OX0 ALCOHOLS PROCESS ECONOMICS PROGRAM. Report No. 21. contributions by Shigeyoshi Takaoka. November A private report by the

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1 Report No. 21 OX0 ALCOHOLS by RICHARD G. DENNEY contributions by Shigeyoshi Takaoka November 1966 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE I I MENLO PARK, CALIFORNIA

2 I INTRODUCTION II SUMMARY... General Aspects... Technical Aspects III INDUSTRY STATUS IV CHEMISTRY OF OXO ALCOHOL PRODUCTION... Stoichiometry... Mechanisms... Hydroformylation... Aldol Condensation... Kinetics... Product Distribution... Catalyst Addition and Removal... Metal Cycle... Organic Salts Cycle... Inorganic Salt Cycle... Anionic Transfer Cycle... Hydrogenation... V PROCESSES FOR OXO ALCOHOL PRODUCTION... Low Pressure One-Step Process... Review of Processes... Process Description... Process Discussion... Cost Estimates... Aldox Process... Review of Processes... Process Description... Process Discussion... Cost Estimates... Oxo-aldol Process... Review of Processes... Process Description... Process Discussion... Cost Estimates iii

3 CONTENTS V (continued) Other 0x0 Processes Review of Processes Process Description Process Discussion Cost Estimates APPENDIX A DESIGN AND COST BASIS 225 APPENDIX B HANDLING AND SAFETY. 231 APPENDIX C PHYSICAL DATA. 235 APPENDIX D RAW MATERIAL AND PRODUCT SPECIFICATIONS 245 CITED REFERENCES : SUPPLEMENTARY REFERENCES iv

4 ILLUSTRATIONS History of 0x0 Capacity and Consumption in the United States Proposed Structures of Cobalt Hydrocarbonyl. Hydroformylation Rates of Olefins Specific Hydroformylation Rates of Olefins..,... Effect of 0x0 Reactor Liquid Hourly Space Velocity on Process Unit and Utilities Investment. Effect of Plant Capacity on Total Fixed Capital Cost.. Effect of Raw Material Costs and By-Product Credit on Net Total Production Costs Effect of Plant Capacity and Production Rate on Net Total Production Cost. Effect of C4 Aldehyde Recycle on Selectivity to Ca Products.. Reaction and Catalyst Recovery. Aldehyde Separation and C4 Alcohol Production 2-Ethylhexanol Production and Heavy Ends Reprocessing.. Effect of Plant Capacity on Total Fixed Capital Costs Effect of Raw Material Costs and By-Product Credit on 2-Ethylhexanol Net Total Production Costs 116 Effect of Plant Capacity and Production Rate on 2-Ethylhexanol Net Total Production Cost V

5 ILLUSTRATIONS Reaction and Catalyst Recovery..,. 127 Aldehyde Separation and C4 Alcohol Production Ethylhexanol Production and Heavy Ends Reprocessing. 131 Effect of Plant Capacity on Capital Cost C4 Aldehydes and Alcohols by the 0x0 Process Effect of Plant Capacity on Capital Cost Effect of Raw Material Cost and By-Product Credit on 2-Ethylhexanol Net Total Production Cost 157 Oxo Alcohols by the Oxo-Aldol Process Effect of Plant Capacity and Production Rate on Net Total Production Cost 159 Cobalt Concentration in Liquid Reactants As a Function of Reaction Temperature and Carbon Monoxide Partial Pressure Stability of Cobalt Carbonyl Catalyst As A Function of Reaction Temperature and Carbon Monoxide Partial Pressure Typical Oil Soluble Organic Soap 0x0 Catalyst Cycle Typical Water Soluble Organic Cobalt Salt 0x0 Catalyst Cycle. 175 Typical Inorganic Cobalt Salt 0x0 Catalyst Cycle..,. 179 Typical Anionic Transfer 0x0 Catalyst Cycle 183 Oxo Alcohols by a Low Pressure Two-Step Process Oxo Reaction and Catalyst Recovery Hydrogenation and Alcohol Finishing. 199 Effect of Plant Capacity on Total Fixed Capital Cost Effect of Raw Material Costs and By-Product Credit on Net Total Production Cost 219 vi

6 ILLUSTRATIONS Effect of Plant Capacity and Production Rate on Net Total Production Cost. 221 Vapor-Liquid Equilibrium for Butyl Alcohol and 0x0 Heavy Ends. 239 Vapor-Liquid Equilibrium for Butyl Alcohol and 0x0 Light Ends. 240 Vapor-Liquid Equilibrium for Isobutyl and Normal Butyl Alcohol. 241 Equilibrium Constants for Hydrogen and Carbon Monoxide atlooof Vapor Pressure--Aldehydes. 243 Vapor Pressure--Alcohols.., vii

7 TABLES a Summary of Costs of Evaluated Processes. Summary of Technical Aspects of Evaluated Processes. Oxo Plant Capacities Americas... Oxo Plant Capacities Europe... Oxo Plant Capacities Asia and Australia 0x0 Alcohols by a One-Step Process Summary of Processes.. Major Process Equipment and Utilities Summary. Process Unit and Utilities Investment.. Total Capital Investment Production Costs. Summary of Esso Research & Engineering Processes Major Process Equipment and Utilities Summary Aldox Reaction and Catalyst Recovery Sections.. Aldehyde Separation and C+ Alcohol Production Section 2-Ethylhexanol Production and Heavy Ends Reprocessing Sections ix

8 TABLES Oxo Alcohols by the Aldox Process Process Unit and Utilities Investment, Total Capital Investment Production Costs x0 Aldehyde by the Hydroformylation of Olefins Summary of Mitsubishi Processes Effect of Reaction Temperature on the Reaction Rate and Normal Iso-Ratio in the Hydroformylation of Propylene to Butyraldehydes Oxo Alcohols by the Oxo-Aldol Process Major Process Equipment and Utilities Summary Oxo Alcohols by the Oxo-Aldol Process 0x0 Reaction and Catalyst Recovery.. Aldehyde Separation and C+ Alcohol Production 2-Ethylhexanol Production and Heavy Ends Reprocessing.. Process Unit and Utilities Investment Total Captial Investment Production Cost Oxo Alcohols by the Hydroformylation of Olefins Summary of Other Processes Comparison of 0x0 Catalysts Recovery and Recycle Methods Hydrogenation of 0x0 Aldehydes to Alcohols Summary of Processes 189 X

9 TABLES Comparison of 0x0 Alcohols Pretreatment Methods Major Process Equipment and Utilities Summary... Process Unit and Utilities Investment.. Oxo Alcohols by a Low Pressure Two-Step Process Total Capital Investment.. Production Costs 38 Heats of Combustion and Vaporization for Various Compounds Associated with 0x0 Alcohols 39 Specifications and Typical Properties of 0x0 Alcohols xi