Report No. 2A PROPYLENEOXIDE AND ETHYLENEOXIDE Supplement A by YEN-CHEN YEN February 1967 A private report by the PROCESS ECONOMICS PROGRAM I STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA I CONTENTS I INTRODUCTION. ....................... 1 II SUMMARY .......................... 3 General Aspects ..................... 3 Technical Aspects ..................... 5 III INDUSTRY STATUS ...................... 13 IV CHEMISTRY ......................... 25 Propylene Oxide by the Electrochemical Chlorohydrin Process 25 Propylene Oxide by Liquid-Phase Oxidation with Oxygen ... 25 Propylene Oxide by Vapor-Phase Oxidation without Silver Catalyst .......................... 29 Propylene Oxide by Perphthalic Acid Process ........ 29 Isopropanol Hydroperoxide Formation ........... 31 Cyclohexanol Hydroperoxide Formation ........... 32 Formation of Monoperphthalic Acid ............ 32 Oxidation of Propylene by Monoperphthalic Acid ...... 33 Propylene Oxide by Cumene Hydroperoxide or Ethylbenzene Hydroperoxide Process ................... 34 Cumene Oxidation to Hydroperoxide ............ 36 Ethylbenzene Oxidation to Hydroperoxide ......... 39 Oxidation of Propylene by Cumene Hydroperoxide or Ethylbenzene Hydroperoxide ................ 40 Hydrogenation ...................... 41 Dehydration ....................... 42 V PROPYLENE OXIDE BY CHLOROHYDRIN PROCESSES ......... 45 Process Description .................... 47 Process Discussion ..................... 53 Cost Estimates ....................... 55 VI PROPYLENE OXIDE BY VAPOR-PHASE SILVER-CATALYZED OXIDATION . 61 VII PROPYLENE OXIDE BY VAPOR-PHASE OXIDATION WITHOUT SILVER CATALYSTS ......................... 69 Review of Processes .................... 69 Process Based on a Union Carbide Patent .......... 73 Process Based on an Osaka Soda Patent ........... 81 iii CONTENTS VIII PROPYLENE OXIDE BY LIQUID-PHASE OXIDATION WITH OXYGEN . 89 IX PROPYLENE OXIDE BY PROCESSES USING PEROXYACIDS OR HYDROPEROXIDES . 97 Review of Processes . 97 Perphthalic Acid Process Using Isopropanol--Description . 101 Perphthalic Acid Process Using Cyclohexanol--Description . 113 Discussion of the Perphthalic Acid Processes . 123 Cost Estimates for Perphthalic Acid Processes . 125 Ethylbenzene Process Description . , . 142 Cumene Process Description . 157 Discussion of Ethylbenzene and Cumene Processes . 165 Cost Estimates of Ethylbenzene and Cumene Processes . 168 Appendix A DESIGN AND COST BASIS . 187 Appendix B HEAT OF FORMATION OF PEROXYACIDS AND HYDROPEROXIDES . 191 Appendix C HANDLING AND SAFETY................. 195 Appendix D RECENT PATENT INFORMATION ON THE MANUFACTURE OF PROPYLENE OXIDE BY PEROXYACIDS OR HYDROPEROXIDES . 197 REFERENCES............................ 203 SUPPLEMENTARY REFERENCES..................... 219 iv ILLUSTRATIONS 1 Propylene Oxide by Electrochemical Chlorohydrin Process . 49 2 Propylene Oxide by Vapor-Phase Oxidation without Silver Catalysts.......................... 75 3 Relationship of Production Costs of Propylene Oxide and Coproducts in Noncatalytic Vapor-Phase Oxidation (as in PEP Report No. 2) . 82 4 Relationship of Production Costs of Propylene Oxide and Coproducts in Vapor-Phase Oxidation without Silver Catalysts 87 5 Propylene Oxide by Perphthalic Acid Process Using Isopropanol 105 6 Propylene Oxide by Perphthalic Acid Process Using Cyclo- hexanol........................... 115 7 Investment for a Plant Raking Propylene Oxide by Perphthalic Acid Process . 139 8 Relationship of Plant Cost to Annual Production--Propylene Oxide by Perphthalic Acid Process . 140 9 Relationship of Production Cost to Annual Production-- Propylene Oxide by Perphthalic Acid Process . 141 10 Propylene Oxide by Ethylbenzene Process . 147 11 Propylene Oxide by Cumene Process . 