Report No. 35 BUTADIENE. March A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE I PARK, CALIFORNIA

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1 Report No. 35 BUTADIENE by GEORGE E. HADDELAND March 1968 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE I MENLO PARK, CALIFORNIA

2 CONTENTS 1 INTRODUCTION SUMMARY INDUSTRY STATUS... History... Butadiene Production... Raw Material Sources... Butadiene from Alcohol... Butadiene End Uses... Butadiene and Butane Prices... Butadiene Production Outside the United States... 4 CHEMISTRY... The Chemistry of C4 Hydrocarbons... Butadiene Properties and Structure... Butane and Butene Structure... The Chemistry of Butadiene Manufacture... Methods of Production... Commercial Routes to Butadiene... Butane and Butene Dehydrogenation... Reaction Products... Dehydrogenation Equilibria... Dehydrogenation Catalysts... Dehydrogenation Rates... C, Separation Methods... Fractional Distillation... Extractive Distillation... Solvent Efficiency in Extractive Distillation... 5 BUTADIENE BY DEHYDROGENATION OF BUTANE... Review of Processes... Phillips Two-Stage Process... Dehydrogenation Catalysts... Houdry Single Stage Process... Process Description... Process Discussion... Cost Estimates... Capital Costs... Production Costs... Discussion of Costs , iii

3 CONTENTS 6 BUTADIENE FROM REFINERY BUTENES... Historical Summary... Process Development... Catalyst Development... Purification... Review of Technology... Isobutene Separation... Feed Preparation... Dehydrogenation... Purification (Cuprous Ammonium Acetate)... Cuprous Ammonium Acetate Extraction Patents... Process Description... Isobutene Separation... Feed Preparation... Dehydrogenation... Purification... Process Discussion... Cost Estimates... Capital Costs... Production Costs... Discussion of Costs... 7 BUTADIENE, BY-PRODUCT OF NAPHTHA CRACKING... Background... Ethylene Production... By-Product Butadiene.... Process Technology... Process Description... Process Discussion... Cost Estimates... Capital Investment... Production Costs... Discussion of Costs BUTADIENE BY OXIDATIVE DEHYDROGENATION Background Oxidative Dehydrogenation of Butenes Advantages of Oxidative Dehydrogenation of Butenes Oxidative Dehydrogenation of Butane Butane Oxy-Halo-Dehydrogenation Review of Processes iv

4 CONTENTS 8 (continued) Catalytic and Noncatalytic Reactors Molten Acceptor Salt Reactor Fixed Acceptor Bed Reactor Fluidized Acceptor Bed Reactor Process Description Oxy-Halo-Dehydrogenation Acceptor Recovery Purification Process Discussion Oxy-Halo-Dehydrogenation Acceptor Recovery Purification Cost Estimates Capital Investment Production Costs Discussion of Costs SOLVENTS FOR C, SEPARATION Introduction Desirable Solvent Properties Comparison of Commercial Solvents Capital and Operating Costs for Several Solvents Other Solvents Azeotropic Distillation ACETYLENE REMOVAL FROM BUTADIENE Adverse Effects of Acetylenes... Acetylene Compounds... Amounts of Acetylenes... Specifications... Removal Methods... Selective Hydrogenation or Polymerization... Other Methods... Process Description... Process Discussion... Cost Estimates... Capital Investment... Production Costs... Discussion of Costs V

5 CONTENTS APPENDIX A DESIGN AND COST BASIS APPENDIX B PHYSICAL DATA APPENDIX C SPECIFICATIONS APPENDIX D MATERIALS OF CONSTRUCTION, HANDLING, SAFETY, AND POLLUTION CITED REFERENCES vi

6 ILLUSTRATIONS 3.1 Butadiene Production in the United States Some Reactions of Butadiene Equilibrium Constants for Reactions Involved in the Production of Butadiene Calculated Thermodynamic Equilibria for n-butane and n-butene Dehydrogenation at 1.0 Atm and 0.1 Atm Butadiene by Dehydrogenation of Butane Estimated Butadiene Total Production Costs for Various Plant Sizes, Operating Rates, and Raw Material Costs.., Equilibrium Curves for Isobutene in Hydrocarbon and 65% Sulfuric Acid Extraction Rate for Isobutene by 65% Sulfuric Acid Effect of Temperature upon the Absorption of Hydrocarbons in CAA Solution Schematic CAA Extraction Process Butadiene from Refinery Butenes Estimated Butadiene Net Production Cost for Various Plant Sizes, Operating Rates, Refinery Butenes Values and By-Product Credits Butadiene Separation: BASF Scheme Butadiene, By-Product of Naphtha Cracking Effect of Naphtha Raw Material Cost and Butene and Isobutene By-Product Credits on the Net Production Costs of Ethylene and Butadiene Change in Butadiene Net Production Cost with Ethylene and Butadiene Plant Capacities vii

