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t.. - 2, SRI INTERNATIONAL Manlo Park, California 94025 Abstract

Process Economics Program Report No. 76B

AROMATIC

(April 1981)

The processes for making by and by amination of are updated. The former process is more economical than the latter under most conditions. Another process, using reduction, is evaluated. This process is economic if the coproduced iron oxide is sold as . Other processes for making aniline are discussed.

Two processes for making , a precursor of aniline, are evaluated. The newly developed adiabatic process has some cost advantage over the conventional nitration process.

Several important aniline derivatives are evaluated: N,N- made from by a liquid process, N-ethylaniline and

N,N-diethylaniline jointly made from ethanol by a gas phase process, o-ethylaniline and 2,6-diethylaniline,jointly made from ethylene by a batch process, and from aniline condensation. Other derivatives of aniline are described.

PEP'80 YCY Report No. 76B

AROMATIC AMINES

SUPPLEMENT B

by YEN-CHEN YEN

FENG -HSIN HUANG

I 1 April 1981

A private report by the PROCESS ECONOMICS PROGRAM

Menlo Park, California 94025 For detailed marketing data and information, the reader is referred to one of the SRI programs specializing in marketing research. The CHEMICAL ECONOMICS HANDBOOK Program covers most major chemicals and chemical products produced in the United States and the WORLD Program covers major hydrocarbons and their derivatives on a worldwide basis. In addition, the SKI DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, prod- uct, and plant for the United States and Western Europe.

ii CONTENTS

0 1 INTRODUCTION...... 1

2 SUMMARY ...... 3 General Aspects--Aniline...... 3 General Aspects--Aniline Derivatives...... 6 Technical Aspects ...... 6 Nitrobenzene by the Conventional Nitration Process...... 6 Nitrobenzene by the Adiabatic Nitration Process ...... 6 Aniline by Reduction of Nitrobenzene ...... 9 Aniline by Phenol Ammonolysis ...... 9 Aniline from Nitrobenzene by Iron Reduction ...... 10 N,N-Dimethylaniline from Aniline and Methanol ...... 10 N-Ethylaniline and N,N-Diethylaniline from Aniline and Ethanol ...... 11 ortho-Ethylaniline and 2,6-Diethylaniline from Aniline and Ethylene...... 11

3 INDUSTRY STATUS...... 13 Producers and Production Capacity of Aniline...... 13 l Markets for Aniline ...... 13 Aniline Derivatives ...... 13 U.S. Production Statistics for Aniline...... 18

4 NITROBENZENE MANUFACTURE...... 23 Review of Processes ...... 23 Tubular Reactor or Pump Reactor ...... 23 Adiabatic Nitration Process Using Mixed Acid...... 24 Nitration Without ...... 25 A Conventional Nitration Process for Making Nitrobenzene. ... 26 Process Description ...... 26 Process Discussion ...... 37 Cost Estimates ...... 38 An Adiabatic Nitration Process for Making Nitrobenzene. .... 42 Process Description ...... 42 Process Discussion ...... 49 Cost Estimates ...... 49

5 ANILINE FROM NITROBENZENE BY HYDROGEN REDUCTION ...... 55 Review of Processes ...... 55 Process Description ...... 55 Process Discussion ...... 67 Cost Estimates ...... 68

iii CONTENTS

...... 79 6 ANILINE FROM PHENOL BY AMMONOLYSIS. 0 Review of Processes ...... 79 Process Description ...... 79 ProcessDiscussion ...... 91 Cost Estimates ...... 91

7 ANILINE FROM NITROBENZENE BY IRON REDUCTION ...... 99 0 Chemistry ...... 99 Review of Processes ...... 99 A Process for Producing Aniline from Nitrobenzene by Iron Reduction, with Coproduction of Pigment...... 100 Process Description ...... 100 Process Discussion ...... 110 Cost Estimates ...... 110

