Report No. 29 ETHYLENE by SHIGEYOSHI TAKAOKA August 1967 A private report by the PROCESS ECONOMICS PROGRAM I STANFORD RESEARCH INSTITUTE MENLO I PARK, CALIFORNIA
CONTENTS 1 INTRODUCTION........................ 1 2 SUMMARY... 3 3 INDUSTRY STATUS....................... 11 4 CHEMISTRY... 35 Introduction... 35 Thermal Cracking... 35 Reaction Mechanism... 37 Reaction Rate Constant... 41 Equilibrium Approach... 43 Heat of Reaction... 45 Molar Expansion... 45 Reaction Variables... 45 Contact Time... 45 Temperature.... 49 Pressure... 50 Feedstock... 50 Steam... 51 Autothermic Cracking... 52 5 REVIEW OF PROCESSES... Introduction... 55 Thermal Cracking Processes... 56 Direct Heating Process... 56 Indirect Heating Process... 69 Autothermic Cracking Processes... 91 Other Processes... 111 Recovery and Purification Processes... 119 Quenching... 119 Removal of Acid Gases... 125 Removal of Water... 126 Removal of Acetylenic Materials... 127 Demethanization... 131 Low Temperature Straight Fractionation... 131 Selective Absorption... 139 Selective Adsorption... 145 Ethylene Purification... 145 Propylene Purification... 151 iii
CONTENTS ETHYLENE BY FIRED TUBULAR HEATER... Process Description... Process Discussion... Capital Costs.... Production Costs... ETHYLENE FROM CRUDE OIL BY AUTOTHERMIC CRACKING... Process Description... Process Discussion... Capital Costs.... Production Costs... ETHYLENE SYNTHESIS FROM CARBON MONOXIDE AND HYDROGEN... Introduction... Process Description... Process Discussion... Cost Estimates... Capital Costs.... Production Costs... 157 157 195 201 215 233 233 253 256 263 271 271 272 281 283 283 288 APPENDIXA DESIGN AND COST BASIS, DEFINITIONS... 295 APPENDIX B PHYSICALDATA... 299 APPENDIX C RAW MATERIAL AND PRODUCT SPECIFICATIONS... 301 APPENDIX D SAFETY, STORAGE, AND TRANSPORTATION... 305 REFERENCES... 309 SUPPLEMENTARY REFERENCES... 341 iv
ILLUSTRATIONS 4.1 4.2 4.3 4.4 6.1.... 6.2... 6.3... 6.4 Ethylene by Fired Tubular Heater Effect of Plant Capacity on Capital Costs in Ethane and Propane Pyrolysis..................... 6.5 6.6 6.7 6.8 6.9 6.10 6.11 6.12 6.13 7.1 Effect of Conversion on Heat Required to Decompose Ethane and Propane.......,............ Yield of Products from Ethane Pyrolysis at 1500'F..... Yield of Products from Propane Pyrolysis at 1500 F.... Combustion Product Distribution in Autothermic Cracking of Ethane...,............ Ethylene by Fired Tubular Heater Effect of Plant Capacity on Capital Costs in Naphtha Pyrolysis... Effect of Ethylene Yield in Furnace Effluent on Capital Costs in Naphtha Pyrolysis................ Effect of Raw Material Cost and By-Product Credit on Ethylene Production Cost in Ethane Pyrolysis....... Effect of Raw Material Cost and By-Product Credit on Ethylene Production Cost in Propane Pyrolysis....... Effect of Raw Material Cost and By-Product Credit on Ethylene Production Cost in Naphtha Pyrolysis....... Effect of Operating Level and Production Capacity on Ethylene Production Cost in Ethane Pyrolysis....... Effect of Operating Level and Production Capacity on Ethylene Production Cost in Propane Pyrolysis....... Effect of Operating Level and Production Capacity on Ethylene Production Cost in Naphtha Pyrolysis....... Effect of Ethylene Yield in Furnace Effluent on Production Costs in Naphtha Pyrolysis...................... 46 47 48 54 163 173 185 212 213 214 225 226 227 228 229 230 231 241 V
ILLUSTRATIONS 7.2 Ethylene from Crude Oil Cracking Effect of Yield on Capital Costs............. 262 7.3 Ethylene from Crude Oil Cracking Effect of Raw Material Costs and By-Product Credit on Production Cost...................... 267 7.4 Ethylene from Crude Oil Cracking Effect of Operating Level and Plant Capacity on Production Cost...................... 268 7.5 Ethylene from Crude Oil Cracking Effect of Yield on Production Cost............ 269 8.1... 275 8.2 Effect of Raw Material Costs on Ethylene Production Cost. 293 8.3 Effect of Operating Level and Production Capacity on Ethylene Production Cost-................. 294 Vi
TABLES 2.1 2.2 3.1 3.2 3.3 3.4 3.5 5.1 5.2 5.3 5.4 5.5 5.6 5.7 5.8 5.9 5.10 5.11 Summary of Ethylene Processes............... Sensitivity Analysis of the Ethylene Processes...... Plant Capacities, United States.............. Plant Capacities, Americas (except United States)..... Plant Capacities, Europe................. Plant Capacities, Asia, Australia, and Africa....... Plant Capacities, Soviet Bloc Countries.......... Typical Commercial Yields from Fired Tubular Heaters... Ethylene by Direct Heating Ethylene by Indirect Heating (Pebble Bed Reactor) Ethylene by Indirect Heating (Fluidized Bed Reactor) Ethylene by Indirect Heating (Regenerative Furnace) Ethylene by Autothermic Cracking Ethylene by Other Thermal Cracking Processes Ethylene by Thermal Cracking Quenching Processes Summary of Patents.................... Demethanization by Low Temperature Straight Fractionation Summary of Patents.................... Demethanization by Selective Absorption Summary of Patents.................... Ethylene Purification Summary of Patents.................... 5 7 17 21 23 29 33 59 61 73 79 85 95 113 1.21 135 141 147 Vii
TABLES 5.12 6.1 6.2 6.3 6.4 6.5 6.6 6.7 6.8 6.9 6.10 6.11 6.12 6.13 6.14 6.15 Propylene Purification Summary of Patents................. Total Capital Investment.............. Production Costs..................... Stream Flows....................... Stream Flows....................... Stream Flows....................... Total Capital Investment.................... Total Capital Investment................. Production Costs..................... Production Costs......................... 155 163 167 171 179 183 191 203 205 207 209 210 211 219 221 223 viii
TABLES 7.1 7.2 7.3 7.4 7.5 8.1 8.2 8.3 8.4 8.5 Stream Flows....................... Total Capital Investment................. Production Costs..................... Stream Flows,...................... Total Capital Investment................. Production Costs..................... 239 247 259 261 265 275 279 285 287 291 ix