Report No. 29A ETHYLENE-PROPYLENE Supplement A by SHIGEYOSHI TAKAOKA With contributions by KIICHIRO OHYA March 1971 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE I I MENLO PARK, CALIFORNIA
CONTENTS 1 INTRODUCTION..,.........,........... 1 2 SUMMARY... 3 General Aspects... 3 Technical Aspects... 9 3 INDUSTRY STATUS... 15 Ethylene... 15 Propylene... 37 4 ETHYLENE AND PROPYLENE BY PYROLYSIS OF LIGHT AND MIDDLE HYDROCARBONS IN A FIRED TUBULAR HEATER... 41 Chemistry... 41 Reaction Mechanisms... 41 Reaction Rate Constants... 44 Reaction Variables... 46 Review of Processes... 47 Design Case for Pyrolysis of Gas Oil... 57 Process Description... 57 Process Discussion... 67 Cost Estimates... 69 Capital Costs... 69 Production Costs... 70 Cost Comparisons... 70 5 ETHYLENE AND PROPYLENE FROM CRUDE OIL..,...,..... 79 Review of Processes... Thermal Cracking Using Heat Carriers... Autothermic Cracking... Catalytic Cracking... Arc Cracking... Design Case for Autothermic Cracking in a Forced-Circulating Fluidized Bed Process Description... Process Discussion... Cost Estimates... Capital Costs... Production Costs... 79 79 87 88 89 89 89 103 106 106 107 V
CONTENTS 6 ETHYLENE BY OTHER PROCESSES... 119 Autothermic Cracking of Other than Crude Oil... 119 Catalytic Cracking of Other than Crude Oil... 120 Propylene Disproportionation... 125 Ethane Dehydrogenation... 126 7 PROPYLENE BY CATALYTIC DEHYDROGENATION OF PROPANE... 131 Chemistry... 131 Review of Processes... 135 Process Description... 136 Process Discussion... 144 Cost Estimates... 146 Capital Costs... 146 Production Costs... 147 8 PROPYLENE BY OXIDATIVE DEHYDROGENATION OF PROPANE....,. 155 Chemistry............. 155 Dehydrogenation by Oxygen.... 155 Dehydrogenation by Halogens... 156 Dehydrogenation by Sulfur.... 156 Review of Processes........ 158 Using Oxygen.......... 161 Using Halogens......... 163 Using Sulfur.......... 166 Using Carbon Monoxide...... 168 Design Case Using Iodine..... 168 Process Description....... 168 Process Discussion....... 177 Cost Estimates......... 180 Capital Costs......... 180 Production Costs....... 181 9 PROPYLENE BY OTHER PROCESSES... 189 Thermal Cracking of Isobutane... 189 Catalytic Cracking of Paraffinic Hydrocarbons... 194 Oxidative Cracking of Isopentane... 195 Catalytic Conversion of Ethylene... 197 Hydrogen Transfer from Propane to Ethylene... 198 Disproportionation Reaction Between Ethylene and Butene-2.. 198 Other Processes... 199 vi
CONTENTS 10 RECOVERY AND PURIFICATION OF ETHYLENE AND PROPYLENE... 201 Quenching... 201 Nitric Oxide Removal... 203 Water Removal... 203 Acetylenic Materials Removal... 204 Demethanization... 207 Ethylene Purification... 208 Propylene Purification... 208 APPENDIX A DESIGN AND COST BASIS AND DEFINITIONS...,.... 211 APPENDIX B PHYSICAL DATA..,...,.........,... 217 APPENDIX C PRODUCT SPECIFICATIONS AND BY-PRODUCTS COMPOSITIONS. 221 APPENDIX D STORAGE, TRANSPORTATION, AND WASTE DISPOSAL,,... 225 CITED REFERENCES......................... 231 PATENT REFERENCES BY COMPANY......,............ 265 Vii
ILLUSTRATIONS 4.1 4.2 4.3 4.4 4.5 4.6 4.7 5.1 5.2 5.3 5.4 5.5 5.6 Reaction Velocity Constants for Heavy Hydrocarbons Relative to n-pentane.................... Ethylene by Pyrolysis of Gas Oil in a Fired Tubular Heater....................... Ethylene by Pyrolysis of n-butane in a Fired Tubular Heater Block Flow Diagram and Material Balance........... Ethylene by Pyrolysis of Gas Oil in A Fired Tubular Heater Effect of Ethylene Yield in Furnace Effluent on Capital cost............................ Ethylene by Pyrolysis of Gas Oil in A Fired Tubular Heater Effect of Gas Oil Price and By-Product Credit on Net Production Cost...............,....... Ethylene by Pyrolysis of Gas Oil in a Fired Tubular Heater Effect of Operating Level and Plant Capacity on Net Production Cost....................... Ethylene by Pyrolysis of Gas Oil in A Fired Tubular Heater Effect of Ethylene Yield in Furnace Effluent on Production cost.........,..................... Effect of Yield on Capital Cost............... Effect of Capital on Capital Cost.............. Effect of Raw Materials Cost and By-Products Credit on Production Cost....................... Effect of Operating Level and Plant Capacity on Production cost..........,................. Effect of Yield on Production Cost............. 45 59 66 73 75 76 77 95 111 112 115 116 117 ix
