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Report No. 75

DIBASIC ACIDS FOR NYLON MANUFACTURE

by YEN-CHEN YEN

October 1971

A private report by the

PROCESS ECONOMICS PROGRAM

STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA CONTENTS

INTRODUCTION, ...... 1

SUMMARY ...... 3 General Aspects ...... 3 Technical Aspects ...... 7

INDUSTRY STATUS ...... 15 Applications and Consumption of Sebacic Acid ...... 15 Applications and Consumption of Azelaic Acid ...... 16 Applications of Dodecanedioic and Suberic Acids ...... 16 Applications of Cyclododecatriene and Cyclooctadiene .... 17 Producers ...... 17 Prices ...... 18

DIBASIC ACIDS FOR MANUFACTURE OF POLYAMIDES ...... 21

CYCLOOLIGOMERIZATIONOF BUTADIENE ...... 29 Chemistry ...... 29 Ziegler Catalyst ...... 30 Nickel Catalyst ...... 33 Other Catalysts ...... 34 Co-Cyclooligomerization ...... 34 Mechanism ...... 35 By-products and Impurities ...... 37 Review of Processes ...... 38 A Process for Manufacture of Cyclododecatriene ...... 54 Process Description ...... 54 Process Discussion ...... 60 Cost Estimates ...... 60 A Process for Manufacture of Cyclooctadiene ...... 65 Process Description ...... 65 Process Discussion ...... 70 Cost Estimates ...... 70 A Process for Manufacture of Cyclodecadiene ...... 74

DODECANEDIOIC ACID FROM CYCLODODECATRIENE ...... 77 Chemistry ...... 77 Hydrogenation of Cyclododecatriene ...... 77 Oxidation of Cyclododecane ...... 81 Oxidation of Cyclododecanol or Cyclododecanone ...... 81

V CONTENTS

6 (continued) Epoxidation of Cyclododecatriene ...... 81 Ozonization of Cyclododecene ...... 82 Review of Processes ...... 82 Hydrogenation of Cyclododecatriene ...... 82 Dodecanedioic Acid from Cyclododecane ...... 87 Dodecanedioic Acid from Cyclododecatriene Through Epoxidation ...... 91 Purification ...... 97 A Process via Cyclododecane ...... 98 Process Description ...... 98 Process Discussion ...... 111 Cost Estimates ...... 112 A Process via Cyclododecene ...... 120 Process Description ...... 120 Process Discussion ...... 128 Cost Estimates ...... 129

7 SUBERIC ACID FROM CYCLOOCTADIENE AND SEBACIC ACID FROM CYCLODECADIENE ...... 133 Chemistry ...... 133 Review of Processes ...... 133 A Process for Suberic Acid from Cyclooctadiene via Cyclooctane ...... 137 Process Description and Discussion ...... 137 Cost Estimates ...... 139 A Process for Sebacic Acid from Cyclodecadiene via Cyclodecane ...... 150 Process Description and Discussion ...... 150 Cost Estimates ...... 155

8 SEBACIC ACID FROM CASTOR OIL ...... 163 Chemistry ...... 163 Review of Processes ...... 164 Process Description ...... 167 Process Discussion ...... 176 Cost Estimates ...... 176

9 SEBACIC ACID FROM ADIPIC ACID ...... 185 Chemistry ...... 185 Review of Processes ...... 187

vi CONTENTS

9 (continued) Process Description ...... 191 Process Discussion ...... 201 Cost Estimates ...... 201

10 AZELAIC ACID FROM OLEIC ACID ...... 209 Chemistry ...... 209 Review of Processes ...... 211 Process Description ...... 214 Process Discussion ...... 222 Cost Estimates ...... 222

11 DIBASIC ACIDS FROM FATTY ACIDS OR PARAFFINS . . . . , . . . 227 Chemistry ...... 227 Review of Processes ...... 229 Process Description ...... 241 Process Discussion ...... 253 Cost Estimates ...... 255

12 OTHER PROCESSES FOR PREPARATION OF DODECANEDIOIC ACID . . . 265 From Malonic Acid and Butadiene ...... 265 From Cyclohexanone ...... 265 From Castor Oil or Ricinoleic Acid ...... 266 From 1,10-Decanediol ...... 267 From Pentane ...... 267 From l0-Undecenoic ...... 267 By Fermentation ...... 268

13 OTHER PROCESSES FOR PREPARATION OF SEBACIC ACID ...... 269 From Decalin (Decahydronaphthalene)...... 269 From Butadiene via Isosebacic Acid ...... 272 From Furfural 273 From Butadiene Through 1,4-Dichloro-2-butene ...... 273 From Octadiene ...... 274 From Resorcinal ...... 274 From Pentin Acid...... 275 From 1-Cyclodecanol-2-one ...... 275 From lo-Undecenoic Acid ...... 275 From Tetrachlorononane ...... 275 From Tetrahydrofurfural Chloride ...... 276 By Fermentation ...... 276

