PROCESS ECONOMICS PROGRAM Abstract SRI INTERNATIONAL Menlo Park, California 94025 Process Economics Program Report No. 5C VINYL CHLORIDE (December 1982) This report covers the manufacture of vinyl chloride and its precursor, ethylene dichloride. The processes evaluated for ethylene dichloride (EDC) manufacture include three processes for the chlorination of ethylene (EDC withdrawn as a liquid, EDC withdrawn as a vapor with rectification, and EDC withdrawn as a vapor without rectification), four processes for oxychlorination of ethylene (varying in the use of oxygen or air, and fluidized bed or fixed bed), and a process in an early stage of development using trimethylamine hydrochloride instead of HCl in oxychlorination. The processes evaluated for making vinyl chloride include the pyrolysis of EDC, the hydrochlorination of acetylene (two versions-- fixed bed and fluidized bed), and a process in an early stage of development using laser initiation for cleavage of EDC. Integrated processes starting from ethylene, or ethylene and acetylene--with or without some purchased HCl or EDG-are evaluated in ten variations. Processes are compared in the following respects: The use of acetylene compared with the use of ethylene, the use of chlorine compared with the use of HCl, and integrated production compared with separate production of EDC and vinyl chloride in two regions. PEP'81 YCY LCH C-FC
February 1983 ADDENDUM TO VINYL CHLORIDE REPORT NO. SC It has recently been brought to our attention that Mitsui Engineering and Shipbuilding Co., Ltd. was the contractor for the following plants in Japan: Central Chemical Nissan Petrochemical (in conjunction with Hitachi) Sun-Arrow Toyo Soda, both the Shin Nanyo and Yokkaichi plants (in conjunction with Hitachi) The above information should be inserted in Table 3.3 (p.18).
I a 0 I E 0 on u a D E kl Report No. 5C VINYL CHLORIDE SUPPLEMENT C.by YEN-CHEN YEN with contributions by LIN CHAIO HSU and CHiN-FWU CHIOU December 1982 A private report by the 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 UANDROOK Program covers most major chemicals and chemical products produced in the United States and the WORLD PE'lROCURMICALS Program covers major hydrocarbons 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 4 5 6 INTRODUCTION... SUMMARY... INDUSTRY STATUS.... Producers, Production Capacity, and Processes... Demand and Supply... Trade... COMPARISON OF PROCESSES FOR MAKING VINYL CHLORIDE... The Use of Chlorine Compared with the Use of Hydrogen Chloride... Vinyl Chloride from Ethylene or Acetylene... Integration Versus Separate Production of EDC and Vinyl Chloride.... VINYL CHLORIDE BY HYDROCHLORINATION OF ACETYLENE.... Review of Processes... Vinyl Chloride from Acetylene by Hydrochlorination in Fluidized Bed, Almost Complete Recovery of Vinyl Chloride and Mercury.... Process Description... Process Discussion.... Cost Estimates.... Vinyl Chloride from Acetylene by the Simpler, Conventional Hydrochlorination Process.... ETHYLENE DICHLORIDE BY CHLORINATION OF ETHYLENE... Chemistry... Review of Processes... Feed... Reaction Medium and Catalyst.... Product Withdrawal from the Reactor... Cooling... Reactor... Removal of Ferric Chloride.... Purification of EDC... Waste Streams... 1 3 11 11 11 12 27 27 29 31 33 33 35 35 48 49 56 67 67 68 68 74 74 75 75 76 76 79 iii
