Report No. 6

ACRYLIC ACID AND ACRYLIC ESTERS

by RICHARD G. DENNEY

Contributions by Robert E. Johnk

September 1965

a A private report by the

PROCESS ECONOMICS PROGRAM

0 STANFORD RESEARCH INSTITUTE MENLO PARK. CALIFORNIA CONTENTS

I INTRODUCTION ...... 1

II SUMMARY ...... 3

III INDUSTRY STATUS ...... 13

IV CHEMISTRY OF ACRYLIC ACID PRODUCTION ...... 23

V CHEMISTRY OF ACRYLIC ESTERS PRODUCTION ...... 41

VI PROCESSES FOR ACRYLIC ACID MANUFACTURE ...... 49 Acetylene Process ...... 49 Review of Processes ...... 49 Process Description ...... 56 Process Discussion ...... 64 Cost Estimates ...... 68 B-Propiolactone Process ...... 75 Review of Processes ...... 75 Process Description ...... 77 Process Discussion ...... 85 Cost Estimates ...... 87 Acrylonitrile Process ...... 95 Review of Processes ...... 95 Process Description ...... 97 Process Discussion ...... 103 Cost Estimates ...... 105 Propylene Oxidation Process ...... 114 Review of Processes ...... 1 l,? Process Description ...... 129 Process Discussion ...... 136 Cost Estimates ...... 138 Other Processes ...... 146 Maleic Acid Process ...... 146 Lactic Acid Process ...... 147 Ethylene Cyanohydrin Process ...... 148

iii CONTENTS

VII PROCESSES FOR LOWER ACRYLIC ESTER MANUFACTURE ...... 151 Acetylene Process ...... 151 Review of Processes ...... 151 Process Description ...... 163 Process Discussion ...... 172 Cost Estimates ...... 175 B-Propiolactone Process ...... 184 Review of Processes ...... 184 Process Description ...... 185 Process Discussion ...... 191 Cost Estimates ...... 192 Acrylonitrile Process ...... 199 Review of Processes ...... 199 Process Description ...... 208 Process Discussion ...... 216 Cost Estimates ...... 217 Esterification Process ...... 225 Review of Processes ...... 225 Process Description ...... 231 Process Discussion ...... 237 Cost Estimates ...... 238 Other Processes ...... 245 Saturated Ester Process ...... 245 Ethylene Cyanohydrin Process ...... 246

VIII PROCESSES FOR HIGHER ACRYLIC ESTER MANUFACTURE 247 Esterification Process ...... 247 Review of Processes ...... 247 Cost Estimates ...... 249 Transesterification Process ...... 250 Review of Processes ...... 250 Cost Estimates ...... 250

IX INTEGRATED PROCESSES ...... 253

iv CONTENTS

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Appendix A DESIGN AND COST BASIS ...... 273

Appendix B PHYSICAL DATA ...... 275

Appendix C RAW MATERIAL AND PRODUCT SPECIFICATIONS ...... 279

Appendix D HANDLING AND SAFETY ...... 283

CITED REFERENCES ...... 287

SUPPLEMENTARY REFERENCES ...... 302

V ILLUSTRATIONS

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1 Acrylic Acid by High Pressure Catalytic Acetylene Process Side Reactions ...... 30 2 Acrylic Acid by Catalytic Acetylene Process ...... 59 3 Acrylic Acid by Catalytic Acetylene Process Effect of Pressure on Reaction Time ...... 66 4 Acrylic Acid by B-Propiolactone Process ...... 81 5 Acrylic Acid by Acrylonitrile Process (Hypothetical Process) ...... 99 6 Vapor Phase Propylene Oxidation Effect of Temperature on Propylene Conversion ...... 120 7 Vapor Phase Propylene Oxidation Effect of Temperature on Selectivity to Acrylic Acid . . . . . 121 a Vapor Phase Propylene Oxidation Effect of Temperature on per Pass Yield of Acrylic Acid . . . . 122 9 Vapor Phase Propylene Oxidation Effect of Space Velocity on Propylene Conversion ...... 125 10 Vapor Phase Propylene Oxidation Effect of Conversion on Selectivity to Acrylic Acid ...... 126 11 Acrylic Acid by Propylene Oxidation ...... , ...... 131 12 Lower Acrylic Esters by Stoichiometric-Catalytic Acetylene Process ...... 165 13 Lower Acrylic Esters by @-Propiolactone Process ...... 187 14 Acid Hydrolysis of Acrylonitrile to Acrylamide Effect of Reaction Time ...... 204 15 Lower Acrylic Esters by Acrylonitrile Process ...... 211