ILLUSTRATIONS 7.1 7.2 7.3 7.4 8.1 8.2 8.3 9.1 B.l D.l D.2 Effect of Propane Conversion on Selectivity to Propylene.. 134...... 141 Effect of Propane Price on Net Production Cost.,..... 153 Effect of Operating Level and Plant Capacity on Net Production Cost....................... 154...... 173 Effect of Propane Price and Benzene Credit on Net Production Cost....................... 187 Effect of Operating Level and Plant Capacity on Net Production Cost....................... 188 Propylene by Catalytic Cracking of Light Naphtha Effect of Temperature on Yield............... 196 Heat of Formation of Hydrocarbons.............. 219 Erected Cost of Ethylene Storage Tanks........... 226 Costs of Ethylene Transportation by Tanker......... 228
TABLES 2.1 Summary of Ethylene Processes............... 2.2 Summary of Propylene Processes............,.. 3.1 Ethylene and Propylene Plant Capacities, United States.............. 3.2 3.3 3.4 3.5 4.1 4.2 4.3 4.4 Ethylene and Propylene Plant Capacities, Americas (except United States)...,. Ethylene and Propylene Plant Capacities, Europe.................. Ethylene and Propylene Plant Capacities, Asia, Australia, and Africa....... Ethylene and Propylene Plant Capacities, Soviet Bloc Countries.......... Typical Yield Structures from Fired Tubular Heaters.... Ethylene and Propylene by Pyrolysis in a Fired Tubular Heater Patent Summary....................... Ethylene by Pyrolysis of Gas Oil in a Fired Tubular Heater Utilities Summary..................... Ethylene by Pyrolysis of Gas Oil in a Fired Tubular Heater Stream Flows........................ 4.5 Ethylene by Pyrolysis of Gas Oil in a Fired Tubular Heater Total Capital Investment.......,.......... 4.6 Ethylene by Pyrolysis of Gas Oil in a Fired Tubular Heater Production Costs.......,.............. 4.7 Ethylene by Pyrolysis in a Fired Tubular Heater Production Costs Comparison for n-butane and Propane Processes...,... 78 5.1 Ethylene and Propylene from Crude Oil Patent Summary,........,............. 81 5.2 Ethylene and Propylene from Crude Oil Typical Processes...................... 85 5.3 Major Process Equipment and Utilities Summary........ 95 5 8 17 21 23 29 33 49 53 58 65 72 74 Xi
TABLES 5.4 5.5 5.6 6.1 6.2 6.3 6.4 7.1 7.2 7.3 7.4 7.5 8.1 8.2 8.3 8.4 Stream Flows........................ 101 Total Capital Investment.................. 109 Production Costs...................... 113 Ethylene by Autothermic Cracking Patent Summary....................... 121 Ethylene by Catalytic Cracking Patent Summary,...................... 123 Ethylene by Disproportionation of Propylene Patent Summary....................... 127 Ethylene by Dehydrogenation of Ethane Patent Summary....................... 129 Patent Summary........ :.............. 137 Major Process Equipment and Utilities Summary....... 141 Stream Flows........................ 143 Total Capital Investment.................. 149 Production Costs...................... 151 Propylene by Oxidztive Dehydrogenation of Propane Patent Summary....................... 159 Major Process Equipment and Utilities Summary....... 171 Stream Flows.................... '.... 175 Total Capital Investment.........,........ 183 xii
TABLES 8.5 Production Costs...................... 185 9.1 Propylene by Other Processes Summary of Processes.................... 191 B.l Heats of Formation of the Vapor for Selected Compounds at1520'f............a... 218 C.l Ethylene Specifications.................. 221 c.2 Propylene Specifications.......,.......... 222 c.3 Composition of Pyrolysis Gasoline............. 223 c.4 Composition of C4 Fraction Obtained in Naphtha Pyrolysis.. 224 c.5 Composition of C, Fraction Obtained in Naphtha Pyrolysis., 224 Xiii