Report No. 37A

ACETIC ACID AND ACETIC ANHYDRIDE Supplement A

by SHIGEYOSHI TAKAOKA

March 1973

A private report by the

PROCESS ECONOMICS PROGRAM

I STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA I CONTENTS

1 INTRODUCTION . . . , ...... 1

2 SUMMARY ...... 3 Acetic Acid ...... 3 Acetic Anhydride ...... 12

3 INDUSTRY STATUS ...... 17 Acetic Acid ...... 17 Acetic Anhydride ...... 18

4 ACETIC ACID BY OXIDATION OF ACETALDEHYDE . . , . . . . . 23 Chemistry ...... 23 Review of Processes ...... 24 Cost Estimates ...... 25 Capital Costs ...... 25 Production Costs ...... 26

5 ACETIC ACID BY OXIDATION OF PARAFFINIC HYDROCARBONS . . . . 33 Chemistry ...... 33 Review of Processes ...... 33 Cost Estimates ...... 33

6 ACETIC ACID BY OLEFIN OXIDATION ...... 41 Oxidation of Ethylene ...... 41 Oxidation of Propylene ...... 47 Direct Oxidation of n-Butylenes ...... 51 Chemistry ...... 51 Review of Processes ...... 52 Process Description ...... 62 Process Discussion ...... 70 Cost Estimates ...... 72 Capital Costs ...... 72 Production Costs ...... 73 Indirect Oxidation of n-Butylenes ...... 78

V CONTENTS

7 ACETIC ACID SYNTHESIS FROM METHANOL AND CARBON MONOXIDE . . 83

Chemistry ...... 83 Review of Processes ...... 86 Feed Condition ...... 86 Catalyst ...... 88

Reaction Temperature and Pressure ...... , 89

Conversion and Selectivity ...... 89

Purification ...... 0 89 Process Description ...... m 90

Process Discussion ...... 96

Cost Estimates ...... 98

Capital Cost ...... 98

Production Costs ...... 99

8 ACETIC ACID BY OTHER PROCESSES ...... , ...... 107

9 SEPARATION AND PURIFICATION OF ACETIC ACID . . , ...... 109 Removal of Water . . , ...... , ...... , 109 Removal of Formic Acid ...... , ...... 109

10 ACETIC ANHYDRIDE VIA KETENE PRODUCED FROM ACETIC ACID . . . 113 Chemistry ...... , ...... 113 Review of Processes ...... 114 Ketene by Thermal Decomposition of Acetic Acid . . , . , . 114 Acetic Anhydride from Ketene and Acetic Acid . , . . . . . 123 Process Description ...... 124 Process Discussion . , ...... , ...... 133 Cost Estimates ...... , ...... 137 Capital Costs ...... , ...... 137 Production Cost: ...... , . . . . . , ...... 137 Design Variation Based on a Rotary Compressor Absorption System . , . . . . . , ...... , ...... 145

11 ACETIC ANHYDRIDE VIA KETENE PRODUCED FROM ACETONE , . . . . 147 Chemistry ...... , 147 Review of Processes ...... 149 Process Description ...... 151 Process Discussion ...... i ...... # . 159 Cost Estimates ...... 162 Capital Costs ...... , . 162 Production Costs ...... , . 162

vi CONTENTS

12 ACETIC ANHYDRIDE BY OXIDATION OF ACETALDEHYDE ...... 169 Chemistry ...... 169 Review of Processes ...... 171 Feed Specification ...... 172 Catalyst ...... 177 Temperature and Pressure ...... 178 Conversion and Selectivity ...... 178 By-Products ...... 179 Process Description ...... 179 Process Discussion ...... 187 Cost Estimates ...... 190 Capital Costs ...... 190 Production Costs ...... 190

13 ACETIC ANHYDRIDE BY OTHER PROCESSES ...... 197 Ketene by Other Processes ...... 197 Acetic Anhydride by Other Processes ...... 198

