- Report No. 35Al

a BUTADIENE

Prior to Supplement A

by GEORGE E. HADDELAND

March 1972 - A private report by the

PROCESS ECONOMICS PROGRAM a STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA I CONTENTS

INTRODUCTION...... 1

SUMMARY ...... 3 Butadiene by Oxidative Dehydrogenation ...... General Aspects ...... Technical Aspects ...... Butadiene Separation by Extractive Distillation ...... General Aspects ...... Technical Aspects ......

OXIDATIVE DEHYDROGENATION OF n-BUTENES TO 1,3-BUTADIENE , . . 11 Review of Technology and Processes ...... 11 Process Development ...... 11 Oxidative Dehydrogenation Technology ...... 14 Summary of Patents ...... 20 Oxidative Dehydrogenation Processes ...... 25 Description of Process Used in This Study ...... 26 Process Discussion ...... 37 Cost Estimates ...... 38 Capital Investment ...... 38 Production Costs ...... 39 Discussion of Costs ...... 39 Conclusions ...... 41

BUTADIENE SEPARATION BY EXTRACTIVE DISTILLATION ...... 51 Review of Extractive Distillation Technology ...... 51 Solvent Properties ...... 51 Solvent Selection ...... 54 Summary of Patents ...... 57 Description of Extractive Distillation Processes ...... 63 BASF’s N-Methylpyrrolidone Process ...... 66 Nippon Zeon's Dimethylformamide Process ...... 75 Phillips Petroleum's Furfural Process ...... 80 Shell's Acetonitrile Process ...... 86 Union Carbide's Dimethylacetamide Process ...... 92 Discussion of Process Designs ...... 99 Cost Estimates ...... 100 Capital Investment ...... 100 Production Costs ...... 100 Discussion of Costs ...... 101 Conclusions ...... 103

V CONTENTS

APPENDIX A COEFFICIENTS OF RELATIVE VOLATILITY FOR C4 HYDROCARBONS ...... 113

APPENDIX B RELATIVE VOLATILITIES OF C, HYDROCARBONS . . , , . . 119

APPENDIX C SPECIFIC GRAVITIES ...... 123

APPENDIX D BOILING POINTS OF EXTRACTIVE SOLVENTS ...... 127

APPENDIX E TYPICAL C, FRACTIONS FROM NAPHTHA CRACKING ...... 129

APPENDIX F PRODUCT SPECIFICATIONS ...... 131

CITED REFERENCES ...... 133

PATENT REFERENCES BY COMPANY ...... 147

vi FIGURES

3.1 Possible Modification of Existing Commercial Operations To Include Oxidative Dehydrogenation of Butenes . , . , . . 13 3.2 Effect of Pressure on n-Butane Dehydrogenation Equilibrium . 15 3.3 Rate of Conversion of Butene-1 to Oxygenated Products at 842 F, a Reaction Time of 9.77 set, and Varying Butene-1 and Oxygen Partial Pressures ...... , ...... 18 3.4 Catalytic Dehydrogenation of Butane to Butenes and Oxidative Dehydrogenation of Butenes to Butadiene , . . . , 31 3.5 Butadiene from Butane by the Houdry Process in Combination with Oxidative Dehydrogenation and by the Houdry Process Alone Estimated Capital and Production Costs ...... , . . . . 47 3.6 Butadiene from Butenes.by Catalytic Dehydrogenation and by Oxidative Dehydrogenation Estimated Capital and Production Costs ...... , . . . . 48 3.7 Butadiene from Ethylene Plant By-Product Q's Estimated Capital and Production Costs ...... , . . . . 49 4.1 Basic Components of Extractive Distillation Systems . . . , 59 4.2 Butadiene Separation by Extractive Distillation BASF's N-Methylpyrrolidone Process , ...... , . . . . 69 4.3 Rate of Butadiene Dimerization as a Function of Temperature ...... 73 4.4 BASF Process Concentration Profile ...... 74 4.5 Butadiene Separation by Extractive Distillation Nippon Zeon's Dimethylformamide Process ...... 77 4.6 Butadiene Separation by Extractive Distillation Phillips Petroleum's Furfural Process , . . . , , . . . . . 83 4.7 Butadiene Separation by Extractive Distillation Shell's Acetonitrile Process ...... 89 4.8 Butadiene Separation by Extractive Distillation Union Carbide's Dimethylacetamide Process . . . . , . . . . 95 4.9 Estimated Costs of Butadiene Separation from C, Hydrocarbons by Extractive Distillation . . , ...... 109

