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Caprolactam, Supplement A Report No. 7-A CAPROLACTAM SUPPLEMENT A by HAROLD C. RIES March 1868 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA I CONTENTS 1 INTRODUCTION . 1 2 SUMMARY.......................... 3 3 INDUSTRY STATUS. 17 4 CAPROLACTAM BY THE PHOTONITROSATION OF CYCLOHEXANE .... 27 Chemistry ......................... 27 Review of Processes .................... 29 Photochemical Lamps ................... 30 PNC Reactors ...................... 33 PNC Processes ...................... 35 Nitrosyl Chloride Production .............. 37 Caprolactam Purification ................ 38 8 Process Description .................... 42 Nitrosyl Chloride Production .............. 44 Photonitrosation of Cyclohexane ............. 45 Rearrangement ...................... 47 Caprolactam Purification ................ 48 Ammonium Sulfate Recovery ................ 49 Process Discussion .................... 68 Costs ........................... 72 Capital Investment ................... 72 Production Costs .................... 81 5 CYCLOHEXANONE FROM CYCLOHEXANE .............. 87 Review of Processes .................... a7 Cyclohexane Oxidation .................. 87 Dehydrogenation of Cyclohexanol ............. 87 Stamicarbon Process ................... 90 Process Description .................... 92 Cyclohexane Oxidation (I.F.P. Process) ......... 92 Cyclohexanone from Mixed Oil .............. 96 costs ........................... 97 E Capital Investment ................... 97 100 8 Production Costs .................... 8 iii CONTENTS CYCLOHEXANONE OXIME FROM CYCLOHEXANONE . 105 Chemistry . ................ 105 Hydroxylamine Preparation ................ 105 Oximation . ................ 106 Review of Processes . ................ 107 Hydroxylamine Preparation ................ 107 Oximation . ................ 109 Process Description . .. ................ 112 Hydroxylamine Production ................ 112 Oximation . ................ 113 Process Discussion . ................ 113 costs . ................ 118 Capital Investment . ................ 118 Production Costs . ................ 120 7 CYCLOHEXANONE OXIME BY NITROCYCLOHEXANE ROUTE . 123 Chemistry ......................... 123 Review of Processes .................... 123 Nitration of Cyclohexane ................ 123 Cyclohexanone Oxime from Nitrocyclohexane ........ 124 Process Description .................... 126 Nitrocyclohexane Production ............... 126 Reduction of Nitrocyclohexane .............. 127 By-Product Handling ................... 128 costs ........................... 138 Capital Investment ................... 138 Production Costs .................... 138 8 CAPROLACTAM FROM CYCLOHEXANONE OXIME ........... 143 Chemistry ......................... 143 Review of Processes .................... 143 Ion Exchange Process ................... 148 Process Description ................... 148 Process Discussion ................... 148 Vapor-Phase Process .................... 153 Process Description ................... 153 Process Discussion ................... 154 Rearrangement in Oleum .................. 160 costs ........................... 162 Capital Investment ................... 162 Production Costs .................... 165 iV CONTENTS 9 CAPROLACTAM BY CAPROLACTONE ROUTE . 171 Review of Processes . .......... 171 Caprolactone from Cyclohexanone . .......... 171 Preparation of Peracetic Acid . .......... 174 Caprolactam from Caprolactone . .......... 175 Miscellaneous Routes to Caprolactone .......... 177 Process Description . .......... 179 Caprolactone from Cyclohexanone . .......... 179 Caprolactam from Caprolactone . .......... 179 Process Discussion . .......... 190 costs . .......... 191 Capital Investment . .......... 191 Production Costs . .......... 196 10 COMPLETE PROCESSES . 201 Introduction . 201 costs........................... 201 Caprolactam via Cyclohexanone and Rearrangement in Oleum 201 Caprolactam via Cyclohexanone and Vapor-Phase Rearrangement . 209 Caprolactam via Nitrocyclohexane and Vapor-Phase Rearrangement . 215 Caprolactam by Hexahydrobenzoic Acid Process . 221 Comparison of Processes . 227 11 CHEMISTRY OF OTHER PROCESSES . 235 Hexahydrobenzoic Acid Route . 235 Techni-Chem Process . 236 Preparation of 2-Nitrocyclohexanone from Cyclohexanone . 236 Conversion of 2-Nitrocyclohexanone to a-Aminocaproic Acid . 239 12 REVIEW OF OTHER PROCESSES ................. 241 Hexahydrobenzoic Acid Route ................ 241 Benzoic Acid from Toluene ................ 241 Catalysts ....................... 242 Reaction Media .................... 242 Reactors ....................... 243 Benzoic Acid Purification ............... 243 Hexahydrobenzoic Acid Production ............ 244 Nitrosylsulfuric Acid .................. 247 Caprolactam from Hexahydrobenzoic Acid ......... 