CONTENTS 6 ETHYLENE DICHLORIDE BY CHLORINATION OF ETHYLENE (Continued) Ethylene Dichloride by Chlorination, Liquid Product... Process Description.................. Process Discussion................... Cost Estimates..................... Ethylene Dichloride by Chlorination, Gaseous Product, Rectification at the Reactor.......... Process Description.................. Process Discussion................... Cost Estimates..................... Ethylene Dichloride by Chlorination, Gaseous Product, No Rectification at the Reactor......... 7 ETHYLENE DICHLORIDE BY OXYCHLORINATION OF ETHYLENE.... Chemistry... Review of Processes... Reaction Conditions... Reactors... Use of Air or Oxygen.... Feed Composition.... Catalyst.... Throughput.... Recovery... Residual Gas.... Fluidized Bed, with Air... Process Description... Process Discussion.... Cost Estimates.... Fluidized Bed, with Oxygen.... Process Description... Process Discussion.... Cost Estimates.... Fixed Bed, with Air... Process Description... Process Discussion.... Cost Estimates.... 80 80 ii: 94 94 99 99 105 107 107 108 108 112 113 114 114 115 115 124 128 128 138 138 143 143 150 150 156 156 166 166 iv
CONTENTS 7 ETHYLENE DICHLORIDE BY OXYCHLORINATION OF ETHYLENE (Continued) Fixed Bed, with Oxygen... Process Description... Cost Estimates.... Comparison of Processes... 8 VINYL CHLORIDE FROM ETHYLENE DICHLORIDE BY PYROLYSIS... Chemistry... Review of Processes... Feeds... Reactor... Heat Recovery... Separation.... Purification of VC.... Purification EDC.... Hydrogen Chloride... Process Description... Process Discussion.... Cost Estimates.... 9 INTEGRATED PROCESSES FOR MARING VINYL CHLORIDE.... Vinyl Chloride by Integrated Ethylene Chlorination, Ethylene Oxychlorination, and Ethylene Dichloride Pyrolysis, Case A, Conventional Balanced Process.... Process Description... Process Discussion.... Cost Estimates,... Vinyl Chloride by Integrated Ethylene Chlorination, Ethylene Oxychlorination, and Ethylene Dichloride Pyrolysis, Case B, Energy Efficient Balanced Process... Process Description... Process Discussion.... Cost Estimates.... Alternatives to Cases A and B... Vinyl Chloride by Integrated Ethylene Oxychlorination and Ethylene Dichloride Pyrolysis, Part of Ethylene Dichloride Purchased... Vinyl Chloride by Integrated Ethylene Oxychlorination and Ethylene Dichloride Pyrolysis, Part of Hydrogen Chloride Purchased... 171 171 179 184 185 185 186 187 187 188 188 188 189 189 198 206 206 211 212 212 224 224 230 230 240 240 247 249 249 V
CONTENTS 9 INTEGRATED PROCESSES FOR MAKING VINYL CHLORIDE (Continued) Vinyl Chloride by Integrated Ethylene Dichloride Pyrolysis and Acetylene Hydrochlorination.,.,,.,. Vinyl Chloride by Integrated Ethylene Chlorination, Ethylene Chloride Pyrolysis, and Acetylene Hydrochlorination.................... 10 OTHER PROCESSES FOR MAKING ETHYLENE DICHLORIDE.... Ethylene Dichloride by Oxychlorination, Chlorine Derived from Ammonium Chloride.... Ethylene Dichloride by Oxychlorination, Chlorine Derived from Trinuzthylamine Hydrochloride... Chemistry... Process Description... Process Discussion.... Cost Estimates.... Ethylene Dichloride by an Electrolytic Process Using Hydrochloric Acid... 11 OTHER PROCESSES FOR MAKING VINYL CHLORIDE........ Vinyl Chloride Directly from Ethylene. Vinyl Chloride from Ethane....... Other Processes............ Vinyl Chloride from Ethylene Dichloride Laser Process............. Process Description...,..... Process Discussion....,..... Cost Estimates..................... ljy'the............ 262 262 269 269 271 271 272 278 278 283 285 285 285 287 293 293 297 298 Appendix A PHYSICAL DATA... CITEDREFERENCES....................... PATENT REFERENCES BY COMPANY................. 303 305 325 Vi
ILLUSTRATIONS 4.1 4.2 5.1 5.2 6.1 6.2 6.3 7.1 7.2 7.3 7.4 7.5 8.1 Comparison of Chlorine and Hydrogen Chloride as Raw Materials for Vinyl Chloride.......... Comparison of Ethylene and Acetylene as Eaw Materials for Vinyl Chloride.......... Vinyl Chloride from Acetylene, Negligible Mercury.......... Vinyl Chloride from Acetylene, Negligible Mercury Effect of Operating Level, Plant Capacity, and Raw Material Rices on Production Cost and Product Value..................... Ethylene Dichloride by Chlorination, Liquid Product..................... Ethylene Dichloride by Chlorination, Gaseous Product, Rectification............. Ethylene Dichloride by Chlorination, Gaseous