Report No. 7 CAPROLACTAM PART II by HAROLD C. RIES ROBERT G. MULLER November 1965 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA I CONTENTS PART II VIII INTRODUCTION. 237 IX SUMMARY ............. 239 Orientation ........... ....... 239 General Aspects ......... ....... 242 Technical Aspects ........ ....... 251 X CYCIGHEXANONE FROM PHENOL . 257 Chemistry ............ ....... 257 Review of Processes ....... ....... 259 Raw Materials ......... ....... 261 Process Description ....... ....... 262 Process Discussion ........ ....... 264 costs .............. ....... 269 Capital Investment ....... ....... 269 Production Costs ........ ....... 269 XI CYCLOHEXANONE FROM CYCLOHEXANOL . 275 Chemistry of Dehydrogenation . ....... 275 Review of Processes . ....... 277 Vapor Phase . ....... 277 Liquid Phase . ....... 279 Other Processes . ....... 280 Process Description, Vapor Phase . ....... 281 Process Discussion . ....... 282 Process Description, Liquid Phase ....... 287 Process Discussion . ......... 287 Costs . ......... 291 Capital Investment . ......... 291 Production Costs . ......... 299 Mixed Feed--Vapor Phase . ......... 303 XII CYCLOHEXANOL AND CYCLOHEXANONE FROM CYCLOHEXANE . 307 Introduction . ......... 307 Review of Processes . ......... 307 Process Description . ......... 310 Costs . ......... 315 Capital Investment . ......... 315 Production Costs . ......... 315 iii CONTENTS XIII CYCLOHEXANONEOXIME FROM CYCLOHEXANONE .......... 321 Chemistry ........................ 321 Oximation ....................... 321 Preparation of Hydroxylamine .............. 325 Review of Processes ................... 327 Oximation ....................... 327 Preparation of Hydroxylamine .............. 332 Process Description ................... 333 HydroxylaminePreparation ............... 333 Oximation of Cyclohexanone ............... 335 Materials of Construction ............... 335 costs .......................... 341 Capital Investment ................... 341 Production Costs .................... 341 XIV CAPROLACTAM FROM CYCLOHEXANONE OXIME ........... 347 Introduction. ...................... 347 Chemistry ........................ 347 Review of Processes ................... 350 VaporPhase ...................... 350 Reactors ........................ 351 Process Description ................... 351 costs .......................... 358 Capital Investment ................... 358 Production Costs .................... 358 xv CAPROLACTAM FROM CAPROLACToNE .............. 365 Chemistry ........................ 365 Oxidation of Cyclohexanone to Caprolactone ....... 365 Ammonolysis of Caprolactone .............. 370 Review of Processes ................... 372 Oxidation of Cyclohexanoneto Caprolactone ....... 373 Ammonolysis of Caprolactone .............. 377 Preparation of Peracetic Acid ............. 379 Process Description ................... 383 Oxidation of Cyclohexanoneto Caprolactone ....... 383 Ammonolysis of Caprolactone .............. 395 Purificationof Caprolactam .............. 396 Preparation of Peracetic Acid ............. 397 Raw Materials ..................... 399 iV CONTENTS a Materials of Construction ................ 399 costs .......................... 400 Capital Investment ................... 400 Production Costs .................... 400 Variations Affecting Cost ............... 407 XVI PURIFICATION OF CAPROLACTAM . 411 XVII COMPLETE CAPROLACTAM PROCESSES .............. 413 Introduction. ...................... 413 Capital Investment .................... 415 Production Costs ..................... 415 XVIII OTHER PROCESSES ..................... 423 Caprolactam from Aniline ................. 423 Hydrogenation of Aniline to Cyclohexylamine ...... 424 Oxidation of Cyclohexylamine .............. 425 Cyclohexylamine from Cyclohexanol or Cyclohexanone ... 426 Schmidt Reaction ..................... 426 Miscellaneous Processes ................. 428 APPENDIX D Design and Cost Basis . 431 APPENDIX E Physical Data . 435 APPENDIX F Raw Material and Product Specifications . 439 445 a APPENDIX G I.F.P. Cyclohexanone Process . Cited References . 