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
CONTENTS 1 INTRODUCTION....................... 1 2 SUMMARY......................... 3 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... 3 15 15 16 18 21 22 23 27 35 35 35 36 37 37 37 37 37 43 45 46 48 48 48 49 51 51 51, 52 56 57 67 68 68 69 70 iii
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... 79 79 79 79 80 82 82 85 86 86 90 94 94 95 96 96 111 112 112 112 115 125 125 125 127 130 132 138 139 139 140 141 8 BUTADIENE BY OXIDATIVE DEHYDROGENATION.......... 149 Background... 149 Oxidative Dehydrogenation of Butenes... 150 Advantages of Oxidative Dehydrogenation of Butenes... 155 Oxidative Dehydrogenation of Butane... 159 Butane Oxy-Halo-Dehydrogenation... 159 Review of Processes... 165 iv
CONTENTS 8 (continued) Catalytic and Noncatalytic Reactors... 167 Molten Acceptor Salt Reactor... 171 Fixed Acceptor Bed Reactor... 172 Fluidized Acceptor Bed Reactor... 173 Process Description... 174 Oxy-Halo-Dehydrogenation... 174 Acceptor Recovery... 175 Purification... 176 Process Discussion... 187 Oxy-Halo-Dehydrogenation... 187 Acceptor Recovery... 188 Purification... 189 Cost Estimates... 190 Capital Investment... 190 Production Costs... 191 Discussion of Costs... 192 9 SOLVENTS FOR C, SEPARATION... 201 Introduction... 201 Desirable Solvent Properties... 201 Comparison of Commercial Solvents... 202 Capital and Operating Costs for Several Solvents... 205 Other Solvents... 209 Azeotropic Distillation... 210 10 ACETYLENE REMOVAL FROM BUTADIENE............. 213 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... 213 213 214 214 215 215 219 221 224 224 224 224 224 V
CONTENTS APPENDIX A DESIGN AND COST BASIS.............. 231 APPENDIX B PHYSICAL DATA.................. 237 APPENDIX C SPECIFICATIONS................. 251 APPENDIX D MATERIALS OF CONSTRUCTION, HANDLING, SAFETY, AND POLLUTION.................. 253 CITED REFERENCES....................... 257 vi
ILLUSTRATIONS 3.1 Butadiene Production in the United States......... 17 3.2 Some Reactions of Butadiene................ 25 4.1 Equilibrium Constants for Reactions Involved in the Production of Butadiene.................. 42 4.2 Calculated Thermodynamic Equilibria for n-butane and n-butene Dehydrogenation at 1.0 Atm and 0.1 Atm...... 44 5.1 Butadiene by Dehydrogenation of Butane.......... 63 5.2 Estimated Butadiene Total Production Costs for Various Plant Sizes, Operating Rates, and Raw Material Costs.., 77 6.1 Equilibrium Curves for Isobutene in Hydrocarbon and 65% Sulfuric Acid....................... 84 6.2 Extraction Rate for Isobutene by 65% Sulfuric Acid.... 84 6.3 Effect of Temperature upon the Absorption of Hydrocarbons in CAA Solution............... 91 6.4 Schematic CAA Extraction Process............. 92 6.5 Butadiene from Refinery Butenes.............. 101 6.6 Estimated Butadiene Net Production Cost for Various Plant Sizes, Operating Rates, Refinery Butenes Values and By-Product Credits.................... 123 7.1 Butadiene Separation: BASF Scheme............ 131 7.2 Butadiene, By-Product of Naphtha Cracking......... 133 7.3 Effect of Naphtha Raw Material Cost and Butene and Isobutene By-Product Credits on the Net Production Costs of Ethylene and Butadiene................. 146 7.4 Change in Butadiene Net Production Cost with Ethylene and Butadiene Plant Capacities................ 147 vii
ILLUSTRATIONS 7.5 Estimated Influence of Butadiene Feed Concentration upon Extraction Plant Investment and Butadiene Production cost........................... 148 8.1 Hydrogen Iodide Acceptor Systems............. 169 8.2 Butadiene by the Oxy-Halo-Dehydrogenation of Butane.... 179 8.3 Estimated Butadiene Production Cost by the Oxy-Halo- Dehydrogenation of Butane for Various Plant Sizes, Operating Rates, Butane Costs and Oxygen Costs...... 199 10.1 Selective Hydrogenation of Acetylenes........... 223 B.l Relative Volatilities, "a," of C, Hydrocarbons Relative to 1,3-Butadiene..................... 244 B.2 Relative Volatilities of C, Hydrocarbons in Acetone, Acetonitrile, and Furfural Solvents............ 245 B.3 Acetonitrile--Water Liquid-Vapor Equilibrium 1...... 246 B.4 Solubility of Iodine in Aqueous Hydrogen Iodide and in Water......................... 247 B.5 Vapor Pressures of Hydrogen and Iodine.......... 248 B.6 Solubilities of 1,3-Butadiene, l-butene, and n-butane in Dimethylformamide..................... 249 viii
