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Adipic Acid

Adipic Acid

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- a Report No. 3

ADIPIC ACID

. by HAROLD C. RIES

March 1965

A private report by the

PROCESS ECONOMICS PROGRAM

STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA I CONTENTS

I INTRODUCTION ...... 1

II SUMMARY ...... 3

III INDUSTRY STATUS ...... 9

IV CHEMISTRY OF INTERMEDIATES PRODUCTION . . . . . 13 Oxidation of ...... 13 Noncatalytic, Liquid Phase Oxidation of Cyclohexane . . . 13 Catalytic Air Oxidation of Cyclohexane in the Liquid Phase ...... 15 Esterification during Air Oxidation of Cyclohexane . . . . 21 Phenol ...... 25

V CHEMISTRY OF ADIPIC ACID PRODUCTION FROM INTERMEDIATES . . . 29 Nitric Acid Oxidation of Intermediates ...... 29 Other Reactions ...... 33 Discussion ...... 34

VI PROCESSES FOR ADIPIC ACID MANUFACTURE . . . . . , . . . . . 37

Part A Intermediates from Catalytic Air Oxidation of Cyclohexane

Review of Processes ... 37 Impure Cyclohexane Feed 39 Recovery of Cyclohexane from Off-Gas...... 40 Control of Hydroperoxides ...... 40 Oxidation Reactors ...... 42 Ester Hydrolysis ...... 43 By-products Control ...... 44 Cyclohexane Separation 44 Reaction in Presence of Solvents...... 45 Process Description ...... 45 Raw Materials ...... 52

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VI Continued

Part B Adipic Acid by Nitric Acid Oxidation of Intermediates

Review of Processes ...... 53 Catalysts ...... 53 Reactor ...... 54 By-product Control ...... 54 Safety ...... 55 Recovery and Purification of Products ...... 55 Process Description ...... 58 Raw Materials ...... 71

Part C Hydrogenation of Phenol

Review of Processes ;22 Vapor Phase Hydrogenation...... Temperature Control ...... 73 Catalysts ...... 73 Liquid Phase Hydrogenation ...... 74 Process Description ...... 75 Nitric Acid Oxidation of ...... 80 Raw Materials ...... 80

Part D Air Oxidation of Cyclohexane with Esterification

Review of Processes ...... 82 Process Description ...... 85

Part E Dehydrogenation of Cyclohexanol

Review of Processes ...... 91 Process Description ...... 92

Part F Air Oxidation Of Intermediates

Review of Processes ...... 97 Process Description ...... , . 98

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VII ECONOMICS OF ADIPIC ACID MANUFACTURE ...... 105

Part A Air Oxidation of Cyclohexane and Nitric Acid Oxidation of KA

Capital Investment ...... 105 Production Costs ...... 105 Variations Affecting Costs ...... 111 I.F.P. Process ...... 113

Part B Phenol Hydrogenation and Nitric Acid Oxidation of Cyclohexanol

Capital Investment ...... 117 Production Costs ...... 117

Part C Miscellaneous Routes

Capital Investment ...... 122 Production Costs ...... 122 (1) Boric Acid Modified Air Oxidation of Cyclohexane and Nitric Acid Oxidation of Intermediates . . . . . 122 (2) Three Step Process ...... 122 (3) Air Oxidation of Cyclohexane and Air Oxidation of EA. 129