Product, Rectification Effect of Operating Level, Plant Capacity, and Raw Material Prices on Production Cost and Product Value..................... Ethylene Dichloride by Oxychlorination in Fluidized Bed Using Air............... Ethylene Dichloride by Oxychlorination in Fluidized Bed Using Oxygen............. Ethylene Dichloride by Oxychlorination in Fluidized Bed Using Oxygen Effect of Operating Level, Plant Capacity, and Raw Material Rices on Production Cost and Product Value..................... Ethylene Dichloride by Oxychlorination in Fixed Bed Using Air................. Ethylene Dichloride by Oxychlorination in Fixed Bed Using Oxygen............... Vinyl Chloride from Ethylene Dichloride by Pyrolysis...................... 28 30 331 55 335 337 104 339 341 155 343 347 349 Vii
ILLUSTRATIONS 8.2 Vinyl Chloride from Ethylene Dichloride by Pyrolysis Effect of Operating Level, Plant Capacity, Raw Material Price, and By-Product Credits on Production Cost and Product Value.......... 9.1 Integration Schemes for Vinyl Production........ 9.2 Vinyl Chloride from Ethylene by a Balanced Process (Case A)............. 9.3 Vinyl Chloride from Ethylene by a Balanced Process (Case A) Effect of Operating Level, Plant Capacity, and Raw Material Rices on Production Cost and Roduc t Value..................... 9.4 Vinyl Chloride from Ethylene by a Balanced Process (Case B)............. 9.5 Vinyl Chloride from Ethylene by a Balanced Process (Case B) Effect of Operating Level, Plant Capacity, and Raw Material Prices on Production Cost and Product Value..................... 11.1 Vinyl Chloride frm Ethylene Dichloride by Laser Process.................... A-l Explosive Region of a Gaseous Mixture Containing Ethylene, Oxygen, and Inerts........ 210 351 353 229 357 246 361 304 viii
TABLES 2.1 2.2 2.3 2.4 2.5 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 5.1 5.2 5.3 Vinyl Chloride from Acetylene cost Summary.................... Ethylene Dichloride by Chlorination Cost Summary... Ethylene Dichloride by Oxychlorination Cost Sumnary.................... Vinyl Chloride from Ethylene Dichloride cost summary.................... Vinyl Chloride by Integrated Processes cost sunmlary.................... Producers of Vinyl Chloride and Ethylene Dichloride in the United States................ Producers of Vinyl Chloride and Ethylene Dichloride in Western Europe.................. Producers of Vinyl Chloride and Ethylene Dichloride In Japan... Producers of Vinyl Chloride and Ethylene Dichloride in Eastern Europe.................. Producers of Vinyl Chloride and Ethylene Dichloride in Canada, Mexico, and OPEC............. Producers of Vinyl Chloride and Ethylene Dichloride in Countries Other Than USA, Europe, Japan, Canada, Mexico, and OPEC.............. Vinyl Chloride Capacity; Using Ethylene or Acetylene Process.................. Vinyl Chloride Demand................ International Trade of EDC, VCM, and PVC...... Vinyl Chloride from Acetylene............ Vinyl Chloride from Acetylene, Negligible Mercury Design Bases and Assumptions............ Vinyl Chloride from Acetylene, Negligible Mercury StreamFlows.................... 41 4 5 8 9 10 13 15 18 19 20 22 24 25 25 34 36 IX
TABLES 5.4 5.5 5.6 5.7 5.8 5.9 5.10 5.11 5.12 6.1 6.2 6.3 6.4 Vinyl Chloride from Acetylene, Negligible Mercury Major Equipment................... Vinyl Chloride from Acetylene, Negligible Mercury Utilities Summary.................. Vinyl Chloride from Acetylene, Negligible Mercury Total Capital Investment.............. Vinyl Chloride from Acetylene, Negligible Mercury Vinyl Chloride from Acetylene, Tolerable Mercury Design Bases and Assumptions............ Vinyl Chloride from Acetylene, Tolerable Mercury Major Equipment................... Vinyl Chloride from Acetylene, Tolerable Mercury Utilities Summary.................. 61 Vinyl Chloride from Acetylene, Tolerable Mercury Total Capital Investment.............. Vinyl Chloride from Acetylene, Tolerable Mercury 64 Ethylene Dichloride by Liquid Phase Chlorination of Ethylene Patent Summary... Ethylene Dichloride by Gas Phase Chlorination of Ethylene and Other Chlorination Processes Patent Summary... Recovery and Purification of Ethylene Dichloride from Chlorination Patent Summary..........L........ Ethylene Dichloride by Chlorination, Liquid Product Design Bases and Assumptions............ 44 47 51 53 57 58 62 69 72 77 81 X