Vii CONTENTS

14 OTHER PROCESSES FOR PREPARATION OF AZELAIC ACID ...... 277 From an Acetylene Compound and Butadiene ...... 277 From Cyclooctadiene ...... 278 From Resorcinol and Acrylic Acid ...... 278 From Cyclohexanone ...... 278 From Ethylene and Chlorocyanogen ...... 279 From Cyclooctanone ...... 279 From Thiophene ...... 279 From Cyclopentanone-CarboxylicAcid ...... 280 By Fermentation ...... 280

15 OTHER PROCESSES FOR PREPARATION OF SUBERIC ACID ...... 281 From Acetylene via Cyclooctatetraene ...... 281 From Chloromethyl-methyletherand Butadiene ...... 282 From Acetylene and Carbon Monoxide ...... 282 From Ethylene and Carbon Tetrachloride via Tetrachloroheptane ...... 283 From Acrylic Acid via 1-Hexene-6-oic Methyl Ester ..... 283 0- From Acrolein via Hexanediol ...... 283 From Resorcinol Through 1,3-Cyclohexanedione ...... 284 From Butadiene and Acetylene ...... 286 From 1,5-Hexadiene ...... 286 By Fermentation ...... 286

APPENDIX A DESIGN AND COST BASIS ...... 287

APPENDIX B SPECIFICATIONS AND TYPICAL ANALYSES ...... 291

APPENDIX C PHYSICAL DATA ...... 295

CITED REFERENCES ...... 303 0

PATENT REFERENCES BY COMPANY ...... 357

Viii ILLUSTRATIONS

5.1 Cyclododecatriene from Butadiene . . . . . , . , ...... 57 5.2 Cyclododecatriene from Butadiene Production Costs as Different Production Levels . . . . . , 64 5.3 Cyclooctadiene from Butadiene ...... , . , . 67 5.4 Cyclooctadiene from Butadiene Production Costs at Different Production Levels . . , . . . 73 6.1 Dodecanedioic Acid from Cyclododecatriene Summary of Routes ...... , ...... 79 6.2 Dodecanedioic Acid from Cyclododecatriene via Cyclododecane ...... , . . . , ...... 103 6.3 Dodecanedioic Acid from Cyclododecatriene via Cyclododecane Production Costs at Different Production Levels ...... 119 6.4 Dodecanedioic Acid from Cyclododecatriene via Cyclododecene ...... , 125 6.5 Dodecanedioic Acid from Cyclododecatriene via Cyclododecene Production Costs at Different Production Levels , . . . . , 132 7.1 Suberic Acid from Cyclooctadiene Summary of Routes ...... , . . , . . 134 7.2 Suberic Acid from Cyclooctadiene via Cyclooctane Purification Section ...... 143 7.3 Suberic Acid from Cyclooctadiene via Cyclooctane Production Costs at Different Production Levels , . . . , . 149 7.4 Sebacic Acid from Cyclodecadiene via Cyclodecane Purification Section ...... 153 7.5 Sebacic Acid from Cyclodecadiene via Cyclodecane Production Costs at Different Production Levels ., . . . . . 161 8.1 Sebacic Acid from Castor Oil . , ...... 173 8.2 Sebacic Acid from Castor Oil Production Costs at Different Production Levels ...... 183 9.1 Sebacic Acid from Adipic Acid by Electrolysis . , . . . . . 195 9.2 Sebacic Acid from Adipic Acid by Electrolysis Production Costs at Different Production Levels , . . , . . 207 10.1 Azelaic Acid from Oleic Acid ...... 219 ILLUSTRATIONS

10.2 Azelaic Acid from Oleic Acid Production Costs at Different Production Levels . , . . . . 226 11.1 Dibasic Acids from Tallow by Oxidation . , . . . . . , . . . 245 11.2 Dibasic Acids from Tallow by Oxidation Production Costs at Different Production Levels ...... 263 l C.1 Solubilities of Dibasic Acid in Water ...... , . . . . 296 C.2 Solubilities of Sebacic Acid, Azelaic Acid, and Suberic Acid in 25% Aqueous Nitric Acid , ...... 297 c.3 Solubilities of Sebacic Acid, Azelaic Acid, and Suberic Acid in 40% Aqueous Nitric Acid ...... 298 C.4 Solubilities of Sebacic Acid, Azelaic Acid and Suberic Acid in 58% Aqueous Nitric Acid . . , ...... 299 C.5 Vapor Pressures of Selected Compounds . , ...... 301 TABLES

