Acetic Acid, March 1968

Report No. 37

ACETIC ACID

by SHIGEYOSHI TAKAOKA

March 1968

A private report by the

PROCESS ECONOMICS PROGRAM

I
STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA
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 Acetic Acid, March 1968

CONTENTS

1 INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . 1

2 SUMMARY . . . . . . . . . . . . . . . . . . . * . . . . . . 3

3 INDUSTRY STATUS . . . . . . . . . . . . . . . . . . . . . . 13

4 ACETIC ACID BY OXIDATION OF ACETALDEHYDE . . . . . . . . . . 21

Introduction . . . . . . . ................. 21
Chemistry . . . . . . . . ................. 21
Reaction Mechanism . . . ................. 21
Kinetics . . . . . . . . ................. 24
Review of Processes . . . ................. 26
Feed Specification . . . ................. 27
Temperature . . . . . . ................. 31
Pressure . . . . . . . . ................. 31
Catalyst . . . . . . . . ................. 31
Explosion . . . . . . . ................. 32
Purification . . . . . . ................. 32
Material of Construction ................. 33
Process Description . . . ................. 34
Process Discussion . . . . ................. 41
Cost Estimates . . . . . . ................. 43
Capital Costs . . . . . ................. 43
Production Costs . . . . ................. 48

5 ACETIC ACID BY OXIDATION OF PARAFFINIC HYDROCARBONS .... 53

Introduction ........................ 53
Chemistry. ......................... 53
Reaction Mechanism .................... 53
Initiation ........................ 55
Propagation ...................... 55
Termination ...................... 62
Kinetics ........................ 63
Review of Processes .................... 66
Feed Specifications ................... 66
Temperature ....................... 72
Pressure ......................... 72
Catalyst ......................... 73
Oxidation Products .................... 74

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 Acetic Acid, March 1968

CONTENTS

5 (continued)
Type of Reactor .................. * . 75
Purification ................... . . 75
Material of Construction ............. . . 77
Process Description .................. . . 77
Process Discussion .................. . . 97
Cost Estimates .................... . . 102
Capital Costs .................... . . 102
Production costs .................. . . 110

6 ACETIC ACID BY OLEFIN OXIDATION ............ . . 121

Introduction ..................... . . 121
Chemistry ....................... . . 121
Review of Processes .................. . . 122
Vapor-Phase Catalytic Oxidation Processes ...... . . 127
Liquid-Phase Noncatalytic Oxidation Processes .... . . 128
Liquid-Phase Two-Step Process Using n-Butene .... . . 129
Process Description .................. . . 129
Process Discussion .................. . . 145
Cost Estimates .................... . . 148
Capital Costs .................... . . 148
Production Costs .................. . . 149

7 ACETIC ACID SYNTHESIS FROM METHANOL AND CARSON MONOXIDE . . 159

Introduction ..................... . . 159
Chemistry ............. i ......... . . 159
Reaction Mechanism ................. . . 159
Kinetics ...................... . . 162
Review of Processes .................. . . 164
Feed Specifications ................. . . 164
Temperature ..................... . . 170
Pressure ..................... . . 170
Catalyst. ...................... . . 170
Reaction Time .................... . . 171
Recovery and Purification of Catalyst and Acetic Acid . . 171
Material of Construction .............. . . 172

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 Acetic Acid, March 1968

CONTENTS

(continued)
Process Description ......... ........... 173
Process Discussion ......... ........... 181
Cost Estimates ........... ........... 185
Capital Costs ........... ........... 185
I 186
0 Production Costs ......... ...........

