetate from Ethylene by Liquid Processes: Treatment of Spent Catalyst Solution and Preparation of Catalyst Solution Patent Summary...........,......,... 91 Vinyl Acetate from Ethylene by Single-Stage Liquid Process Major Process Equipment and Utilities Summary..,,.., 98 5.6 Vinyl Acetate from Ethylene by Single-Stage Liquid Process Stream Flows........,.............. 103 5.7 Vinyl Acetate from Ethylene by Single-Stage Liquid Process Total Capital Investment................. 111 5.8 Vinyl Acetate from Ethylene by Single-Stage Liquid Process Production Costs...,,.....,.,........ 113. 5.9 Vinyl Acetate from Ethylene by Single-Stage Liquid Process: Alternative Way To Regenerate Catalyst and To Remove High-Boiling Impurities Major Process Equipment and Utilities Summary: Catalyst Regeneration Section.......,........... 121 Xii
TABLES 5.10 5.11 5.12 5.13 5.14 6.1 6.2 6.3 6.4 7.1 7.2 7.3 9.1 9.2 9.3 9.4 Vinyl Acetate from Ethylene by Single-Stage Liquid Process: Alternative Way To Regenerate Catalyst and To Remove High-Boiling Impurities Capital Investment: Catalyst Regeneration Section.,.. 123 Major Process Equipment and Utilities Summary...,... 127 Stream Flows....................... 131 Total Capital Investment................. 135 Production Costs...,...............,. 137 Vinyl Acetate from Ethane Major Process Equipment and Utilities Summary....,.. 145 Vinyl Acetate from Ethane Stream Flows,....................,. 149 Vinyl Acetate from Ethane Total Capital Investment...............,, 152 Vinyl Acetate from Ethane Production Costs............,........ 153 Vinyl Acetate from Acetylene in Vapor Phase Patent Summary...................... 157 Vinyl Acetate from Acetylene in Vapor Phase Total Capital Investment.,......,........ 160 Vinyl Acetate from Acetylene in Vapor Phase Production Costs..................... 161 Vinyl Esters Other than Vinyl Acetate from Acetylene Patent Summary...................... 167 Vinyl Esters by Transvinylation and Vinyl Acetate Patent Summary.,..........,.......,. 173 Vinyl Propionate from Acetylene by Vapor Process Total Capital Investment................. 175 Vinyl Propionate from Acetylene by Vapor Process Production Costs..................... 176 Xiii
TABLES 9.5 Vinyl Ester of Versatic Acid from Acetylene Major Process Equipment and Utilities Summary....... 179 9.6 Vinyl Ester of Versatic Acid from Acetylene Stream Flows..,.,,.......,...,.... 181 9.7 Vinyl Ester of Versatic Acid from Acetylene Total Capital Investment...........,..... 182 9.8 Vinyl Ester of Versatic Acid from Acetylene Production Costs.,.,...,...........,. 183 xiv