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t.. - 2, SRI INTERNATIONAL
Manlo Park, California 94025
Abstract
Process Economics Program Report No. 76B
AROMATIC AMINES
(April 1981)
The processes for making aniline by hydrogenation and by amination
of phenol are updated. The former process is more economical than the
latter under most conditions. Another process, using iron reduction, is
evaluated. This process is economic if the coproduced iron oxide is
sold as pigment. Other processes for making aniline are discussed.
Two processes for making nitrobenzene, a precursor of aniline, are
evaluated. The newly developed adiabatic nitration process has some cost
advantage over the conventional nitration process.
Several important aniline derivatives are evaluated: N,N-dimethylaniline
made from methanol by a liquid phase 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 diphenylamine from aniline condensation. Other
derivatives of aniline are described.
PEP'80 YCY
Report No. 76B
I 1
AROMATIC AMINES
SUPPLEMENT B
by YEN-CHEN YEN
FENG -HSIN HUANG
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 PETROCHEMICALS 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
0 1
2
3
l
4
5
CONTENTS
INTRODUCTION. . . . . . . . . . . . . . . . . . . . . . . . . . 1
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 Hydrogen 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
INDUSTRY STATUS. ....................... 13
Producers and Production Capacity of Aniline. ......... 13 Markets for Aniline ...................... 13 Aniline Derivatives ...................... 13 U.S. Production Statistics for Aniline. ............ 18
NITROBENZENE MANUFACTURE. ................... 23
Review of Processes ...................... 23 Tubular Reactor or Pump Reactor ............... 23 Adiabatic Nitration Process Using Mixed Acid. ........ 24 Nitration Without Sulfuric Acid ............... 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
ANILINE FROM NITROBENZENE BY HYDROGEN REDUCTION ........ 55
Review of Processes ...................... 55 Process Description ...................... 55 Process Discussion ...................... 67 Cost Estimates ........................ 68
iii
CONTENTS
6 ANILINE FROM PHENOL BY AMMONOLYSIS. ..............
Review of Processes ...................... Process Description ...................... Process Discussion ...................... Cost Estimates ........................
79 0
79 79 91 91
7 ANILINE FROM NITROBENZENE BY IRON REDUCTION ..........
Chemistry ........................... Review of Processes ...................... A Process for Producing Aniline from Nitrobenzene by Iron Reduction, with Coproduction of Pigment. ......... Process Description ..................... Process Discussion ..................... Cost Estimates .......................
99 0
99 99
100 100 110 110
8 OTHER PROCESSES FOR PRODUCING ANILINE .............
Processes Starting from Nitrobenzene. ............. Reduction by Carbon Monoxide. ................ Reduction by Methane. .................... Reduction by Cyclohexene. .................. Reduction by Hydrazine. ................... Reduction by Hydrogen Sulfide ................ Reduction by Cyclohexanol in Conjunction with Water and Cyclohexylamine .................. Electrolytic Reduction ................... Coproduction of Styrene from Ethylbenzene .......... Reduction by Metal Chelate Polymers ............. Direct Amination Processes ................. Thallium Intermediate .................... By Hydroxylamine ......................
Processes Starting from Cyclohexane .............. Amination of Cyclohexane. .................. Amination of Cyclohexanol-Cyclohexanone ...........
Process Starting from Chlorobenzene ..............
117
117 117 117 118
0
118 118
118 118 119 119 120 120 120 121 121 121 121
9 N-ALKYLANILINES ........................
Chemistry ........................... Review of Processes ...................... N,N-Dimethylaniline by Liquid Phase Methylation ofAniline .; ........................
123
123 124 0
131 Process Description . . . . . . . . . . . . . . . : . . . . . 131
iv
CONTENTS
9 N-ALKYLANILINES (continued)
Process Discussion. .................... Cost Estimates ......................
Manufacture of N,N-Diethylaniline ..............
N-Ethylaniline and N,N-Diethylaniline by Vapor Phase Ethylation of Aniline .................... Process Description .................... Process Discussion .................... Cost Estimates ......................