ACETIC ACID BY OTHER PROCESSES . . . . . . . . . . . . . . 195

SEPARATION AND PURIFICATION OF ACETIC ACID . . . . . . . . 201

Azeotropic Distillation ...... ........... 201
Liquid-Liquid Extraction ...... ........... 202
Extractive Distillation ....... ........... 202
.A Other Processes ........... ........... 203

I APPENDIX A DESIGN AND COST BASIS, DEFINITIONS ........ 209

APPENDIX B PHYSICAL PROPERTIES ............... 213

APPENDIX C RAW MATERIAL AND PRODUCT SPECIFICATIONS ..... 215

APPENDIX D SAFETY ...................... 217

8 -.
APPENDIX E MATERIAL OF CONSTRUCTION ............. 219

REFERENCES .......................... 221

SUPPLEMENTARY REFERENCES ................... 247

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 Acetic Acid, March 1968

ILLUSTRATIONS

4.1 Acetic Acid by Acetaldehyde Oxidation . . . . . . . . . . . . 37

4.2 Acetic Acid by Acetaldehyde Oxidation
Effect of Plant Capacity on Process Unit Investment . . . . . 47
4.3 Effect of Acetaldehyde Cost on Acetic Acid Production Cost. . 51
4.4 Acetic Acid by Acetaldehyde Oxidation
Effect of Operating Level and Production Capacity on
Production Cost....................... 52
5.1 Effect of Air-Flow gate and Temperature on n-Butane
Oxidation.......................... 64
5.2 Acetic Acid by Oxidation of Naphtha . . . . . . . . . . . . . 83
5.3 Acetic Acid by Oxidation of n-Butane . . . . . . . . . . . . 91
5.4 Acetic Acid by Oxidation of Naphtha
Effect of Plant Capacity on Fixed Capital . . . . . . . . . . 108
5.5 Acetic Acid by Oxidation of n-Butane (Column Reactor)
Effect of Plant Capacity on Fixed Capital . . . . . . . . . . 109
5.6 Effect of Naphtha Cost and By-Product Credit on
Net Production Cost of Acetic Acid (Tubular Reactor) . . . . 113
5.7 Effect of n-Butane Cost and By-Product Credit on
Net Production Cost of Acetic Acid (Column Reactor) . . . . . 117
5.8 Effect of Operating Level and Production Capacity on
Total Production Cost of Acetic Acid by Oxidation of
Naphtha (Tubular Reactor) . . . . . . . . . . . . . . . . . . 118
5.9 Effect of Operating Level and Production Capacity on
Total Production Cost of Acetic Acid by Oxidation of
n-Butane (Column Reactor) . . . . . . . . . . . . . . . . . . 119
6.1 Acetic Acid from n-Butenes . . . . . . . . . . . . . . . . . 135
6.2 Effect of n-Butenes Cost and By-Product Credit on
Acetic Acid Production Cost . . . . . . . . . . . . . . . . . 157
6.3 Effect of Operating Level and Production Capacity on
Net Production Cost of Acetic Acid from n-Butenes . . . . . . 158
7.1 Acetic Acid from Methanol and Carbon Monoxide . . . . . . . . 177

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 Acetic Acid, March 1968

ILLUSTRATIONS

7.2 Acetic Acid from Methanol and Carbon Monoxide

Effect of Plant Capacity on Capital Cost . . . . . . . . . . 190
7.3 Acetic Acid from Methanol and Carbon Monoxide
Effect of Raw Material Cost on Production Cost . . . . . . . 193
7.4 Effect of Operating Level and Production Capacity on
Production Cost of Acetic Acid from Methanol and Carbon
Monoxide . . . . . . . . . . . . . . . . . . . . . . . . . . 194
9.1 Process Unit Investment of Acetic Acid Recovery Plant . . . . 205
9.2 Operating Cost of Acetic Acid Recovery Plant . . . . . . . . 206
E.l Material Selection Chart for Acetic Acid . . . . . . . . . . 219

