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a

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Report No. 3

ADIPIC ACID

by HAROLD C. RIES

March 1965

A private report by the

PROCESS ECONOMICS PROGRAM

STANFORD RESEARCH INSTITUTE

I MENLO PARK, CALIFORNIA

CONTENTS

I INTRODUCTION ........................

II SUMMARY ..........................

III INDUSTRY STATUS ..... ................

IV CHEMISTRY OF ADIPIC ACID INTERMEDIATES PRODUCTION . . . . .

Oxidation of Cyclohexane . . . . . . . . . . . . . . . . . . Noncatalytic, Liquid Phase Oxidation of Cyclohexane . . . Catalytic Air Oxidation of Cyclohexane in the Liquid

Phase . . . . . . . . . . . . . . . . . . . . . . . . . Esterification during Air Oxidation of Cyclohexane . . . .

Phenol Hydrogenation . . . . . . . . . . . . . . . . . . . .

13

13 13

15 21 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

Raw Materials . . . . . . . . . . . . . . . . . . . . . . 52

Intermediates from Catalytic Air Oxidation of Cyclohexane

Review of Processes Impure Cyclohexane Feed

...

Recovery of Cyclohexane from Off-Gas ..................................... Control of Hydroperoxides ................ Oxidation Reactors .................... Ester Hydrolysis ..................... By-products Control Cyclohexane Separation

..................

Reaction in Presence of Solvents ................ Process Description ....................

1

3

9

37 39 40 40 42 43 44 44 45 45

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CONTENTS

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 ...................................... Vapor Phase Hydrogenation

;22

Temperature Control .................... 73 Catalysts ......................... 73 Liquid Phase Hydrogenation ................ 74

Process Description ..................... 75 Nitric Acid Oxidation of Cyclohexanol ........... 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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l CONTENTS

VII ECONOMICS OF ADIPIC ACID MANUFACTURE . . . . .

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 . . . . . . . . . . . . . . . . . . . . . Production Costs . . . . . . . . . . . . . . . . . . . . . .

117 117

Part C

Miscellaneous Routes

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

(1) Boric Acid Modified Air Oxidation of Cyclohexane and Nitric Acid Oxidation of Intermediates . . . . .

(2) Three Step Process . . . . . . . . . . . . . . . . . (3) Air Oxidation of Cyclohexane and Air Oxidation of EA.

122 122

122 122 129

VIII OTHER PROCESSES . . . . . . . . . . . . . . . . . . . . . . 135

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

Appendix B PHYSICAL DATA. . . . . . . . . . . . . . . . . . . .

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

CITED REFERENCES.........................

143

147

151

155

SUPPLEMENTARY REFERENCES . . . . . . . . . . . . . . . . . . . . . 167

105

V

ILLUSTRATIONS

Figure Page

4

10

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12

Kinetic Effects of Air Oxidation of Cyclohexane . . . . . . .

Proposed Reaction Mechanism for Air Oxidation of Cyclohexane.

Proposed Reaction Mechanism for Nitric Acid Oxidation to Adipic Acid....... . . . . . . . . . . . . . . . . . .

Speculative Mechanism for Nitric Acid Oxidation to Adipic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Air Oxidation of Cyclohexane to Crude KA . . . . . . . . . .

Adipic Acid by Nitric Acid Oxidation of Intermediates . . . .

Cyclohexanol by Hydrogenation of Phenol . . . . . . . . . . .

Effect of Boric Acid on Oxidation of Cyclohexane . . . . . .

Boric Acid Modified Air Oxidation of Cyclohexane to Inter- mediates . . . . . . . . . . . . . . . . . . . . . . . . . .

Crude Cyclohexane from Cyclohexanol . . . . . . . . . . . . .

Adipic Acid by Air Oxidation of Intermediates . . . . . . . .

Effect of Conversion and Selectivity on Costs of Adipic Acid

. 17

. 22

. 31

. 35

. 47

. 61

. 77

. 84

. 89

. 95

.lOl

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TABLES

Number Page

6

7

8

9

10

11

12

13

14

15 16

17

18

19

20

21 22

23

24

Plant Capacities--Americas . . . . . . . . . . . . . . . . 11 Plant Capacities--Western Europe . . . . . . . . . . . . . 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 Adipic Acid by Nitric Acid Oxidation of Intermediates-- Stream Flows . . . . . . . . . . . . . . . . . . . . . . . 65 Cyclohexanol by Hydrogenation of Phenol--Major Process Equipment List . . . . . . , . . . . . . . . . . . . . , . 76 Boric Acid Modified Air Oxidation of Cyclohexane--Major Process Equipment List . . . . . . . . . . . . . . . . . . 87 Dehydrogenation of Cyclohexanol--Major Process Equipment List.,.....,................... 94 Adipic Acid by Air Oxidation of Intermediates--Major Process Equipment List . . . . . . . . . . . . . . . . . . 99 Adipic Acid Manufacture from Cyclohexane: Air (1st Stage), HN03 (2nd Stage)-dapital Investment . . . . . . . 107 Overall Capital Investment, Air-Nitric Acid Process-- 50 MM Lb/Yr Adipic Acid Plant . . . . . . . . . . . . . . 109 Adipic Acid Manufacture from Cyclohexane: Air (1st Stage), HNO3 (2nd Stage)--Production Costs . . . . . . . . 110 I.F.P. Process--Capital Investment for 88.2 MM Lb/Yr KA Plant......................... 114 Comparison of I.F.P. and Previous Process . . . . . . . . 115 Adipic Acid Manufacture from Cyclohexane by I.F.P.-- Process Production Costs . . . . . . . . . . . . . . . . . 116 Adipic Acid Manufacture from Phenol: Hydrogenation (1st Stage), HN03 Oxidation (2nd Stage)--Capital Investment . . . . . . . . . . . . . . . . . . . . . . . . 118 Overall Capital Investment, Phenol Process--50 MM Lb/Yr Adipic Acid Plant . . . . . . . . . . . . . . . . . . . . 119 Adipic Acid Manufacture from Phenol: Hydrogenation (1st Stage), HN03 Oxidation (2nd Stage)--Production Costs . . . 120 Boric Acid Modified Air Oxidation of Cyclohexane-- Capital Investment . . . . . . . . . . . . . . . . . . . . 123 Dehydrogenation of Cyclohexanol--Capital Investment . . . 124 Adipic Acid by Air Oxidation of Intermediates--Capital Investment . . . . . . . . . . . . . . . . . . . . . . . . 125 Overall Capital Investment, Modified Air-Nitric Acid Process-- 50 MM Lb/Yr Adipic Acid Plant . . . . . . . . , . 126 Adipic Acid Manufacture (1st Stage: Boric Acid Modified Air Oxidation of Cyclohexane; 2nd Stage: Nitric Acid Oxidation of Intermediates--Production Cost . . . . . . . 127

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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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