ETHYLENE-PROPYLENE PROCESS ECONOMICS PROGRAM. Report No. 29A. Supplement A. by SHIGEYOSHI TAKAOKA With contributions by KIICHIRO OHYA.

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1 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

2 CONTENTS 1 INTRODUCTION.., , SUMMARY... 3 General Aspects... 3 Technical Aspects INDUSTRY STATUS Ethylene Propylene ETHYLENE AND PROPYLENE BY PYROLYSIS OF LIGHT AND MIDDLE HYDROCARBONS IN A FIRED TUBULAR HEATER Chemistry Reaction Mechanisms Reaction Rate Constants Reaction Variables Review of Processes Design Case for Pyrolysis of Gas Oil Process Description Process Discussion Cost Estimates Capital Costs Production Costs Cost Comparisons ETHYLENE AND PROPYLENE FROM CRUDE OIL..,..., 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 V

3 CONTENTS 6 ETHYLENE BY OTHER PROCESSES Autothermic Cracking of Other than Crude Oil Catalytic Cracking of Other than Crude Oil Propylene Disproportionation Ethane Dehydrogenation PROPYLENE BY CATALYTIC DEHYDROGENATION OF PROPANE Chemistry Review of Processes Process Description Process Discussion Cost Estimates Capital Costs Production Costs PROPYLENE BY OXIDATIVE DEHYDROGENATION OF PROPANE....,. 155 Chemistry Dehydrogenation by Oxygen Dehydrogenation by Halogens Dehydrogenation by Sulfur Review of Processes Using Oxygen Using Halogens Using Sulfur Using Carbon Monoxide Design Case Using Iodine Process Description Process Discussion Cost Estimates Capital Costs Production Costs PROPYLENE BY OTHER PROCESSES Thermal Cracking of Isobutane Catalytic Cracking of Paraffinic Hydrocarbons Oxidative Cracking of Isopentane Catalytic Conversion of Ethylene Hydrogen Transfer from Propane to Ethylene Disproportionation Reaction Between Ethylene and Butene Other Processes vi

4 CONTENTS 10 RECOVERY AND PURIFICATION OF ETHYLENE AND PROPYLENE Quenching Nitric Oxide Removal Water Removal Acetylenic Materials Removal Demethanization Ethylene Purification Propylene Purification APPENDIX A DESIGN AND COST BASIS AND DEFINITIONS..., APPENDIX B PHYSICAL DATA..,..., , APPENDIX C PRODUCT SPECIFICATIONS AND BY-PRODUCTS COMPOSITIONS. 221 APPENDIX D STORAGE, TRANSPORTATION, AND WASTE DISPOSAL,, CITED REFERENCES PATENT REFERENCES BY COMPANY......, Vii

5 ILLUSTRATIONS 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 ix

6 ILLUSTRATIONS B.l D.l D.2 Effect of Propane Conversion on Selectivity to Propylene Effect of Propane Price on Net Production Cost., Effect of Operating Level and Plant Capacity on Net Production Cost Effect of Propane Price and Benzene Credit on Net Production Cost Effect of Operating Level and Plant Capacity on Net Production Cost Propylene by Catalytic Cracking of Light Naphtha Effect of Temperature on Yield Heat of Formation of Hydrocarbons Erected Cost of Ethylene Storage Tanks Costs of Ethylene Transportation by Tanker

7 TABLES 2.1 Summary of Ethylene Processes Summary of Propylene Processes , Ethylene and Propylene Plant Capacities, United States 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 Ethylene by Pyrolysis of Gas Oil in a Fired Tubular Heater Total Capital Investment , Ethylene by Pyrolysis of Gas Oil in a Fired Tubular Heater Production Costs , Ethylene by Pyrolysis in a Fired Tubular Heater Production Costs Comparison for n-butane and Propane Processes..., Ethylene and Propylene from Crude Oil Patent Summary, , Ethylene and Propylene from Crude Oil Typical Processes Major Process Equipment and Utilities Summary Xi

8 TABLES Stream Flows Total Capital Investment Production Costs Ethylene by Autothermic Cracking Patent Summary Ethylene by Catalytic Cracking Patent Summary, Ethylene by Disproportionation of Propylene Patent Summary Ethylene by Dehydrogenation of Ethane Patent Summary Patent Summary : Major Process Equipment and Utilities Summary Stream Flows Total Capital Investment Production Costs Propylene by Oxidztive Dehydrogenation of Propane Patent Summary Major Process Equipment and Utilities Summary Stream Flows ' Total Capital Investment , xii

9 TABLES 8.5 Production Costs Propylene by Other Processes Summary of Processes B.l Heats of Formation of the Vapor for Selected Compounds at1520'f a C.l Ethylene Specifications c.2 Propylene Specifications , c.3 Composition of Pyrolysis Gasoline c.4 Composition of C4 Fraction Obtained in Naphtha Pyrolysis c.5 Composition of C, Fraction Obtained in Naphtha Pyrolysis., 224 Xiii