8 OTHER PROCESSES FOR PRODUCING ANILINE ...... 117 Processes Starting from Nitrobenzene...... 117 Reduction by Monoxide...... 117 Reduction by Methane...... 117 0 Reduction by Cyclohexene...... 118 Reduction by ...... 118 Reduction by Hydrogen Sulfide ...... 118 Reduction by Cyclohexanol in Conjunction with Water and ...... 118 Electrolytic Reduction ...... 118 Coproduction of Styrene from Ethylbenzene ...... 119 Reduction by Metal Chelate Polymers ...... 119 Direct Amination Processes ...... 120 Thallium Intermediate ...... 120 By Hydroxylamine ...... 120 Processes Starting from Cyclohexane ...... 121 Amination of Cyclohexane...... 121 Amination of Cyclohexanol-Cyclohexanone...... 121 Process Starting from ...... 121

9 N-ALKYLANILINES ...... 123 Chemistry ...... 123 Review of Processes ...... 124 0 N,N-Dimethylaniline by Liquid Phase Methylation ofAniline .; ...... 131 Process Description ...... : . . . . . 131

iv CONTENTS

9 N-ALKYLANILINES (continued) Process Discussion...... 137 Cost Estimates ...... 137 Manufacture of N,N-Diethylaniline ...... 142 N-Ethylaniline and N,N-Diethylaniline by Vapor Phase Ethylation of Aniline ...... 144 Process Description ...... 144 Process Discussion ...... 149 Cost Estimates ...... 149

10 RING ALKYLATED ...... 159 Chemistry ...... 159 Review of Processes ...... 160 A Process for Manufacturing o-Ethylaniline and 2.6-Diethylaniline...... 160 Process Description ...... 160 Process Discussion ...... 173 Cost Estimates ...... 174

11 OTHER ANILINE AND NITROBENZENE DERIVATIVES ...... 183 Diphenylamine ...... 183 ...... 187 ...... 187 Acetoacetanilide ...... 188 Aniline Hydrochloride ...... 188 2-Anilinoethanol...... 188 AnilinomethanesulfonicAcid ...... 188 Chloranil...... 189 Cyclohexylamine...... 189 m-Chloroaniline ...... 189 ...... 189 Metanilic Acid ...... 189

APPENDIX A DESIGN AND COST BASIS ...... 191

APPENDIX B PHYSICAL DATA...... 195

APPENDIX C SIZING OF BATCH COLUMN ...... 199

CITED REFERENCES ...... 201

PATENT REFERENCES By COMPANY ...... 211

V ILLUSTRATIONS

4.1 Nitrobenzene by Conventional Nitration Process...... 215 4.2 Nitrobenzene by Adiabatic Nitration Process ...... 217 5.1 Aniline by Vapor-Phase Catalytic Reduction of Nitrobenzene ...... 219 5.2 Aniline Production from Via Nitrobenzene Effect of Operating Level and Plant Capacity on Production Cost...... 78 6.1 Aniline by Ammonolysis of Phenol...... 221 6.2 Aniline by Ammonolysis of Phenol Effect of Operating Level and Plant Capacity on Production Cost, ...... 96 7.1 Aniline by Bechamp Reduction of Nitrobenzene. . . , . . . . . 223 7.2 Aniline by Bechamp Reduction of Nitrobenzene Effect of Operating Level and Plant Capacity on Production Cost...... 115 7.3 Comparison of Various Processes for Aniline Production Effect of Operating Level on Product Value...... 116 9.1 N,N-Dimethylaniline by Liquid Phase Methylation of Aniline...... 225 9.2 N,N-Dimethylaniline by Liquid Phase Methylation of Aniline Effect of Operating Level and Plant Capacity on Production Cost and Product Value...... 141 9.3 N-Ethylaniline and N,N-Diethylaniline by Vapor Phase Methylation of Aniline. . . , ...... 227 9.4 Production Costs and Product Values of N,-Ethylaniline and N,N-Diethylaniline at Different Production Levels . . . . 158 10.1 o-Ethylaniline and/or 2,6-DiethylanilineManufacture. . . . . 229 10.2 o-Ethylaniline and 2,6-Diethvlaniline Effect of Operating Level and Plant Capacity on Production Cost...... 180 10.3 o-Ethylaniline and 2,6-Diethylaniline Effect of Operating Level and Plant Capacity on Product Value . . . , ...... 181