APPENDIX A DESIGN AND COST BASIS ...... 201

APPENDIX B PHYSICAL PROPERTIES ...... 207

APPENDIX C ACETIC ANHYDRIDE SPECIFICATIONS , ...... 211

APPENDIX D SAFETY ...... 213

APPENDIX E STORAGE AND HANDLING , ...... 215

CITED REFERENCES ...... 217

PATENT REFERENCES BYCOMPANY ...... 237

vii ILLUSTRATIONS

4.1 Acetic Acid by Acetaldehyde Oxidation Effect of Operating Level and Plant Capacity on Net Production Cost ...... 27

6.1 Effect of Steam Content on Conversion of n-Butylenes and Selectivity to Acetic Acid . , ...... 53 6.2 Effect of Oxygen Content and Temperature on Conversion of n-Butylenes and Selectivity to Acetic Acid ...... , ...... 54 6.3 Effect of Residence Time and Temperature on Conversion of n-Butylenes and Selectivity to Acetic Acid ...... 55 6.4 Acetic Acid by Direct Oxidation of n-Butylenes ...... 67 6.5 Acetic Acid by Direct Oxidation of n-Butylenes Effect of n-Butylenes Cost on Acetic Acid Production Cost ...... 76 6.6 Acetic Acid by Direct Oxidation of n-Butylenes Effect of Operating Level and Plant Capacity on Acetic Acid Production Cost ...... , ...... 77 7.1 Acetic Acid by Low Pressure Carbonylation of Methanol . , 93 7.2 Acetic Acid by Low Pressure Carbonylation of Methanol Effect of Raw Material Cost on Net Production Cost . . . . 103 7.3 Acetic Acid by Low Pressure Carbonylation of Methanol Effect of Operating Level and Plant Capacity on Net Production Cost ...... , ...... 104 10.1 Acetic Anhydride via Ketene Produced from Acetic Acid . . 129 10.2 Acetic Anhydride via Ketene Produced from Acetic Acid Effect of Plant Capacity on Capital Investment ...... 141 10.3 Acetic Anhydride via Ketene Produced from Acetic Acid Effect of Acetic Acid Price on Net Production Cost of Acetic Anhydride . , ...... , . . . , . . , . 143 10.4 Acetic Anhydride via Ketene Produced from Acetic Acid Effect of Operating Level and Plant Capacity on Net Production Cost of Acetic Anhydride ...... 144 10.5 Acetic Anhydride via Ketene Produced from Acetic Acid Reaction Section Using Rotary Compressor . . . . , . . . . 146

ix ILLUSTRATIONS

11.1 Acetic Anhydride via Ketene Produced from Acetone . . . . 155 11.2 Acetic Anhydride via Ketene Produced from Acetone Effect of Plant Capacity on Capital Investment ...... 165 11.3 Acetic Anhydride via Ketene Produced from Acetone Effect of Raw Material Price on Net Production Cost of Acetic Anhydride ...... , , . . . . 167 11.4 Acetic Anhydride via Ketene Produced from Acetone Effect of Operating Level and Plant Capacity on Net Production Cost of Acetic Anhydride . . , ...... 168 12.1 Acetic Anhydride by Oxidation of Acetaldehyde . , . . . . 183 12.2 Acetic Anhydride by Oxidation of Acetaldehyde Effect of Plant Capacity on Capital Investment ...... 193 12.3 Acetic Anhydride by Oxidation of Acetaldehyde Effect of Acetaldehyde Price and Acetic Acid By-Product Credit on Net Production Cost of Acetic Anhydride ...... 195 12.4 Acetic Anhydride by Oxidation of Acetaldehyde Effect of Operating Level and Plant Capacity on Net Production Cost of Acetic Anhydride . , ...... 196 TABLES

2.1 Summary of Acetic Acid Processes ...... 5 2.2 Summary of Technical Characteristicsof Evaluated Acetic Acid Processes ...... 9

2.3 Summary of Acetic Anhydride Processes ...... 13

3.1 Acetic Acid and Acetic Anhydride Plant Capacities North and South America ...... 19

3.2 Acetic Acid and Acetic Anhydride Plant Capacities Europe and USSR ...... 20

3.3 Acetic Acid and Acetic Anhydride Plant Capacities Asia ...... 21

4.1 Acetic Acid by AcetaldehydeOxidation with Air Total Capital Investment ...... 28

4.2 Acetic Acid by AcetaldehydeOxidation with Oxygen Total Capital Investment ...... 29

4.3 Acetic Acid by AcetaldehydeOxidation with Air Production Costs ...... 30

4.4 Acetic Acid by AcetaldehydeOxidation with Oxygen Production Costs ...... 31

5.1 Acetic Acid by Oxidation of Paraffinic Hydrocarbons Patent Summary ...... 35 5.2 Acetic Acid by Oxidation of n-Butane Total Capital Investment ...... 37