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Acetic Acid, March 1968

TABLES

2.1 Summary of Acetic Acid Processes . . . . . . . , . . , . . 4

2.2 Summary of Technical Characteristics of Evaluated

Acetic Acid Processes . . . . . . . . . . . . . . . . . . 7

3.1 Acetic Acid Plant Capacities

North and South America . . . . . . . . . . . . . . . . . 15

3.2 Acetic Acid Plant Capacities

Europe and U.S.S.R. . . . . . . . . . . . . . , . . . . . 17

3.3 Acetic Acid Plant Capacities

Asia . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

4.1 Acetic Acid by Acetaldehyde Oxidation

Summary of Processes . . . . . . . . . . . . . . . . . . . 29

4.2 Acetic Acid by Acetaldehyde Oxidation

Major Process Equipment and Utilities Summary . . . . . . 37

4.3 Acetic Acid by Acetaldehyde Oxidation

Stream Flows....................... 39

4.4 Acetic Acid by Acetaldehyde Oxidation

Process Unit and Utilities Investment . . . . . . . . . . 45

4.5 Acetic Acid by Acetaldehyde Oxidation

Total Capital Investment . . . . . . . . . . . . . . . . . 46

4.6 Acetic Acid by Oxidation of Acetaldehyde

Production Costs . . . . . . . . . . . . . . . . . . . . . 49

5.1 Acetic Acid by Oxidation of Paraffinic Hydrocarbons

Summary of Processes . . . . . . . . . . . . . . . . . . . 67

5.2 Acetic Acid by Oxidation of Naphtha (Tubular Reactor)

Major Process Equipment and Utilities Summary . . . . . . 82

5.3 Acetic Acid by Oxidation of Naphtha (Tubular Reactor)

Stream Flows....................... 87

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 Acetic Acid, March 1968

TABLES

5.4 Acetic Acid by Oxidation of n-Butane (Column Reactor)

Major Process Equipment and Utilities Summary . . . . . . 91

5.5 Acetic Acid by Oxidation of n-Butane (Column Reactor)

Stream Flows . . . . . . . . . . . . . . . . . . . . . . 95

5.6 Acetic Acid by Oxidation of Naphtha (Tubular Reactor)

Process Unit and Utilities Investment . . . . . . . . . . 104

5.7 Acetic Acid by Oxidation of n-Butane (Column Reactor)

Process Unit and Utilities Investment . . . . . . . . . . 105

5.8 Acetic Acid by Oxidation of Naphtha (Tubular Reactor)

Total Capital Investment . . . . . . . . . . . . . . . . 106

5.9 Acetic Acid by Oxidation of n-Butane (Column Reactor)

Total Capital Investment . . . . . . . . . . . . . . . . 107

5.10 Acetic Acid by Oxidation of Naphtha (Tubular Reactor)

Production Costs . . . . . . . . . . . . . . . . . . . . 111

5.11 Acetic Acid by Oxidation of n-Butane (Column Reactor)

Production Costs . . . . . . . . . . . . . . . . . . . . 115

6.1 Acetic Acid by Olefin Oxidation

Summary of Processes . . . . . . . . . . . . . . . . . . 123

6.2 Acetic Acid from n-Butenes

Major Process Equipment and Utilities Summary . . . . . . 133

6.3 Acetic Acid from n-Butenes

Stream Flows . . . . . . . . . . . . . . . . . . . . . . 141

6.4 Acetic Acid from n-Butenes

Process Unit and Utilities Investment . . . . . . . . . . 151

6.5 Acetic Acid from n-Butenes

Total Capital Investment . . . . . . . . . . . . . . . . 153

6.6 Acetic Acid from n-Butenes

Production Costs . . . . . . . . . . . . . . . . . . . . 155
 ..-.

Acetic Acid, March 1968

TABLES

7.1 Acetic Acid from Methanol and Carbon Monoxide

Summary of Processes . . . . . . . . . . . . . . . . . . . 165

7.2 Acetic Acid from Methanol and Carbon Monoxide

Major Process Equipment and Utilities Summary . . . . . . 177

7.3 Acetic Acid from Methanol and Carbon Monoxide

Stream Flows....................... 179

7.4 Acetic Acid from Methanol and Carbon Monoxide

Process Unit and Utilities Investment . . . . . . . . . . 188

7.5 Acetic Acid from Methanol and Carbon Monoxide

Total Capital Investment . . . . . . . . . . . . . . . . . 189

7.6 Acetic Acid from Methanol and Carbon Monoxide

Production Costs . . . . . . . . . . . . , . . . . . . . , 191

8.1 Acetic Acid by Other Processes

Summary of Patents.................... 197
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