Report No. 91 ISOMERIZATION OF PARAFFINS FOR GASOLINE by EARL D. OLIVER and RYOSUKE HASHIMOTO OCTOBER 1974 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE I MENLO PARK, CALIFORNIA
CONTENTS LIST OF ABBREVIATIONS... GLOSSARY.,... xv xvii INTRODUCTION. 1 SUMMARY... General Aspects... Current Situation... Processes. Summary of Evaluations... Technical Aspects... Chemistry. Processes. INDUSTRY STATUS... History and Prospects for Isomerization... Capacities.. Production, Consumption, and Operating Rates. Raw Materials 3 3 3 4 5 11 11 12 17 17 20 20 20 PROCESS COMPARISONS AND ANALYSIS... 27 LOW-TEMPERATURE ISOMERIZATION Chemistry.. Kinetics.. Poisons.. Review of Processes... UOPPene# BP Isomerizatio;... Process Description... Process Discussion... Cost Estimates SRIDesign. UOPDesign. BPDesign. ISOMERIZATION OVER ZEOLITE CATALYSTS... Review of Processes... Process Description... Process Discussion... Cost Estimates 35 35 40 41 42 87 88 89 98 99 99 106 106 111 111 112 122 123 vii
CONTENTS 7 ISOMERIZATION WITH RECYCLE OF NORMAL PENTANE......... Review of Processes... Process Description... Process Discussion... Cost Estimates 131 131 131 144 144 8 ISOMERIZATION WITH RECYCLE OF nc5, nc6, and MP........ 151 Review of Processes... Process Description... Process Discussion... Cost Estimates 151 151 166 166 9 ISOMERIZATION WITH RECYCLE OF NORMAL PARAFFINS........ Chemistry.. Review of Processes... Union Carbide Total Isomerization Process. BP Normal Paraffin Extraction... UOP Molex@ Process... Process Description... Process Discussion... Cost Estimates 173 173 176 176 180 180 182 191 193 10 ISOMERIZATION OF BUTANE........... 201 Chemistry.. Review of Processes... British Petroleum Process. Universal Oil Products: Butameg Process. Process Description... Process Discussion... Cost Estimates APPENDIX A DESIGN AND COST BASIS APPENDIX B PHYSICAL DATA... APPENDIX C HANDLING AND SAFETY. CITED REFERENCES. PATENT REFERENCES BY COMPANY... 201 201 211 211 212 222 222 231 235 237 239 271 viii
4.1 4.2 5.1 5.2 5.3 5.4 6.1 6.2 7.1 7.2 8.1 8.2 9.1 9.2 10.1 10.2 10.3 Cost, Capacity, and Octane Gain.............. Cost of Octane Gain.................... Equilibrium Composition: Vapor Phase.,..........,............. BP Isomerization Process with Cs/C, or Ce Feedstock....,.........,, Isomerization dver Zeolite Catalyst..,..... Isomerization with Recycle of nc,, nc,, and BP...,.,. Isomerization with Recycle of ncr, nc,, and MP on Production Cost.....,...................... Equilibrium Composition of Butanes: Vapor Phase........................ 29 30 38 93 105 108 117 129 137 149 159 171 187 199 202 217 229 IX
TABLES 2.1 3.1 3.2 4.1 5.1 5.2 5.3 5.4 5.5 5.6 5.7 5.8 5.9 5.10 6.1 6.2 6.3 6.4 6.5 Summary of Evaluations... Plants for Normal Paraffin Isomerization.. Plants for Butane Isomerization... Various Octane Gains and Costs... Friedel-Crafts Isomerization of Normal Paraffins Patent Summary.... Hydroisomerization of Normal Paraffins... Design Bases and Assumptions StreamFlows Summary of Waste Products. Total Capital Investment.. Production Costs... BP Isomerization Process Material Balance... BP Isomerization Process Capital and Operation Cost Estimates, Utilities and Chemical Requirements for 8,400 BSD C,/C, Unit... Design Bases and Assumptions Stream Flows Summary of Waste Products. Total Capital Investment.. 7 21 25 33 43 47 90 92 95 97 101 103 109 110 113 115 119 121 125 xi
TABLES 6.6 7.1 7.2 7.3 7.4 7.5 7.6 7.7 8.1 8.2 8.3 8.4 8.5 6.6 8.7 9.1 9.2 Production Costs...................... 127 Patent Summary....................... 132 Design Bases and Assumptions................ 134 Major Process Equipment and Utilities Summary....... 136 StreamFlows........................ 139 Summary of Waste Products................. 143 Total Capital Investment.................. 145 Production Costs. i.................... 147 Isomerization with Recycle of ncs, ncs, and MP Patent Summary.................,..... 152 Isomerization with Recycle of nc,, nc,, and MP Design Bases and Assumptions................ 156 Isomerization with Recycle of nc,, ncs, and MP Major Process Equipment and Utilities Summary....... 157 Isomerization with Recycle of ncs, nc,, and MP StreamFlows 161 Isomerization with Recycle of ncs, ncs, and MP Summary of Waste Products................. 165 Isomerization with Recycle of ncs, ncs, and IMP Total Capital Investment..........,....... 167 Isomerization with Recycle of ncs, nce, and MP Production Costs...................... 169 Patent Summary....................... 177 Design Bases and Assumptions................ 183 xii
TABLES 9.3 9.4 9.5 9.6 9.7 9.8 10.1 10.2 10.3 10.4 10.5 10.6 10.7 10.8 B.1 B.2 StreamFlows Summary of Waste Products. Total Capital Investment.. Production Costs... Costs of Total Isomerization Process from the Literature.. Friedel-Crafts Patent Summary.... Hydroisomerization of Butane Patent Summary.... Design Bases and Assumptions StreamFlows Summary of Waste Products. Total Capital Investment.. Production Costs... Properties of Hydrocarbons. Composition of Feedstock.. 185 189 190 195 197 200 203 205 213 215 219 221 225 227 236 236 Xiii