PROCESS ECONOMICS PROGRAM SRI INTERNATIONAL Menlo Park, California 94025 Abstract Process Economics Program Report No. 1D ISOCYANATES (July 1983) In this report, SRI reviews the technology for making commercial and experimental nonaromatic isocyanates. The commercial isocyanates include hexamethylene diisocyanate, hydrogenated MDI, isophorone diisocyanate, dimer diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, and trimethylhexamethylenediisocyanate. The experimental nonaromatic isocyanates that we reviewed include 1,6,11- undecane triisocyanate, lysine-ethylester triisocyanate, trans- cyclohexane diisocyanate, and tetramethylxylylenediisocyanate. We evaluated eight phosgenation processes and one nonphosgenation process. We also evaluated two processes which manufacture respec- tively an adduct of hexamethylene diisocyanate and a blocked isophorone diisocyanate. PEP'82 YRC/CN Report No. 1D ISOCYANATES SUPPLEMENT D by YU-REN CHIN wlth contributions by CHIEN NIEH c0 I July 1983 aa A private report by the m PROCESS ECONOMICS PROGRAM Menlo Park, California 94025 For detailed marketing data and information, the reader is referred to one of the SRI programs specializing in marketing research. The CHEMICAL ECONOMICS HANDBOOK Program covers most major chemicals and chemical products produced in the United States and the WORLD PETROCHEMICALS Program covers major hjdrocarbons and their derivatives on a worldwide basis. In addition, the SRI DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, prod- uct, and plant for the United States and Western Europe. ii CONTENTS 1 INTRODUCTION. ....................... 1 2 SUMMARY .......................... 3 General Aspects ...................... 3 Technical Aspects ..................... 4 Economic Aspects. ..................... 5 3 INDUSTRY STATUS ...................... 15 Markets .......................... 15 Producers ......................... 16 4 HEXAMETHYLENE DIISOCYANATE. ................ 19 Chemistry ......................... 19 Process Description .................... 21 Phosgenation of Hexamethylenediamine. .......... 21 Phosgene and HCl Recovery ................ 23 Process Discussion. .................... 27 Cost Estimates. ...................... 27 5 HYDROGENATED MDI. ..................... 39 Chemistry ......................... 39 Review of Processes .................... 40 Process Description--Manufactureof MDA .......... 43 Cost Estimates--Manufacture of MDA. ............ 44 Process Description--Manufactureof Hydrogenated MD1 fromMDA .......................... 49 Hydrogenation of MDA. .................. 49 Phosgenation of Hydrogenated MDA. ............ 51 Recovery of Phosgene and HCl. .............. 52 Process Discussion--Manufactureof Hydrogenated MD1 fromMDA .......................... 58 Cost Estimates--Manufacture of Hydrogenated MD1 fromMDA .......................... 58 6 ISOPHORONE DIISOCYANATE .................. 71 Chemistry ......................... 71 Review of Processes .................... 74 Process Description .................... 74 Cyanoketone Production. ................. 77 Isophorone Diamine Production .............. 77 Isophorone Diisocyanate Production. ........... 78 Product Purification and Phosgene Recovery. ....... 78 iii CONTENTS 6 ISOPHORONE DIISOCYANATE (Continued) Process Discussion. , . 86 Cost Estimates. 86 7 XYLYLENE DIISOCYANATE AND HYDROGENATED XYLYLENE DIISOCYANATE. ....................... 95 Chemistry ......................... 95 Review of Processes .................... 96 Process Description--XDA from Xylene. ........... 98 Amnoxidation of Xylene to Isophthalonitrile ....... 98 Hydrogenation of Phthalonitrile ............. 100 Process Discussion--XDA from Xylene ............ 109 Cost Estimates--XDA from Xylene .............. 109 Process Description--H6XDA from XDA ............ 116 Process Discussion--H6XDA from XDA. ........... 121 Cost Estimates--HgXDA from XDA. ............. 121 Process Description--XDI from XDA ............. 127 Phosgenation of XDA ................... 127 Purification of XDI ................... 127 Process Discussion--XDI from XDA. ............ 134 Cost Estimates--XDI from XDA. .............. 134 Economics of the H6XDI Process. .............. 142 Sunnnary.......................... 142 8 TRIMETHYLHEXAMETHYLENEDIISOCYANATE ............ 145 Chemistry ......................... 145 Review of Processes .................... 148 Process Description--TMHDA from Isophorone. ........ 148 Trimethylcyclohexanol Production. ............ 155 Trimethyl Adiponitrile Production ............ 155 Trimethylhexamethylene Diamine Production ........ 156 Process Discussion--TMHDA from Isophorone ......... 162 Cost Estimates--TMHDA from Isophorone ........... 163 Process Description--TMHDI from TMHDA ........... 