TABLES 6.5 6.6 6.7 6.8 6.9 6.10 6.11 6.12 6.13 6.14 6.15 6.16 6.17 7.1 Ethylene Dichloride by Chlorination, Liquid Product Stream Flows.................... Ethylene Dichloride by Chlorination, Liquid Product Major Equipment...,............... Ethylene Dichloride by Chlorination, Liquid Product Utilities Summary.................. Ethylene Dichloride by Chlorination, Liquid Product Total Capital Investment.............. Ethylene Dichloride by Chlorination, Liquid Product, 99.8 pet Production Costs.......,.......... Ethylene Dichloride by Chlorination, Liquid Product, 99.5 pet Ethylene Dichloride by Chlorination, Gaseous Product Design Bases and Assumptions............ Ethylene Dichloride by Chlorination, Gaseous Product, Rectification StreamFlows.................... Ethylene Dichloride by Chlorination, Gaseous Product, Rectification Major Equipment................... Ethylene Dichloride by Chlorination, Gaseous Product, Rectification Utilities Suunmwy................... Ethylene Dichloride by Chlorination, Gaseous Product, Rectification Total Capital Investment.............. Ethylene Dichloride by Chlorination, Gaseous Product, Rectification Ethylene Dichloride by Chlorination, Gaseous Product, No Rectification Ethylene Dichloride by Oxychlorination with Little By-Production Patent Suwary... 83 84 86 89 91 93 94 96 97 98 101 102 106 109 Xi
TABLES 7.2 7.3 7.4 7.5 7.6 7.7 7.8 7.9 7.10 7.11 7.12 7.13 7.14 7.15 Ethylene Dichloride by Oxychlorination Licensed Process.................. 112 Ethylene Dichloride by Oxychlorination with Substantial By-Production Patent Summary... 116 Purification of Hydrogen Chloride Patent summary... Recovery of Ethylene Dichloride Patent Summary... Purification of Ethylene Dichloride Patent Summary... Treatment of Heavy Ends in Ethylene Dichloride and Vinyl Chloride Production Patent summary... 118 119 120 121 Treatment of Residual Gas from Ethylene Dichloride Manufacture Patent Sunmary................... 125 Fluidized Bed Using Air Design Bases and Assumptions............ 129 Fluidized Bed Using Air Stream Flows.................... 131 Fluidized Bed Using Air Major Equipment................... Fluidized Bed Using Air Utilities Sunnnary.................. Fluidized Bed Using Air Total Capital Investment.............. Fluidized Bed Using Air 135 137 139 141 Fluidized Bed Using Oxygen Design Bases and Assumptions............ 143 Xii
TABLES 7.16 7.17 7.18 7.19 7.20 7.21 7.22 7.23 7.24 7.25 7.26 7.27 7.28 Fluidized Bed Using Oxygen Stream Flows.................... Fluidized Bed Using Oxygen Major Equipment................... Fluidized Bed Using Oxygen Utilities Summary.................. Fluidized Bed Using Oxygen Total Capital Investment.............. Fluidized Bed Using Oxygen Fixed Bed Using Air Design Bases and Assumptions............ Fixed Bed Using Air Stream Flows.................... Fixed Bed Using Air Major Equipment................... Fixed Bed Using Air Utilities Sumnary.................. Fixed Bed Using Air Total Capital Investment.............. Fixed Bed Using Air Fixed Bed Using Oxygen Design Bases and Assumptions............ Fixed Bed Using Oxygen Stream Flows.................... 144 147 149 151 153 156 159 163 165 167 169 171 173 Xiii