16 Lower Acrylic Esters by Direct Esterification Process . . . . . 233

vii TABLES

1 Plant Capacities Americas...... 15 2 Plant Capacities 0 Asia...... 17 3 Plant Capacities Western Europe ...... 19 4 Acrylic Acid from Acetylene Summary of Processes ...... 51 5 Acrylic Acid by Catalytic Acetylene Process Major Process Equipment and Utilities Summary ...... 57 6 Acrylic Acid by Catalytic Acetylene Process Stream Flows ...... 61 7 Acrylic Acid by Catalytic Acetylene Process Process Unit and Utilities Investment . . , ...... 69 0 8 Acrylic Acid by Catalytic Acetylene Process Total Capital Investment ...... 71 9 Acrylic Acid by Catalytic Acetylene Process Production Costs ...... 73 10 Acrylic Acid by B-Propiolactone Process Major Process Equipment and Utilities Summary ...... 79 11 Acrylic Acid by B-Propiolactone Process Stream Flows ...... , ...... 83 12 Acrylic Acid by B-Propiolactone Process Process Unit and Utilities Investment ...... 89 13 Acrylic Acid by B-Propiolactone Process Total Capital Investment ...... , ...... 91 14 Acrylic Acid by B-Propiolactone Process Production Costs ...... 93 15 Acrylic Acid by Acrylonitrile Process 0 Major Process Equipment and Utilities Summary ...... 99 16 Acrylic Acid by Acrylonitrile Process Stream Flows ...... 101 17 Acrylic Acid by Acrylonitrile Process Process Unit and Utilities Investment ...... 107 0 ix -

TABLES

18 Acrylic Acid by Acrylonitrile Process Total Capital Investment ...... 109

19 Acrylic Acid by Acrylonitrile Process Production Costs ...... 111

20 Acrylic Acid by Acrolein Oxidation Summary of Processes ...... 115

21 Acrylic Acid by Propylene Oxidation Summary of Processes ...... , ...... 117 22 Acrylic Acid by Propylene Oxidation Major Process Equipment and Utilities Summary ...... 131 23 Acrylic Acid by Propylene Oxidation Stream Flows...... 133 24 Acrylic Acid by Propylene Oxidation Process Unit and Utilities Investment ...... 139 25 Acrylic Acid by Propylene Oxidation Total Capital Investment ...... 141 26 Acrylic Acid by Propylene Oxidation Production Costs ...... 143 27 Lower Acrylic Esters by Stoichiometric-Catalytic Acetylene Process Summary of Processes ...... 152 28 Lower Acrylic Esters by Catalytic Acetylene Process Summary of Processes ...... , ...... 155 29 Lower Acrylic Esters by Catalytic Acetylene Process Summary of Union Carbide Processes ...... 159 30 Lower Acrylic Esters by Stoichiometric-Catalytic Acetylene Process Major Process Equipment and Utilities Summary ...... 165 31 Lower Acrylic Esters by Stoichiometric-Catalytic Acetylene Process Stream Flows...... 167 32 Lower Acrylic Esters by Stoichiometric-Catalytic Acetylene Process Process Unit and Utilities Investment ...... 177 33 Lower Acrylic Esters by Stoichiometric-Catalytic Acetylene Process Total Capital Investment ...... 179 34 Lower Acrylic Esters by Stoichiometric-Catalytic Acetylene Process Production Costs . . . , ...... 181

X TABLES

35 Lower Acrylic Esters by B-Propiolactone Process Major Process Equipment and Utilities Summary ...... 187 36 Lower Acrylic Esters by B-Propiolactone Process 0 Stream Flows...... 189 37 Lower Acrylic Esters by B-Propiolactone Process Process Unit and Utilities Investment ...... 193 38 Lower Acrylic Esters by B-Propiolactone Process Total Capital Investment ...... 196 39 Lower Acrylic Esters by B-Propiolactone Process Production Costs ...... 197 40 Lower Acrylic Esters from Acrylonitrile Summary of Processes . . . , ...... 201 41 Lower Acrylic Esters by Acrylonitrile Process Major Process Equipment and Utilities Summary . , ...... 209 0 42 Lower Acrylic Esters by Acrylonitrile Process Stream Flows ...... 213 43 Lower Acrylic Esters by Acrylonitrile Process Process Unit and Utilities Investment ...... 219 44 Lower Acrylic Esters by Acrylonitrile Process Total Capital Investment ...... 221 45 Lower Acrylic Esters by Acrylonitrile Process Production Costs ...... 223 46 Lower Acrylic Esters by Direct Esterification Summary of Processes ...... 227 47 Lower Acrylic Esters by Direct Esterification Process 0 Major Process Equipment and Utilities Summary ...... , 233 48 Lower Acrylic Esters by Direct Esterification Process Stream Flows...... 235 49 Lower Acrylic Esters by Direct Esterification Process 0 Process Unit and Utilities Investment ...... 239 50 Lower Acrylic Esters by Direct Esterification Process Total Capital Investment ...... 242 51 Lower Acrylic Esters by Direct Esterification Process Production Costs ...... 243

xi 0

TABLES

_. 0

52 Integrated Acrylic Ester Plant Propylene Oxidation Process Total Capital Investment ...... , . . . . , . . 255

53 Integrated Acrylic Ester Plant Propylene Oxidation Process Allocated Production Costs ...... , . 259

54 Integrated Acrylic Ester Plant Catalytic Acetylene Process Total Capital Investment ...... 261 55 Integrated Acrylic Ester Plant Catalytic Acetylene Process Allocated Production Costs ...... , ...... , 263 56 Integrated Acrylic Ester Plant Stoichiometric- Catalytic Acetylene Process Total Capital Investment ...... 267 57 Integrated Acrylic Ester Plant Stoichiometric- Catalytic Acetylene Process Allocated Production Costs ...... 269

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