7 ILLUSTRATIONS 7.5 Estimated Influence of Butadiene Feed Concentration upon Extraction Plant Investment and Butadiene Production cost Hydrogen Iodide Acceptor Systems Butadiene by the Oxy-Halo-Dehydrogenation of Butane Estimated Butadiene Production Cost by the Oxy-Halo- Dehydrogenation of Butane for Various Plant Sizes, Operating Rates, Butane Costs and Oxygen Costs Selective Hydrogenation of Acetylenes B.l Relative Volatilities, "a," of C, Hydrocarbons Relative to 1,3-Butadiene B.2 Relative Volatilities of C, Hydrocarbons in Acetone, Acetonitrile, and Furfural Solvents B.3 Acetonitrile--Water Liquid-Vapor Equilibrium B.4 Solubility of Iodine in Aqueous Hydrogen Iodide and in Water B.5 Vapor Pressures of Hydrogen and Iodine B.6 Solubilities of 1,3-Butadiene, l-butene, and n-butane in Dimethylformamide viii

8 TABLES Summary of Butadiene Processes Summary of Butadiene Purification Cost Components.... Butadiene Producers in the United States Percentage of Butadiene Production by Source United States Consumption of Butadiene Butadiene Producers outside the United States Estimated Butadiene Consumption outside the United States 33 Commercial Routes to Butadiene Catalytic Dehydrogenation of n-butane or n-butane- Butylene Mixtures Summary of Patents A Comparison of Dehydrogenation Catalysts Butadiene by Dehydrogenation of Butane Major Process Equipment and Utilities Summary Butadiene by Dehydrogenation of Butane Stream Flows Butadiene by Dehydrogenation of Butane Process Unit and Utilities Investment Butadiene by Dehydrogenation of Butane Total Capital Investment Butadiene by Dehydrogenation of Butane Production Costs A Comparison of Butene Dehydrogenation Catalysts Catalytic Dehydrogenation of Butenes Summary of Patents ix

9 TABLES 6.3 Butadiene from Refinery Butenes Major Process Equipment and Utilities Summary Butadiene from Refinery Butenes Stream Flows Butadiene from Refinery Butenes Process Unit and Utilities Investment Butadiene from Refinery Butenes Total Capital Investment Butadiene from Refinery Butenes Production Costs Estimated Capital and Operating Costs for Ethylene Typical Yields from Commercial Fired Tubular Heaters Butadiene By-Product of Naphtha Cracking Major Process Equipment and Utilities Summary Butadiene By-Product of Naphtha Cracking Stream Flows Butadiene By-Product of Naphtha Cracking Process Unit and Utilities Investment Butadiene By-Product of Naphtha Cracking Total Capital Investment Butadiene By-Product of Naphtha Cracking Production Costs Oxidative Dehydration of n-butane and Butenes Summary of Patents Butadiene by Oxidative Dehydrogenation of Butenes Summary of Recently Published Research...., Oxy-Halo-Dehydrogenation of Butane and Butenes Summary of Patents.....,

10 TABLES B.l B.2 Butadiene by Oxy-Halo-Dehydrogenation of n-butane Summary of U.S.S.R. Research Butadiene by the Oxy-Halo-Dehydrogenation of Butane Major Process Equipment and Utilities Summary Butadiene by the Oxy-Halo-Dehydrogenation of Butane Stream Flows Butadiene by the Oxy-Halo-Dehydrogenation of Butane Process Unit and Utilities Investment Butadiene by the Oxy-Halo-Dehydrogenation of Butane Total Capital Investment Butadiene by the Oxy-Halo-Dehydrogenation of Butane Production Costs Physical Properties of Solvents for C, Separations Summary of Capital and Operating Costs for Preceding C, Separations Destruction of Acetylenes in Butadiene by Selective Hydrogenation or Polymerization Summary of Patents Selective Hydrogenation of Acetylenes Major Process Equipment, Utilities Summary, and Stream Flows Selective Hydrogenation of Acetylenes Process Unit and Utilities Investment Selective Hydrogenation of Acetylenes Production Costs Comparative Costs for Solvent Extraction of Acetylenes Physical Properties of 1,3-Butadiene Houdry Chrome-Alumina Catalyst Typical Properties Xi

11 TABLES B.3 Hydrocarbon Relative Volatilities B.4 Physical Properties of Extractive Distillation Solvents. 241 B.5 Properties of Cuprous Ammonium Acetate Solution B.6 Solubilities of Hydrocarbons in N-Methylpyrrolidone xii