TABLES 7.29 7.30 7.31 7.32 8.1 8.2 8.3 8.4 8.5 8.6 8.7 8.8 8.9 Ethylene Dichloride by Cxychlorination in Fixed Bed Using Oxygen Major Equipment................... 176 Fixed Bed Using Oxygen Utilities Sumary...,.............. 178 Ethylene Dichloride by Cxychlorination in Fixed Bed Using Oxygen Total Capital Investment.............. 180 Ethylene Dichloride by Cxychlorination in Fixed Bed Using Oxygen 182 Pyrolysis--Reaction and Reactors Patentsummary... 190 Pyrolysis--Recovery of Reaction Products Patentsummary... 192 Purification of Vinyl Chloride Patent Summary................... 194 Purification of Ethylene Dichloride from Cracking Patent Summary................... 196 Pyrolysis Design Bases and Assumptions............ Pyrolysis StreamFlows.................... 198 200 Pyrolysis Major Equipment................... 203 Pyrolysis Utilities Swnary.................. Pyrolysis Total Capital Investment.............. 205 207 xiv
TABLES 8.10 9.1 9.2 9.3 9.4 9.5 9.6 9.7 9.8 9.9 9.10 9.11 9.12 Pyrolysis 208 Process (Case A) Design Bases and Assumptions...,........ 213 Process (Case A) StreamFlows.................... 216 Process (Case A) Major Equipment................... 220 Process (Case A) Utilities Sunwiry.................. 223 Process (Case A) Total Capital Investment.............. 225 Process (Case A) 227 Process (Case B) Design Bases and Assumptions............ 230 Process (Case B) StreamFlows.................... 233 Process (Case B) Major Equipment................... Process (Case B) Utilities Summary.................. 237 239 Process (Case B) Total Capital Investment.............. 242 Process (Case B) Production Costs.... +............. 244 xv
TABLES 9.13 9.14 9.15 9.16 9.17 9.18 9.19 9.20 9.21 9.22 10.1 10.2 10.3 Comparison of Usages in Vinyl Chloride Manufacture..................... Vinyl Chloride from Ethylene and EDC, Integr Proc; Light Ends Sold Production Costs...........,...,.. Vinyl Chloride from Ethylene and EDC, Integr Rot; Light Ends Chlorinated Production Costs...............,.. Vinyl Chloride from Ethylene and EDC, Integr Rot; Light and Heavy Ends Burned Vinyl Chloride from Ethylene and HCL, Integr Proc; Light Ends Sold Vinyl Chloride from Ethylene and HCL, Integr Rot; Light Ends Chlorinated Vinyl Chloride from Ethylene and HCL, Integr Rot; Light and Heavy Ends Burned Vinyl Chloride from EDC and Acetylene; Integr Proc; Light Ends Sold Vinyl Chloride from EDC and Acetylene; Integr Rot; Light Ends Burned Vinyl Chloride from Acetylene, Ethylene, and Chlorine; Integrated Process Ethylene Dichloride by Oxychlorination Using Asnuonium Chloride PatentSunnnary... Ethylene Dichloride by Trimethylamine Hydrochloride Process Design Bases and Assumptions............ Ethylene Dichloride by Trimethylamine Hydrochloride Process Stream Flows for Reaction Section.......... 248 250 252 254 256 258 260 263 265 267 270 273 275 xvi
TABLES 10.4 10.5 10.6 10.7 11.1 11.2 11.3 11.4 11.5 11.6 11.7 11.8 11.9 Ethylene Dichloride by Trimethylamine Hydrochloride Process Major Equipment for Reaction Section........ Ethylene Dichloride by Trimethylamine Hydrochloride Process Utilities Suumuwy.................. Ethylene Dichloride by Trimethylamine Hydrochloride Process Total Capital Investment.............. Ethylene Dichloride by Trimethylamine Hydrochloride Process Vinyl Chloride Directly from Ethylene Patentsunnnary... Vinyl Chloride from Ethane by Lummus Transcat Process and Related Aspects Patentsummary... Vinyl Chloride from Ethane by Processes Other Than the Lummus Process Patentsuamwy... Vinyl Chloride from Ethane by Transcat Process Other Processes for Producing Vinyl Chloride PatentSummary... Laser Process Design Bases and Assumptions............ Laser Process StreamFlows.................... Laser Process Major Equipment................... Laser Process Utilities Sunanary.................. 276 277 279 281 288 289 290 291 292 294 294 295 296 xvii
TABLES 11.10 Laser Process Total Capital Investment.....,....,... 11.11 299 Laser Process 300 xviii