Vii FIGURES

B.l Relative Volatilities of Cr,Hydrocarbons ...... 121 C.1 Specific Gravities of Extractive Distillation Solvents . . . 125 C.2 Specific Gravities of Q Hydrocarbons ...... 126

Viii TABLES

2.1 Summary of Butadiene Production Costs by Oxidative Dehydrogenation . . . , ...... 4 2.2 Summary of Butadiene Separation Costs by Commercial Extractive Distillation Processes . . . . . , . 7 3.1 Oxidative Dehydrogenation of Butenes to Butadiene Patent Summary ...... 21 3.2 Catalytic Dehydrogenation of Butane to Butenes and Oxidative Dehydrogenation of Butenes to Butadiene Major Process Equipment and Utilities Summary ...... 29 3.3 Catalytic Dehydrogenation of Butane to Butenes and Oxidative Dehydrogenation of Butenes to Butadiene Stream Flows ...... , ...... 35 3.4 Catalytic Dehydrogenation of Butane to Butenes and Oxidative Dehydrogenation of Butenes to Butadiene Total Capital Investment , . . . . . , . . . . . , . . . . 43 3.5 Catalytic Dehydrogenation of Butane to Butenes and Oxidative Dehydrogenation of Butenes to Butadiene Production Costs ...... , ...... 45 4.1 Physical Properties of Solvents for C4 Separations . . . . 53 4.2 Relation of Butene and Butadiene Absorption and Selectivity to the Parametric Shift of Several Solvents . . 57 4.3 Butadiene Separation by Extractive Distillation Patent Summary ...... 61 4.4 Commercial Extractive Distillation Processes Installed Since 1960 for Butadiene Separation . . . . , ...... 65 4.5 BASF's N-Methylpyrrolidone Process Major Process Equipment and Utilities Summary . . . , . . . 69

4.6 BASF's N-Methylpyrrolidone Process Stream Flows ...... 71 4.7 Nippon Zeon's Dimethylformamide Process Major Process Equipment and Utilities Summary ...... 77 4.8 Nippon Zeon's Dimethylformamide Process Stream Flows ...... , ...... 79 4.9 Phillips Petroleum's Furfural Process Major Process Equipment and Utilities Summary . , . , . . . 83

iX TABLES

4.10 Phillips Petroleum's Furfural Process Stream Flows . , . . , . . . . . , , . . , . . . . , . . , 85 4.11 Shell's Acetonitrile Process Major Process Equipment and Utilities Summary , . . . . , , 89 4.12 Shell's Acetonitrile Process Stream Flows ...... , . . . , ...... 91 4.13 Union Carbide's Dimethylacetamide Process Major Process Equipment and Utilities Summary . . . , . . . 95 4.14 Union Carbide's Dimethylacetamide Process Stream Flows . . . . . , . . . , ...... , . 97 4.15 Butadiene Separation by Extractive Distillation Total Capital Investment . . , ...... , . . . 105 4.16 Butadiene Separation .byExtractive Distillation Production Costs ...... , ...... 107 4.17 Comparison of Processes for Butadiene Separation by Extractive Distillation . . . . , ...... , . , . 111 A.1 Coefficients of Relative Volatility for C4 Hydrocarbons in Acetonitrile at 122'F ...... 115

A.2 Coefficients of Relative Volatiliiy for C4 Hydrocarbons in Dimethylformamide (DMF) at 122 F ...... 115 A.3 Coefficients of Relative Volatility for C4 Hydrocarbons in Furfural at 150'F , ...... , . . . , ...... , 116 A.4 Coefficients of Relative Volatility for C4 Hydrocarbons in N-Methylpyrrolidone (RMP) at 122'F . . . , ...... 117 A.5 Coefficients of Relative Volatility for C4 Hydrocarbons in Dimethylacetamide (DMAC) at 122 F ...... , 118

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