451 Supplementary References . 467 ILLUSTRATIONS 17 Caprolactam Processes .................... 241 l 18 Cyclohexanone from Phenol .................. 267 19 Vapor Phase Dehydrogenation of Cyclohexanol ......... 283 20 Liquid Phase Dehydrogenation of Cyclohexanol ........ 289 21 Effect of Variables on Costs of Liquid Phase Dehydrogenation of Cyclohexanol ............ 302 22 Cyclohexanol and Cyclohexanone from Cyclohexane ....... 311 23 Effect of Mixing on Rate of Oximation ............ 324 24 Cyclohexanone Oxime from Cyclohexanone ........... 337 0 25 Kinetics of the Beckmann Rearrangement of Cyclohexanone Oxime ................... 348 26 Caprolactam from Oxime ................... 355 27 Caprolactam from Caprolactone ................ 385 28 Caprolactam from Caprolactone ................ 387 29 Effect of Raw Material Costs on Caprolactam Cost ...... 409 30 Effect of By-product Acetic Acid Price on Caprolactam Cost. 410 31 Effect of Caprolactam Yield in Final Purification on Cost . 412 32 Caprolactam Production Costs ................ 422 vii -- - TABLES 55 Caprolactam from Oxime Stream Flows . 357 a 56 Caprolactam from Oxime Process Unit & Utilities Investment ............. 361 57 Caprolactam from Oxime Total Capital Investment .................. 363 58 Caprolactam from Oxime Production Costs . 364 59 Caprolactam from Caprolactone--Sections 100 and 200 Major Process Equipment List . 384 80 Caprolactam from Caprolactone--Sections 300 and 400 Major Process Equipment List . 387 61 Caprolactam from Caprolactone Stream Flows . 389 62 Caprolactam from Caprolactone Process Unit & Utilities Investment . , . 401 63 Caprolactam from Caprolactone Total Capital Investment . 403 64 Caprolactam from Caprolactone Production Costs . 405 a 65 Caprolactam from Phenol Total Capital Investment . 418 66 Caprolactam from Cyclohexane Total Capital Investment . 419 67 Caprolactam from Cyclohexane via Caprolactone Total Capital Investment . 420 68 Caprolactam Processes Production Costs . 421 iX TABLES 26 Process Index. 240 27 Summary of Caprolactam Processes . 247 28 Sensitivity Analysis of Caprolactam Processes . 249 29 Cyclohexanone from Phenol Major Process Equipment List. 266 30 Cyclohexanone from Phenol Process Unit &Utilities Investment . 271 31 Cyclohexanone from Phenol Total Capital Investment . 273 32 Cyclohexanone from Phenol Production Costs . 274 33 Dehydrogenation of Cyclohexanol--Vapor Phase Major Process Equiment List . 283 34 Dehydrogenation of Cyclohexanol--Vapor Phase Stream Flows . 285 35 Dehydrogenation of Cyclohexanol--Liquid Phase Major Process Equipment List . 289 36 Dehydrogenation of Cyclohexanol--Vapor Phase Process Unit & Utilities Investment . , . 293 37 Dehydrogenation of Cyclohexanol--Liquid Phase Process Unit & Utilities Investment . 295 38 Dehydrogenation of Cyclohexanol--Vapor Phase Total Capital Investment . 297 39 Dehydrogenation of Cyclohexanol--Liquid Phase Total Capital Investment . 298 40 Dehydrogenation of Cyclohexanol--Vapor Phase Production Costs . 300 X TABLES 41 Dehydrogenation of Cyclohexanol--Liquid Phase Production Costs . 301 42 Dehydrogenation of Cyclohexanol - Mixed Feed--Vapor Phase Total Capital Investment . 305 43 Dehydrogenation of Cyclohexanol - Mixed Feed--Vapor Phase Production Costs . 366 44 Cyclohexanol and Cyclohexanone from Cyclohexane Major Process Equipment List . 311 45 Cyclohexanol and Cyclohexanone from Cyclohexane StreamFlows . 313 46 Cyclohexanol and Cyclohexanone from Cyclohexane Process Unit & Utilities Investment . 317 47 Cyclohexanol and Cyclohexanone from Cyclohexane Total Capital Investment . , 318 48 Cyclohexanol and Cyclohexanone from Cyclohexane Production Costs . , . , . 319 49 Cyclohexanone Oxime from Cyclohexanone Major Process Equipment List . , , . 337 50 Cyclohexanone Oxime from Cyclohexanone Stream Flows . 339 51 Cyclohexanone Oxime from Cyclohexanone Process Unit & Utilities Investment . 343 52 Cyclohexanone Oxime from Cyclohexanone Total Capital Investment . 344 53 Cyclohexanone Oxime from Cyclohexanone Production Costs . 345 54 Caprolactam from Oxime--Section 400 Major Process Equipment List . 355 Xi .