OXO ALCOHOLS PROCESS ECONOMICS PROGRAM. A private report by the. Report No. 21 A. Supplement A. by PARK L. MORSE. November 1871

Transcription

1 Report No. 21 A OXO ALCOHOLS Supplement A by PARK L. MORSE November 1871 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE I MENLO PARK, CALIFORNIA

2 CONTENTS 1 INTRODUCTION SUMMARY... Technical Aspects... Synthesis Gas... Alcohols by Shell Technology... Alcohols by Kuhlmann Technology... Process Summary... Aldol Processing INDUSTRY STATUS STEAM REFORMING OF METHANE IN PRESENCE OF CARBON DIOXIDE.,. 15 Chemistry... Thermodynamics... Effect of Variables... Energy Balance... Kinetics... Review of Processes... Scope... Summary of Report Construction and Design... Reformer Problems... Processing of Reformer Feed and Effluent... Comparison of Methods for Preparing 0x0 Synthesis Gas REVIEW OF OXO ALCOHOL TECHNOLOGY... Chemistry... Review of Processes... Cycles... Conversion with a Conventional Cobalt Commercial Operation with Conventional Cobalt s... Rhodium and Phosphorus s... Heterogeneous... Conversion of By-Products... Hydrogenation... Alcohol Purification V

3 CONTENTS 6 OXO ALCOHOLS BY ANIONIC TRANSFER OF CATALYST Chemistry Process Description Process Discussion Cost Estimates LONG CHAIN OXO ALCOHOLS USING PHOSPHINE-TYPE CATALYST Process Description Process Discussion Cost Estimates COMBINATIONS OF OXO AND ALDOL PROCESSING Chemistry Review of Processes Aldox Process OxO-Aldol Process Low-Pressure, One-Step Process Cost Estimates APPENDIX A DESIGN AND COST BASIS AND DEFINITIONS APPENDIX B PHYSICAL PROPERTIES AND SPECIFICATIONS..,,., APPENDIX C HANDLING AND SAFETY..,.,.,.., CITED REFERENCES PATENT REFERENCES BYCOMPANY Vi

4 ILLUSTRATIONS 4.1 Steam Reforming of Methane Effect of Temperature and Pressure on K /(PaKpn) P,l, Steam Reforming of Methane Za as a Function of Temperature Equilibrium Constant for Bouduard Reaction Effect of Variables in Steam Reforming of Methane Steam Reforming of Methane Comparison of Kellogg's Predicted Values with Experimental Results., Schematic Drawing of Reformer Tube Chrome-Nickel Content in Creep Resistant Reformer Tube Alloys.., Allowable Stresses for Cast 25 Cr-20 Ni (HK-40) Reformer Tube Alloy..,., Time to Rupture in HK-40 Reformer Tubing Rupture Properties of IN-519 Reformer Tube Alloy Effect of Reformer Tube Diameter on Skin Temperature Comparison of a Pure Pressure Swing Cycle with a Pure Thermal Swing Cycle, Hydroformylation of Heptenes Poisoning Effect of Oxygen in Hydroformylation of Ca-Ca Olefins Effect of Concentration of Propylene Conversion.. 76 Effect of Concentration on n-butanol Yield Effect of CO/Ha Ratio Propylene Conversion Effect of CO/Ha Ratio on n-butanol Yield Hydroformylation with a Phosphorus Effects of Temperature on Aldehyde-Alcohol Distribution, 0.19 mol propene, 110 ml n-dodecyl alcohol, 5.85 mmols Coa(CO), and 23.4 mmols PBua Vii

5 ILLUSTRATIONS B.l B.2 B.3 B.4 B.5 Hydroformylation with a Phosphorus Effect of Total Pressures of Conversion and Selectivity mol propene, 110 ml n-dodecyl alcohol containing 5.85 mmols Co,(CO), and 23.4 mmols PBua Hydroformylation with a Phosphorus Effect of HCo(CO), (PBu3) Concentration on Aldehyde- Alcohol Distribution mol propene, 110 ml n- dodecyl alcohol containing Co,(CO) and PBus at a ratiooflto Effect of Composition on Reaction Rate and Selectivity.., Effect of CO Partial Pressure on Normal to Iso Ratio and Paraffin Formation......, Union Oil 0x0 Process x0 Alcohols by Anionic Transfer of x0 Alcohols by Anionic Transfer of Effect of Operating Level and Plant Capacity on Production Cost , ,..., Effect of Operating Level and Plant Capacity on Production Cost Vapor Pressure for Various Olefins and Paraffins....., 199 Vapor Pressure of Aldehydes Vapor Pressure of Normal Alcohols Vapor Pressure of Branched Alcohols..., Equilibrium Constants for Hydrogen and Carbon Monoxide at looof, , viii

6 TABLES 2.1 0x0 Alcohol Processes Cost Comparison x0 Alcohol Production Process Summary Feed Stocks and the Corresponding 0x0 Alcohols Free World Plant Capacity for 0x0 Alcohols, Equilibrium Constants as a Function of Temperature..... Equilibrium Calculations for Steam Reforming Methane and Carbon Dioxide Known Failures in Cast HK-40 Reformer Tubes Materials of Construction in Reforming Process.,..... Comparison of Pressure Swing, Cryogenic, and Palladium Diffusion Processes Manufacturing Costs for 0x0 Synthesis Gas ,. 5.1 Comparison of 0x0 s Cycles Patent Summary of Cycles Effect of Olefin Type on Hydroformylation Effect of Solvents on the Hydroformylation of Methylacrylate....., Hydroformylation of Olefins Patent Summary Effect of Excess Ligand on Product Distribution of Alpha-Olefin Feed Effect of Solvent Variation , Effect of Temperature.....,.., Effect of Pressure.,..., , IX

7 TABLES Hydroformylation of l-octene with Varying Concentrations of Ligand,., , Hydroformylation of l-octene at Various Pressures Hydroformylation of l-octene with Various Tri- Substituted Phorphorus Ligands Hydroformylation of Higher Alpha-Olefins x0 Alcohol Recovery, Purification, and Hydrogenation Patent Summary x0 Alcohols by Anionic Transfer of Major Process Equipment and Utilities Summary x0 Alcohols by Anionic Transfer of Stream Flows x0 Alcohols by Anionic Transfer of Total Capital Investment...,...., x0 Alcohols by Anionic Transfer of Production Costs , Major Process Equipment and Utilities Summary Stream Flows , Total Capital Investment Production Costs..., ,, 181 Process Information for 2-Ethylhexanol by Oxo-Aldol Process ,

8 TABLES B.l Specifications and Typical Properties for 0x0 Feed Olefins B.2 Specifications for Shell's Long Chain 206 B.3 Physical and Storage Properties of Shell's Long Chain 206 B.4 Specifications and Typical Properties of 0x0 Alcohols,., 207 Xi