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 I MENLO PARK, CALIFORNIA
CONTENTS PART II VIII INTRODUCTION... 237 IX SUMMARY..... 239 Orientation.. General Aspects Technical Aspects............ 239 242 251 X CYCIGHEXANONE FROM PHENOL.... Chemistry...... Review of Processes...... Raw Materials... Process Description...... Process Discussion...... costs...... Capital Investment...... Production Costs...... XI CYCLOHEXANONE FROM CYCLOHEXANOL... Chemistry of Dehydrogenation...... Review of Processes..... Vapor Phase... Liquid Phase... Other Processes...... Process Description, Vapor Phase.... Process Discussion..... Process Description, Liquid Phase... Process Discussion Costs.. Capital Investment Production Costs. Mixed Feed--Vapor Phase.. 257 257 259 261 262 264 269 269 269 275 275 277 277 279 280 281 282 287 287 291 291 299 303 XII CYCLOHEXANOL AND CYCLOHEXANONE FROM CYCLOHEXANE 307 Introduction.... Review of Processes Process Description Costs.. Capital Investment Production Costs. 307 307 310 315 315 315 iii
CONTENTS XIII CYCLOHEXANONE OXIME FROM CYCLOHEXANONE. Chemistry... Oximation... Preparation of Hydroxylamine... Review of Processes. Oximation... Preparation of Hydroxylamine... Process Description. Hydroxylamine Preparation... Oximation of Cyclohexanone... Materials of Construction... costs... Capital Investment. Production Costs.. XIV CAPROLACTAM FROM CYCLOHEXANONE OXIME.. Introduction.... Chemistry... Review of Processes. VaporPhase... Reactors... Process Description. costs... Capital Investment. Production Costs.. xv CAPROLACTAM FROM CAPROLACToNE... Chemistry... Oxidation of Cyclohexanone to Caprolactone... Ammonolysis of Caprolactone... Review of Processes. Oxidation of Cyclohexanone to Caprolactone... Ammonolysis of Caprolactone... Preparation of Peracetic Acid... Process Description. Oxidation of Cyclohexanone to Caprolactone... Ammonolysis of Caprolactone... Purification of Caprolactam... Preparation of Peracetic Acid... Raw Materials... 321 321 321 325 327 327 332 333 333 335 335 341 341 341 347 347 347 350 350 351 351 358 358 358 365 365 365 370 372 373 377 379 383 383 395 396 397 399 iv
CONTENTS 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 APPENDIX G I.F.P. Cyclohexanone Process... 445 Cited References 451 Supplementary References. 467
ILLUSTRATIONS 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 Caprolactam Processes.. 241 Cyclohexanone from Phenol 267 Vapor Phase Dehydrogenation of Cyclohexanol 283 Liquid Phase Dehydrogenation of Cyclohexanol... 289 Effect of Variables on Costs of Liquid Phase Dehydrogenation of Cyclohexanol... 302... 311 Effect of Mixing on Rate of Oximation... 324.. 337 Kinetics of the Beckmann Rearrangement of Cyclohexanone Oxime. 348 Caprolactam from Oxime. 355 Caprolactam from Caprolactone... 385 Caprolactam from Caprolactone... 387 Effect of Raw Material Costs on Caprolactam Cost... 409 Effect of By-product Acetic Acid Price on Caprolactam Cost.. 410 Effect of Caprolactam Yield in Final Purification on Cost.. 412 Caprolactam Production Costs... 422 vii
TABLES 55 56 Caprolactam from Oxime Stream Flows.... 357 Caprolactam from Oxime Process Unit & Utilities Investment... 361 57 Caprolactam from Oxime Total Capital Investment 363 58 59 80 61 62 63 64 65 Caprolactam from Oxime Production Costs.. 364 Caprolactam from Caprolactone--Sections 100 and 200 Major Process Equipment List. 384 Caprolactam from Caprolactone--Sections 300 and 400 Major Process Equipment List. 387 Caprolactam from Caprolactone Stream Flows.... 389 Caprolactam from Caprolactone Process Unit & Utilities Investment,.. 401 Caprolactam from Caprolactone Total Capital Investment... 403 Caprolactam from Caprolactone Production Costs.. 405 Caprolactam from Phenol Total Capital Investment... 418 66 Caprolactam from Cyclohexane Total Capital Investment... 419 67 68 Caprolactam from Cyclohexane via Caprolactone Total Capital Investment... 420 Caprolactam Processes Production Costs.. 421 ix
TABLES 26 27 28 Process Index.... Summary of Caprolactam Processes.... Sensitivity Analysis of Caprolactam Processes... 240 247 249 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. 34 Dehydrogenation of Cyclohexanol--Vapor Phase Stream Flows.... 35 Dehydrogenation of Cyclohexanol--Liquid Phase Major Process Equipment List. 36 Dehydrogenation of Cyclohexanol--Vapor Phase Process Unit & Utilities Investment...,.... 37 Dehydrogenation of Cyclohexanol--Liquid Phase Process Unit & Utilities Investment... 38 Dehydrogenation of Cyclohexanol--Vapor Phase Total Capital Investment... 283 285 289 293 295 297 39 40 Dehydrogenation of Cyclohexanol--Liquid Phase Total Capital Investment... Dehydrogenation of Cyclohexanol--Vapor Phase Production Costs.. 298 300 X
TABLES 41 42 43 44 45 46 47 48 49 50 51 52 53 54 Dehydrogenation of Cyclohexanol--Liquid Phase Production Costs.. Dehydrogenation of Cyclohexanol - Mixed Feed--Vapor Phase Total Capital Investment... Dehydrogenation of Cyclohexanol - Mixed Feed--Vapor Phase Production Costs.. Major Process Equipment List. StreamFlows.... Process Unit & Utilities Investment... Total Capital Investment.., Production Costs..,.,.. Major Process Equipment List...,,. Stream Flows.... Process Unit & Utilities Investment... Total Capital Investment... Production Costs.. Caprolactam from Oxime--Section 400 Major Process Equipment List. 301 305 366 311 313 317 318 319 337 339 343 344 345 355 Xi