5.3 Acetic Acid by Oxidation of Naphtha (TubularReactor) Total Capital Investment ...... 38

5.4 Acetic Acid by Oxidation of n-Butane Production Costa ...... 39

5.5 Acetic Acid by Oxidation of Naphtha (TubularReactor) Production Costs...... 40

6.1 Acetic Acid by Oxidation of Ethylene Patent Summary...... 43 , 6.2 Acetic Acid by Oxidation of Propylene Patent Summary...... 49 6.3 Acetic Acid by Direct Oxidation of n-Butylenes Patent Summary...... 57

Xi TABLES

6.4 Acetic Acid by Direct Oxidation of n-Butylenes Major Process Equipment and Utilities Summary . . , . . , 65 6.5 Acetic Acid by Direct Oxidation of n-Butylenes Stream Flows ...... 69 6.6 Acetic Acid by Direct Oxidation of n-Butylenes Summary of Waste Products . . . , ...... 72 6.7 Acetic Acid by Direct Oxidation of n-Butylenes Total Capital Investment ...... 74 6.8 Acetic Acid by Direct Oxidation of n-Butylenes Production Costs . , ...... 75 6.9 Acetic Acid by Indirect Oxidation of n-Butylenes Total Capital Investment . . . . , ...... , , . 79 6.10 Acetic Acid by Indirect Oxidation of n-Butylenes Production Costs . . . . . , ...... , . . . 81 7.1 Acetic Acid by Low Pressure Carbonylation of Methanol Major Process Equipment and Utilities Summary ...... 92 7.2 Acetic Acid by Low Pressure Carbonylation of Methanol Stream Flows ...... , ...... 95 7.3 Acetic Acid by Low Pressure Carbonylation of Methanol Summary of Waste Products ...... 98 7.4 Acetic Acid by Low Pressure Carbonylation of Methanol Total Capital Investment ...... 100 7.5 Acetic Acid by High Pressure Carbonylation of Methanol Total Capital Investment ...... , . . . . . , . . 101 7.6 Acetic Acid by Low Pressure Carbonylation of Methanol Production Costs . , ...... , . , . 102 7.7 Acetic Acid by High Pressure Carbonylation of Methanol Production Costs ...... 105 10.1 Ketene by Thermal Decomposition of Acetic Acid Patent Summary . . , ...... , ...... 117 10.2 Acetic Anhydride via Ketene Produced from Acetic Acid Major Process Equipment and Utilities Summary . , . . . . 127 10.3 Acetic Anhydride via Ketene Produced from Acetic Acid Stream Flows ...... 131

xii TABLES

10.4 Acetic Anhydride via Ketene Produced from Acetic Acid Summary of Waste Products ...... 136 10.5 Acetic Anhydride via Ketene Produced from Acetic Acid Total Capital Investment ...... 139 10.6 Acetic Anhydride via Ketene Produced from Acetic Acid Production Costs ...... 142 11.1 Acetic Anhydride via Ketene Produced from Acetone Major Process Equipment and Utilities Summary ...... 154 11.2 Acetic Anhydride via Ketene Produced from Acetone Stream Flows ...... 157 11.3 Acetic Anhydride via Ketene Produced from Acetone Summary of Waste Products ...... 161 11.4 Acetic Anhydride via Ketene Produced from Acetone Total Capital Investment ...... 164 11.5 Acetic Anhydride via Ketene Produced from Acetone Production Costs ...... 166 12.1 Acetic Anhydride and Acetic Acid by Oxidation of Acetaldehyde Patent Summary...... 173 12.2 Acetic Anhydride by Oxidation of Acetaldehyde Major Process Equipment and Utilities Summary ...... 182 12.3 Acetic Anhydride by Oxidation of Acetaldehyde Stream Flows...... 185 12.4 Acetic Anhydride by Oxidation of Acetaldehyde Summary of Waste Products ...... 189 12.5 Acetic Anhydride by Oxidation of Acetaldehyde Total Capital Investment ...... , 192 12.6 Acetic Anhydride by Oxidation of Acetaldehyde Production Costs ...... 194

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