B.l Equilibrium Conversion of Phenol to Aniline ...... 198

vii TABLES

0 2.1 Aniline Production Summary of Economics. . . . , ...... 4 2.2 Nitrobenzene Production Summary of Economics...... 5 2.3 Alkylated Anilines Production @ Summary of Economics. . . , ...... 7 3.1 U.S. Producers of Aniline ...... 14 3.2 Aniline Producers Outside of the United States...... 15 3.3 Market Distribution of Aniline in the United States . . . . 17 3.4 Chemicals Made from Aniline . . , ...... 19 3.5 Chemicals Made from Nitrobenzene...... 21 3.6 U.S. Production of Aniline and Some Alkylanilines . . . . . 22 4.1 Nitrobenzene Patent Summary ...... 27 4.2 Nitrobenzene by Conventional Nitration Process 0 Design Bases and Assumptions...... 29 4.3 Nitrobenzene Production by Conventional Nitration Process Stream Flows .,...... 32 4.4 Nitrobenzene Production by Conventional Nitration Process Major Equipment ...... 34 4.5 Nitrobenzene Production by Conventional Nitration Process Utilities Summary ...... 36

4.6 Nitrobenzene Production by Conventional 0 Nitration Process Total Capital Investment. . l . . . . . , ...... 39 4.7 Nitrobenzene Production by Conventional Nitration Process Production Costs ...... , . . . 40 l 4.8 Nitrobenzene by Adiabatic Nitration Process Design Bases and Assumptions...... 43

iX TABLES

4.9 Nitrobenzene Production by Adiabatic Nitration Process Stream Flows...... q ...... 44 4.10 NitrobenzeneProduction by AdiabaticNitration Process Major Equipment . , ...... ,I...... 46 4.11 Nitrobenzene Production by Adiabatic Nitration Process Utilities Process ...... , 48 4.12 Nitrobenzene Production by Adiabatic Nitration Process Total Capital Investment, . . . . , ...... 51 4.13 Nitrobenzene Production by Adiabatic Nitration Process Production Costs. . . . , ...... 52 5.1 Aniline by Vapor-Phase Catalytic Reduction of Nitrobenzene Patent Summary .,...... , ...... 56 5.2 Aniline by Liquid-Phase Catalytic Reduction of Nitrobenzene Patent Summary ...... I ...... 57 5.3 Recovery and Purification of Aniline Patent Summary ...... 58 - 5.4 Aniline by Vapor-Phase Catalytic Reduction of Nitrobenzene Design Bases and Assumptions...... -.... 59 5.5 Aniline by Vapor-Phase Catalytic Reduction of Nitrobenzene Stream Flows ...... 63 5.6 Aniline by Vapor-Phase Catalytic Reduction of Nitrobenzene Major Equipment . . . , ...... 64 5.7 Aniline by Vapor-Phase Catalytic Reduction of Nitrobenzene Utilities Summary, ...... 66 5.8 Aniline by Vapor-Phase Catalytic Reduction of Nitrobenzene Total Capital Investment. . . . , ...... 69 0- 5.9 Aniline by Vapor-Phase Catalytic Reduction of Nitrobenzene Production Costs . . . , ...... , ...... 70 5.10 Aniline Production frcznBenzene via Nitrobenzene (Conventional Process) Total Capital Investment. . . . , ...... 72 0 5.11 Aniline Production from Benzene via Nitrobenzene (Conventional Process) Production Costs ...... 73

X TABLES

5.12 Aniline Production fra Benzene via Nitrobenzene (Adiabatic Process) Total Capital Investment...... , ...... 75 5.13 Aniline Production from Benzene via Nitrobenzene (Adiabatic Process) Production Costs ...... , ...... 76 6.1 Aniline from Ammonolysis of Phenol Patent Summary ...... , ...... 80 6.2 Aniline by Ammonolysis of Phenol Design Bases and Assumptions. . . , . . . . . , ...... 82 6.3 Aniline by Ammonolysis of Phenol Stream Flows ...... 86 6.4 Aniline by Ammonolysis of Phenol Major Equipment ...... 88 6.5 Aniline by Ammonolysis of Phenol Utilities Summary ...... 90 6.6 Aniline by Ammonolysis of Phenol Total Capital Investment...... , ...... 93 6.7 Aniline by Ammonolysis of Phenol Production Costs ...... , ...... 94 6.8 Comparison of Product Value of Aniline Made via Nitrobenzene and Aniline Made from Phenol ...... 97 7.1 Aniline by Bechamp Reduction of Nitrobenzene Patent Summary . . . . . , .., ...... 101 7.2 Aniline by Bechamp Reduction of Nitrobenzene Design Bases and Assumptions...... 102 7.3 Aniline by Bechamp Reduction of Nitrobenzene Stream Flows ...... 105 7.4 Aniline by Bechamp Reduction of Nitrobenzene Major Equipment ...... 107 7.5 Aniline by Bechamp Reduction of Nitrobenzene Utilities Summary ...... 109 7.6 Aniline by Bechamp Reduction of Nitrobenzene Total Capital Investment...... , ...... 112 7.7 Aniline by Bechamp Reduction of Nitrobenzene Production Costs ...... 113