TABLES 2.1 2.2 3.1 3.2 3.3 3.4 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...... 5 7 17 18 22 29 3.5 4.1 5.1 5.2 5.3 Estimated Butadiene Consumption outside the United States 33 Commercial Routes to Butadiene.............. 39 Catalytic Dehydrogenation of n-butane or n-butane- Butylene Mixtures Summary of Patents.................... 53 A Comparison of Dehydrogenation Catalysts........ 55 Butadiene by Dehydrogenation of Butane Major Process Equipment and Utilities Summary...... 61 5.4 Butadiene by Dehydrogenation of Butane Stream Flows... 65 5.5 Butadiene by Dehydrogenation of Butane Process Unit and Utilities Investment.......... 72 5.6 Butadiene by Dehydrogenation of Butane Total Capital Investment................. 73 5.7 Butadiene by Dehydrogenation of Butane Production Costs..................... 75 6.1 A Comparison of Butene Dehydrogenation Catalysts..... 81 6.2 Catalytic Dehydrogenation of Butenes Summary of Patents.................... 87 ix
TABLES 6.3 Butadiene from Refinery Butenes Major Process Equipment and Utilities Summary...... 99 6.4 Butadiene from Refinery Butenes Stream Flows... 107 6.5 Butadiene from Refinery Butenes Process Unit and Utilities Investment.......... 6.6 Butadiene from Refinery Butenes Total Capital Investment................. 6.7 Butadiene from Refinery Butenes Production Costs..................... 117 119 121 7.1 7.2 Estimated Capital and Operating Costs for Ethylene.... 126 Typical Yields from Commercial Fired Tubular Heaters... 128 7.3 Butadiene By-Product of Naphtha Cracking Major Process Equipment and Utilities Summary...... 133 7.4 Butadiene By-Product of Naphtha Cracking Stream Flows... 7.5 Butadiene By-Product of Naphtha Cracking Process Unit and Utilities Investment.......... 7.6 Butadiene By-Product of Naphtha Cracking Total Capital Investment................. 7.7 Butadiene By-Product of Naphtha Cracking Production Costs..................... 6.1 Oxidative Dehydration of n-butane and Butenes Summary of Patents.................... 8.2 Butadiene by Oxidative Dehydrogenation of Butenes Summary of Recently Published Research....,..... 8.3 Oxy-Halo-Dehydrogenation of Butane and Butenes Summary of Patents.....,.............. 135 143 144 145 151 157 161
TABLES 8.4 8.5 8.6 8.7 8.8 8.9 9.1 9.2 10.1 10.2 10.3 10.4 10.5 B.l B.2 Butadiene by Oxy-Halo-Dehydrogenation of n-butane Summary of U.S.S.R. Research............... 166 Butadiene by the Oxy-Halo-Dehydrogenation of Butane Major Process Equipment and Utilities Summary...... 178 Butadiene by the Oxy-Halo-Dehydrogenation of Butane Stream Flows... 183 Butadiene by the Oxy-Halo-Dehydrogenation of Butane Process Unit and Utilities Investment.......... 193 Butadiene by the Oxy-Halo-Dehydrogenation of Butane Total Capital Investment................. 195 Butadiene by the Oxy-Halo-Dehydrogenation of Butane Production Costs..................... 197 Physical Properties of Solvents for C, Separations.... 203 Summary of Capital and Operating Costs for Preceding C, Separations...................... 207 Destruction of Acetylenes in Butadiene by Selective Hydrogenation or Polymerization Summary of Patents... 217 Selective Hydrogenation of Acetylenes Major Process Equipment, Utilities Summary, and Stream Flows.......................... 222 Selective Hydrogenation of Acetylenes Process Unit and Utilities Investment.......... 225 Selective Hydrogenation of Acetylenes Production Costs..................... 227 Comparative Costs for Solvent Extraction of Acetylenes.. 229 Physical Properties of 1,3-Butadiene........... 238 Houdry Chrome-Alumina Catalyst Typical Properties................... 239 Xi
TABLES B.3 Hydrocarbon Relative Volatilities............ 240 B.4 Physical Properties of Extractive Distillation Solvents. 241 B.5 Properties of Cuprous Ammonium Acetate Solution..... 242 B.6 Solubilities of Hydrocarbons in N-Methylpyrrolidone... 243 xii