159 12 Production Costs of Propylene Oxide and Styrene--Ethylbenzene Process........................... 183 13 Investment for Plants of Various Sizes--Propylene Oxide by Ethylbenzene and Cumene Processes . , . , . 184 14 Production and Plant Costs as Functions of Annual Produc- tion--Propylene Oxide by Cumene Process . 185 V TABLES 1 Summary of Costs of Evaluated Processes ........... 4 2 Comparison of Costs of Evaluated Processes with Conventional Chlorohydrin Process .................... 6 Summary of Evaluated Processes ............... 9 Plant Capacities, Americas ................. 15 Plant Capacities, Far East ................. 19 Plant Capacities, Western Europe .............. 21 Propylene Oxide by Electrochemical Chlorohydrin Process Major Process Equipment and Utilities Summary ........ 48 8 Propylene Oxide by Electrochemical Chlorohydrin Process Stream Flows ........................ 51 9 Propylene Oxide by Electrochemical Chlorohydrin Process Process Unit and Utilities Investment ............ 56 10 Propylene Oxide by Electrochemical Chlorohydrin Process Total Capital Investment .................. 57 11 Propylene Oxide by Electrochemical Chlorohydrin Process Production Costs ...................... 58 12 Propylene Oxide by Vapor-Phase Silver-Catalyzed Oxidation Processes, Summary of Patents ................ 63 13 Propylene Oxide by Vapor-Phase Oxidation without Silver Catalysts, Summary of Patents ................ 71 14 Propylene Oxide by Vapor-Phase Oxidation without Silver Catalysts, Stream Flows ................... 77 15 Propylene Oxide by Vapor-Phase Oxidation without Silver Catalysts, Total Capital Investment ............. 84 16 Propylene Oxide by Vapor-Phase Oxidation without Silver Catalysts, Production Costs ................. 85 17 Propylene Oxide by Liquid-Phase Oxidation with Oxygen Summary of Patents ..................... 91 18 Propylene Oxide by Perphthalic Acid Process Using Isopropanol Major Process Equipment and Utilities Summary ........ 105 vii TABLES 19 Propylene Oxide by Perphthalic Acid Process Using Isopropanol Stream Flows , . , . , . , . 109 20 Propylene Oxide by Perphthalic Acid Process Using Cyclo- hexanol, Major Process Equipment and Utilities Summary . 115 21 Propylene Oxide by Perphthalic Acid Process Using Cyclohexanol Stream Flows . 119 22 Propylene Oxide by Perphthalic Acid Process Using Isopropanol Process Unit and Utilities Investment . 127 23 Propylene Oxide by Perphthalic Acid Process Using Isopropanol Total Capital Investment . 129 24 Propylene Oxide by Perphthalic Acid Process Using Isopropanol Production Costs . 131 25 Propylene Oxide by Perphthalic Acid Process Using Cyclo- hexanol, Process Unit and Utilities Investment . 133 26 Propylene Oxide by Perphthalic Acid Process Using Cyclo- hexanol, Total Capital Investment . 135 27 Propylene Oxide by Perphthalic Acid Process Using Cyclo- hexanol, Production Costs . .,. - . 137 28 Propylene Oxide by Ethylbenzene Process Major Process Equipment and Utilities Summary . 147 29 Propylene Oxide by Ethyl,benzeneProcess Stream Flows . 153 30 Propylene Oxide by Cumene Process Major Process Equipment and Utilities Summary . 158 31 Propylene Oxide by Cumene Process Stream Flows . 161 32 Propylene Oxide by Ethylbenzene Process Process Unit and Utilities Investment . 171 33 Propylene Oxide by Ethylbenzene Process Total Capital Investment . 173 34 Propylene Oxide by Cumene Process Process Unit and Utilities Investment . 174 viii TABLES 35 Propylene Oxide by Cumene Process Total Capital Investment . , . 175 36 Propylene Oxide by Ethylbenzene Process (with Styrene as a Coproduct), Production Costs . , . 177 37 Styrene by Ethylbenzene Process (with Propylene Oxide as a Coproduct), Production Costs . , . , . , . 179 38 Propylene Oxide by Cumene Process Production Costs . 181 ix .