xi TABLES

9.1 N-Alkylation of Aniline and Other Aromatic Amines by Alcohol in Liquid Phase Patent summary...... 126 9.2 N-Alkylation of Aniline and Other Aromatic Amines by Alcoholin Gas Phase Patent summary...... 128 9.3 N-Alkylated Aniline Made by Processes Other Than the Reaction Between Alcohol and Aniline Patent summary...... 130 9.4 Purification and Separation of N-Alkylamines Patent summary...... 132 9.5 N,N-Dimethylaniline by Liquid Phase Methylation of Aniline Design Bases and Assumptions. . . , ...... 133 9.6 N,N-Dimethylaniline by Liquid Phase Methylation of Aniline Stream Flows ...... 134 9.7 N,N-Dimethylaniline by Liquid Phase Methylation of Aniline Major Equipment . . . , ...... 135 0 9.8 N,N-Dimethylaniline by Liquid Phase Methylation of Aniline Utilities Summary...... 136 9.9 N,N-Dimethylaniline by Liquid Phase Methylation of Aniline Total Capital Investment...... 138 9.10 N,N-Dimethylaniline by Liquid Phase Methylation of Aniline Production Costs...... 139 9.11 N-Ethylaniline and N,N-Diethylaniline by Vapor Phase Ethylation of Aniline Design Bases and Assumptions, ...... , ...... 143 9.12 N-Ethylaniline and N,N-Diethylaniline by Vapor Phase Ethylation of Aniline 0 StreamFlows ...... 145 9.13 N-Ethylaniline and N,N-Diethylaniline by Vapor Phase Ethylation of Aniline Major Equipment ...... 146 9.14 N-Ethylaniline and N,N-Diethylaniline by Vapor Phase Ethylation of Aniline Utilities Summary...... 148

xii TABLES

9.15A N-Ethylaniline and N,N-Diethylaniline by Vapor Phase Ethylation of Aniline Total Capital Investment...... 150 9.15B N-Ethylaniline and N,N-Diethylaniline by Vapor Phase Ethylation of Aniline 0 Capital Investment by Section ...... , ...... 151 9.16 N-Ethylaniline by Vapor Phase Ethylation of Aniline Production Costs . . . . ; ...... , ...... 152 9.17 N,N-Diethylaniline by Vapor Phase Ethylation of Aniline Production Costs ...... 155 10.1 Ring Alkylated Aniline by Olefin Alkylation Patent Summary ...... 161 10.2 Ring Alkylated Aniline by Other Processes Patent Summary ...... 164 10.3 o-Ethylaniline and 2,6-DiethylanilineManufacture Design Bases and Assumptions...... 166 a 10.4 o-Ethylaniline Manufacture StreamFlows...... 168 10.5 2,6-DiethylanilineManufacture StreamFlows...... 169 10.6 o-Ethylaniline and 2,6-DiethylanilineManufacture Major Equipment ...... 170 10.7A o-Ethylaniline Manufacture Utilities Summary ...... 171 10.7B 2,6-DiethylanilineManufacture Utilities Summary ...... 172 10.8 o-Ethylaniline and 2,6-DiethylanilineManufacture Total Capital Investment ...... 175 10.9 o-Ethylaniline Manufacture Production Costs...... 176 10.10 2,6-DiethylanilineManufacture Production Costs...... 178 11.1 Diphenylaminine by Liquid Phase Condensation of Aniline Total Capital Investment...... 184 11.2 Diphenylaminine by Liquid Phase Condensation of Aniline Production Costs...... 185

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