248 V CONTENTS 12 (continued) Phenol Hydrogenation ................... 251 Miscellaneous Processes .................. 253 APPENDIX A DESIGN AND COST BASIS ............... 259 APPENDIX B PHYSICAL DATA ................... 265 APPENDIX C RAW MATERIAL AND PRODUCT SPECIFICATIONS ...... 273 APPENDIX D HEALTH, SAFETY, AND POLLUTION ........... 275 APPENDIX E MATERIALS OF CONSTRUCTION ............. 279 REFERENCES........................... 281 SUPPLEMENTAL REFERENCES . 317 vi ILLUSTRATIONS 4.1 Effect of Lamp Size on Useful Energy (4,000-7,600Angstrom Band) . 31 4.2 Effect of Lamp Size on Oxime Yield . 31 4.3 Caprolactam by PNC Process . 51 5.1 Cyclohexane Oxidation--I.F.P. Process . 93 6.1 Cyclohexanone Oxime from Cyclohexanone . 115 7.1 Cyclohexanone Oxime by Nitrocyclohexane Process . 131 8.1 Caprolactam from Cyclohexanone Oxime (Ion Exchange Process) . , . 151 8.2 Caprolactam from Cyclohexanone Oxime (Vapor-Phase Process) . 157 9.1 Caprolactam by Caprolactone In-Situ Process . 183 10.1 Caprolactam Production Cost Variation . 233 11.1 Mechanism of HBA Nitrosation to s-Caprolactam . 237 11.2 Side Reactions During HBA Nitrosation to s-Caprolactam . 238 11.3 Possible Reactions in Production of 2-Nitrocyclohexanone 240 B.1 Boiling Points of Aqueous Caprolactam Solutions . 267 B.2 Viscosity of Oily Oxime Salt . 270 Vii TABLES 2.1 Summary of Caprolactam Processes . , . 9 2.2 Sensitivity Analysis of Caprolactam Processes . 11 3.1 Plant Capacities Americas . 19 3.2 Plant Capacities Europe . 21 3.3 Plant Capacities Middle and Far East . 23 3.4 Plant Capacities Soviet Bloc....................... 25 4.1 Caprolactam by PNC Process (Oxime Rearrangement) Major Process Equipment List . 51 4.2 Caprolactam by PNC Process (Oxime Rearrangement) Stream Flows . 61 4.3 Caprolactam by PNC Process (Oxime Rearrangement) Utilities Summary. , . 67 4.4 Caprolactam by PNC Process (Oxime Rearrangement) Process Unit and Utilities Investment , . 75 4.5 Caprolactam by PNC Process (Oxime Rearrangement) Total Capital Investment . 77 4.6 Caprolactam by PNC Process (Oxime Hydrochloride Rearrangement) Utilities Summary. 78 4.7 Caprolactam by PNC Process (Oxime Hydrochloride Rearrangement) Process Unit and Utilities Investment . 79 4.8 Caprolactam by PNC Process (Oxime Hydrochloride Rearrangement) Total Capital Investment . 80 iX TABLES 4.3 Caprolactam by PNC Process (Oxime Rearrangement) Production Costs . 83 4.10 Caprolactam by PNC Process (Oxime Hydrochloride Rearrangement) 85 Production Costs . I 5.1 Reaction Products from Oxidation of Cyclohexane . 94 5.2 Analysis of Cyclohexanol-CyclohexanoneMixture . 95 5.3 Cyclohexanone from Cyclohexane Total Capital Investment . 99 5.4 Cyclohexanone from Cyclohexane Utilities Summary . 102 5.5 Cyclohexanone from Cyclohexane Production Costs . 103 6.1 Cyclohexane Oxime from Cyclohexanone Major Process Equipment List . 114 6.2 Cyclohexanone Oxime from Cyclohexanone Stream Flows . 115 6.3 Cyclohexanone Oxime from Cyclohexanone Utilities Summary . 117 6.4 Cyclohexanone Oxime from Cyclohexanone Process Unit and Utilities Investment . 119 6.5 Cyclohexanone Oxime from Cyclohexanone Production Costs . 121 7.1 Cyclohexanone Oxime by Nitrocyclohexane Process Major Process Equipment List . 130 7.2 Cyclohexanone Oxime by Nitrocyclohexane Process Stream Flows . 133 X TABLES 7.3 Cyclohexanone Oxime by Nitrocyclohexane Process Utilities Summary . , . 137 7.4 Cyclohexanone Oxime by Nitrocyclohexane Process Process Unit and Utilities Investment . 139 7.5 Cyclohexanone Oxime by Nitrocyclohexane Process Production Costs . 141 8.1 Caprolactam fromCyclohexanone Oxime (Ion Exchange Process) Major Process Equipment List . 151 8.2 Caprolactam from Cyclohexanone Oxime (Ion Exchange Process) Stream Flows . 151 8.3 Caprolactam from Cyclohexanone Oxime (Vapor-Phase Process) Major Process Equipment List . , . 157 8.4 Caprolactam from Cyclohexanone Oxime (Vapor-Phase Process) Stream Flows . 157 8.5 Caprolactam from Cyclohexanone Oxime (Vapor-Phase Process) Utilities Summary . 159 8.6 Caprolactam from Cyclohexanone Oxime (Rearrangement in Oleum) Utilities Summary . 161 8.7 Caprolactam from Cyclohexanone Oxime (Vapor-Phase Process) Process Unit and Utilities Investment . .. 163 8.8 Caprolactam from Cyclohexanone Oxime (Rearrangement in Oleum) Process Unit and Utilities Summary . 164 Xi TABLES 8.9 Caprolactam from Cyclohexanone Oxime (Vapor-Phase Process) Production Costs . 167 8.10 Caprolactam from Cyclohexanone Oxime (Rearrangement in Oleum) Production Costs . 169 I 9.1 Caprolactam by Caprolactone In-Situ Process Major Process Equipment List . 182 9.2 Caprolactam by Caprolactone In-Situ Process Stream Flows . 185 9.3 Caprolactam by Caprolactone In-Situ Process Utilities Summary . 189 9.4 Caprolactam by Caprolactone
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