2.1 Manufacture of Sebacic Acid Cost Estimates ...... , 4 2.2 Manufacture of Dodecanedioic Acid, Suberic Acid, and Sebacic Acid via Cycloalkenes . . , ...... Cost Estimates ...... , . , ...... 5 2.3 Azelaic Acid from Oleic Acid Cost Estimates ...... 6 2.4 Dibasic Acids from Tallow Cost Estimates ...... 8 2.5 Manufacture of Cyclododecatriene, Cyclooctadiene, and Cyclodecadiene Cost Estimates ...... 9 3.1 Producers of Dibasic Acids and Precursors ...... 19 4.1 Dibasic Acids for Polyamide Manufacture . . . . , . . . . . 23 5.1 Cyclododecatriene from Butadiene Patent Summary ...... 39 5.2 Cyclooctadiene from Butadiene by Catalytic Oligomerization Patent Summary . . . . . , ...... 47 5.3 Cyclooligomerizationof Butadiene and Ethylene Patent Summary. , ...... , . . . . . , ...... 53 5.4 Cyclododecatriene from Butadiene Major Process Equipment and Utilities Summary ...... 55 5.5 Cyclododecatriene from Butadiene Stream Flows . . . . . , ...... 59 5.6 Cyclododecatriene from Butadiene Total Capital Investment ...... , . 62 5.7 Cyclododecatriene from Butadiene Production Costs . . . . . , ...... 63 5.8 Cyclooctadiene from Butadiene Major Process Equipment and Utilities Summary ...... 66 5.9 Cyclooctadiene from Butadiene Stream Flows ...... 69 5.10 Cyclooctadiene from Butadiene Total Capital Investment ...... 71

xi TABLES

6.12 Dodecanedioic Acid from Cyclododecatriene via Cyclododecene Total Capital Investment ...... 130 6.13 Dodecanedioic Acid from Cyclododecatriene via Cyclododecene Production Costs ...... 131 7.1 Processes Related to Suberic Acid from Cyclootadiene Patent Summary...... 135 7.2 Patents Related to Processes for Sebacic Acid from Cyclodecadiene ...... 138 7.3 Suberic Acid from Cyclooctadiene via Cyclooctane Major Process Equipment and Utilities Summary ...... 141 7.4 Suberic Acid from Cyclooctadiene via Cyclooctane Total Capital Investment ...... 145 7.5 Suberic Acid from Cyclooctadiene via Cyclooctane Production Costs ...... 147 7.6 Sebacic Acid from Cyclodecadiene via Cyclodecane Major Process Equipment and Utilities Summary ...... 151 7.7 Sebacic Acid from Cyclodecadiene via Cyclodecane Total Capital Investment ...... 157 7.8 Sebacic Acid from Cyclodecadiene via Cyclodecane Production Costs ...... 159 8.1 Sebacic Acid from Castor Oil or Related Substances Patent Summary ...... 165 8.2 Sebacic Acid from Castor Oil Major Process Equipment and Utilities Summary ...... 171 8.3 Sebacic Acid from Castor Oil Stream Flows ...... 175 8.4 Sebacic Acid from Castor Oil Total Capital Investment ...... 179 8.5 Sebacic Acid from Castor Oil Production Costs ...... 181 9.1 Sebacic Ester from Adipic Monoester Patent Summary...... 189

Xiii TABLES

9.2 Sebacic Acid from Adipic Acid by Electrolysis Major Process Equipment and Utilities Summary ...... 194

9.3 Sebacic Acid from Adipic Acid by Electrolysis Stream Flows ...... 199

9.4 Sebacic Acid from Adipic Acid by Electrolysis Total Capital Investment , ...... 203 9.5 Sebacic Acid from Adipic Acid by Electrolysis Production Costs ...... 205 10.1 Azelaic Acid from Oleic Acid Patent summary...... 212 10.2 Azelaic Acid from Oleic Acid Major Process Equipment and Utilities Summary ...... 217 10.3 Azelaic Acid from Oleic Acid Stream Flows...... 221 10.4 Azelaic Acid from Oleic Acid Total Capital Investment ...... , , . 224 10.5 Azelaic Acid from Oleic Acid Production Costs. . . , ...... 225 11.1 Dibasic Acids from Fatty Acids or Fatty Oils Literature Summary ...... 231 11.2 Dibasic Acids from Hydrocarbons by Oxidation Literature Summary ...... 235 11.3 Recovery and Purification of Dibasic Acids Patent Summary...... 240 11.4 Dibasic Acids from Tallow by Oxidation Major Process Equipment and Utilities Summary ...... 244 11.5 Dibasic Acids from Tallow by Oxidation Stream Flows ...... 249 11.6 Dibasic Acids from Tallow by Oxidation Total Capital Investment ...... 259 11.7 Dibasic Acids from Tallow by Oxidation Production Costs ...... , . . . . . 261

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