VIII OTHER PROCESSES ...... 135

Appendix A DESIGN AND COST BASIS ...... 143

Appendix B PHYSICAL DATA...... 147

Appendix C RAW MATERIAL AND PRODUCT SPECIFICATIONS ...... 151

CITED REFERENCES...... 155

SUPPLEMENTARY REFERENCES...... 167

V ILLUSTRATIONS

Figure Page

Kinetic Effects of Air Oxidation of Cyclohexane ...... 17 Proposed Reaction Mechanism for Air Oxidation of Cyclohexane. . 22 Proposed Reaction Mechanism for Nitric Acid Oxidation to Adipic Acid...... 31 4 Speculative Mechanism for Nitric Acid Oxidation to Adipic Acid ...... 35 Air Oxidation of Cyclohexane to Crude KA ...... 47 Adipic Acid by Nitric Acid Oxidation of Intermediates . . . . . 61 Cyclohexanol by Hydrogenation of Phenol ...... 77 Effect of Boric Acid on Oxidation of Cyclohexane ...... 84 Boric Acid Modified Air Oxidation of Cyclohexane to Inter- mediates ...... 89 10 Crude Cyclohexane from Cyclohexanol ...... 95 11 Adipic Acid by Air Oxidation of Intermediates ...... lOl 12 Effect of Conversion and Selectivity on Costs of Adipic Acid .112

vi TABLES

Number Page

Plant Capacities--Americas ...... 11 Plant Capacities--WesternEurope ...... 12 Air Oxidation to Crude KA--Major Process Equipment List . 46 Air Oxidation of Cyclohexane to Crude KA--Stream Flows . . 49 Adipic Acid by Nitric Acid Oxidation of Intermediates-- Major Process Equipment List , ...... 59 6 Adipic Acid by Nitric Acid Oxidation of Intermediates-- Stream Flows ...... 65 7 Cyclohexanol by Hydrogenation of Phenol--Major Process Equipment List ...... , ...... , . 76 8 Boric Acid Modified Air Oxidation of Cyclohexane--Major Process Equipment List ...... 87 9 Dehydrogenation of Cyclohexanol--Major Process Equipment List.,.....,...... 94 10 Adipic Acid by Air Oxidation of Intermediates--Major Process Equipment List ...... 99 11 Adipic Acid Manufacture from Cyclohexane: Air (1st Stage), HN03 (2nd Stage)-dapital Investment ...... 107 12 Overall Capital Investment, Air-Nitric Acid Process-- 50 MM Lb/Yr Adipic Acid Plant ...... 109 13 Adipic Acid Manufacture from Cyclohexane: Air (1st Stage), HNO3 (2nd Stage)--ProductionCosts ...... 110 14 I.F.P. Process--Capital Investment for 88.2 MM Lb/Yr KA Plant...... 114 15 Comparison of I.F.P. and Previous Process ...... 115 16 Adipic Acid Manufacture from Cyclohexane by I.F.P.-- Process Production Costs ...... 116 17 Adipic Acid Manufacture from Phenol: Hydrogenation (1st Stage), HN03 Oxidation (2nd Stage)--Capital Investment ...... 118 18 Overall Capital Investment, Phenol Process--50 MM Lb/Yr Adipic Acid Plant ...... 119 19 Adipic Acid Manufacture from Phenol: Hydrogenation (1st Stage), HN03 Oxidation (2nd Stage)--ProductionCosts . . . 120 20 Boric Acid Modified Air Oxidation of Cyclohexane-- Capital Investment ...... 123 21 Dehydrogenation of Cyclohexanol--Capital Investment . . . 124 22 Adipic Acid by Air Oxidation of Intermediates--Capital Investment ...... 125 23 Overall Capital Investment, Modified Air-Nitric Acid Process--50 MM Lb/Yr Adipic Acid Plant ...... , . 126 24 Adipic Acid Manufacture (1st Stage: Boric Acid Modified Air Oxidation of Cyclohexane; 2nd Stage: Nitric Acid Oxidation of Intermediates--ProductionCost ...... 127

vii TABLES

Number Page 25 Overall Capital Investment, Three-Step Process-- 50 MM Lb/Yr Adipic Acid Plant ...... 128 26 Adipic Acid Manufacture, Three Step Process--Production costs...... ,...... 130 27 Overall Capital Investment, Two-Stage Air Oxidation Process--50 MM Lb/Yr Adipic Acid Plant ...... 131 28 Adipic Acid Manufacture by Two-Stage Air Oxidation-- Production Costs ...... 132 29 Summary of Costs for Three Processes ...... 133 30 Summary of Other Processes ...... 137

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