170 Cost Estimates--TMHDI from TMHDA. ............. 176 9 DIMER DIISOCYANATE. .................... 183 Chemistry ......................... 183 Manufacture of Dimer Amine. ................ 184 Manufacture of Dimer Diisocyanate ............. 188 Process Description ................... 188 Cost Estimates. ..................... 189 iv - CONTENTS 10 TRIISOCYANATES. 197 Chemistry . , . 197 Review of Processes . 201 Process Description--1,6,11-UndecaneTriisocyanate. 201 Production of Tetrahydroazepine . , . 205 Production of Undecane Triamine . 205 Production of Undecane Triisocyanate. , . 206 Recovery of Lithium Hydroxide, Phosgene, and HCl. 207 Process Discussion--1,6,11-UndecaneTriisocyanate . , . 216 Cost Estimates--1,6,11-UndecaneTriisocyanate , . 217 Process Description--Lysine-ethylester Triisocyanate . , . 225 Production of Lysine-8-aminoethylesterTri-HCl. 225 Production of Lysine-ethylester Triisocyanate . 227 Recovery of Solvents, Phosgene and HCl. 227 Process Discussion--Lysine-ethylesterTriisocyanate . 235 Cost Estimates--Lysine-ethylester Triisocyanate . 235 11 TRANS-CYCLOHEXANE-1,4-DIISOCYANATE............. 245 Chemistry ......................... 245 Review of Processes .................... 246 Process Description .................... 248 Production of CHDCA ................... 248 Production of CHDI. ................... 250 Purification of CHDI. .................. 251 Process Discussion. .................... 257 Cost Estimates. ...................... 257 12 TETRAMETRYLXYLYLENE DIISOCYANATE. 267 13 ADDUCTS .......................... 269 Biurets .......................... 269 Blocked Isocyanates .,................... 272 Adducts with Polyols. ................... 272 Isocyanurates ....................... 275 A Process for Making Biuret from BDI. ........... 278 Process Description ................... 278 Process Discussion. ................... 282 Cost Estimates. ..................... 282 A Process for Making Blocked IPDI ............. 287 Process Description ................... 287 Process Discussion. ................... 291 Cost Estimates. ..................... 291 V CONTENTS 14 OTHER NONAROMATIC ISOCYANATES . 297 Phosgenation Processes, . 297 Nonphosgenation Processes . 305 Thermal Decomposition of Substituted Urethane . I 305 Thermal Decomposition of Adduct of Furoxan and Vicinal Diketone. 306 Reaction of N-chloroamide with a Tertiary Amine . 307 Oxidation of N-Substituted Formamide. 307 Reaction of Amine and Chloroformate . 308 Reaction of Amide with Alkali Metal Hypobromite . 308 Isocyanates from Substituted Urea . 309 Isocyanates from Carbamic Acid Salt or Acid Chloride. 310 Miscellaneous Processes . 310 APPENDIX A--DESIGN AND COST BASIS. 311 APPENDIX B--PHYSICAL PROPERTIES. 315 CITEDREFERENCES........................ 317 PATENTREFERENCES BYCOMPANY. 325 vi ILLUSTRATIONS 4.1 Hexamethylene Diisocyanate from Hexamethylene Diamine by Phosgenation Flowsheet........................ 329 4.2 Hexamethylene Diisocyanate from Hexamethylene Diamine by Phosgenation Effect of Plant Capacity and Operating Level on Product Values of Plant A and Plant B. , . 37 5.1 MDA from Aniline and Formaldehyde Effect of Operating Level and Plant Capacity on Production Cost. 48 5.2 Hydrogenated MD1 from MDA Flowsheet........................ 333 5.3 Hydrogenated MD1 from MDA Effect of Operating Level and Plant Capacity on Product Value. 67 6.1 Isophorone Diisocyanate FlowSheet........................ 335 6.2 Isophorone Diisocyanate Effect of Operating Level and Plant Capacity on Production Cost. , . 93 7.1 Xylylene Diamine from Xylene by Ammoxidation and Hydrogenation Flow Sheet. ; . 339 7.2 Xylylene Diamine from Xylene by Ammoxidation and Hydrogenation Effect of Operating Level and Plant Capacity on Production Cost. 115 7.3 Hydrogenated Xylylene Diamine from XDA Flowsheet........................ 343 7.4 Hydrogenated Xylylene Diamine from Xylylene Diamine Effect of Operating Level and Plant Capacity on Production Cost. 125 7.5 Xylylene Diisocyanate from Xylene Diamine by Phosgenation Flowsheet........................ 345 vii ILLUSTRATIONS 7.6 Xylylene Diisocyanate from Xylylene Diamine by Phosgenation Effect of Operating Level and Plant Capacity on Production Cost. 141 8.1 Trimethylhexamethylene Diamine from Isophorone FlowSheet........................ 347 8.2 Trimethylhexamethylene Diamine from Isophorone Effect of Operating Level and Plant Capacity on Production Cost. , . 169 8.3 Trimethylhexamethylene Diisocyanate from Trimethylhexamethylene Diamine FlowSheet........................ 351 8.4 Trimethylhexamethylene Diisocyanate from Trimethylhexamethylene Diamine Effect of Operating Level and Plant Capacity on Production Cost. 180 9.1 Dimer Diisocyanate from Dimer Amine FlowSheet.......................