10 RING ALKYLATED ANILINES ...................
Chemistry .......................... Review of Processes ..................... A Process for Manufacturing o-Ethylaniline and 2.6-Diethylaniline. ..................... Process Description .................... Process Discussion .................... Cost Estimates ......................
11 OTHER ANILINE AND NITROBENZENE DERIVATIVES .........
Diphenylamine ........................ Acetanilide ......................... Sulfanilic Acid ....................... Acetoacetanilide ...................... Aniline Hydrochloride .................... 2-Anilinoethanol. ...................... Anilinomethanesulfonic Acid ................. Chloranil.......... ................ Cyclohexylamine. ...................... m-Chloroaniline ....................... Hydrazobenzene ....................... Metanilic Acid .......................
APPENDIX A DESIGN AND COST BASIS . . . . . . . . . . . . . . . 191
APPENDIX B PHYSICAL DATA................... 195
APPENDIX C SIZING OF BATCH DISTILLATION COLUMN . . . . . . . . 199
CITED REFERENCES .......................
PATENT REFERENCES By COMPANY ...................
V
137 137 142
144 144 149 149
159
159 160
160 160 173 174
183
183 187 187 188 188 188 188 189 189 189 189 189
201
211
ILLUSTRATIONS
4.1
4.2
5.1
5.2
6.1
6.2
7.1
7.2
7.3
9.1
9.2
9.3
9.4
10.1
10.2
10.3
B.l Equilibrium Conversion of Phenol to Aniline . . . . . . . . . 198
Nitrobenzene by Conventional Nitration Process. . . . . . . .
Nitrobenzene by Adiabatic Nitration Process . . . . . . . . .
Aniline by Vapor-Phase Catalytic Reduction of Nitrobenzene . . . . . . . . . . . . . . . . . . . . . . .
Aniline Production from Benzene Via Nitrobenzene Effect of Operating Level and Plant Capacity on Production Cost. . . . . . . . . . . . . . . . . . . . . .
Aniline by Ammonolysis of Phenol. . . . . . . . . . . . . . .
Aniline by Ammonolysis of Phenol Effect of Operating Level and Plant Capacity on Production Cost, . . . . . . . . . . . . . . . . . . . . .
Aniline by Bechamp Reduction of Nitrobenzene. . . , . . . . .
Aniline by Bechamp Reduction of Nitrobenzene Effect of Operating Level and Plant Capacity on Production Cost. . . . . . . . . . . . . . . . . . . . . .
Comparison of Various Processes for Aniline Production Effect of Operating Level on Product Value. . . . . . . . . .
N,N-Dimethylaniline by Liquid Phase Methylation of Aniline. . . . . . . . . . . . . . . . . . . .
N,N-Dimethylaniline by Liquid Phase Methylation of Aniline Effect of Operating Level and Plant Capacity on Production Cost and Product Value. . . . . . . . . . . . .
N-Ethylaniline and N,N-Diethylaniline by Vapor Phase Methylation of Aniline. . . , . . . . . . . . . .
Production Costs and Product Values of N,-Ethylaniline and N,N-Diethylaniline at Different Production Levels . . . .
o-Ethylaniline and/or 2,6-Diethylaniline Manufacture. . . . .
o-Ethylaniline and 2,6-Diethvlaniline Effect of Operating Level and Plant Capacity on Production Cost. . . . . . . . . . . . . . . . . . . . . .
o-Ethylaniline and 2,6-Diethylaniline Effect of Operating Level and Plant Capacity on Product Value . . . , . . . . . . . . . . . . . . . . . .
vii
215
217
219
78
221
96
223
115
116
225
141
227
158
229
180
181
0 2.1
2.2
@
2.3
3.1
3.2
3.3
3.4
3.5
3.6
4.1
0 4.2
4.3
4.4
4.5
0 4.6
4.7
l 4.8
TABLES
Aniline Production Summary of Economics. . . . , . . . . . . . . . . . . . . .
Nitrobenzene Production Summary of Economics. . . . . . . . . . . . . . . . . . . .
Alkylated Anilines Production Summary of Economics. . . , . . . . . . . . . . . . . . . .
U.S. Producers of Aniline . . . . . . . . . . . . . . . . .
Aniline Producers Outside of the United States. . . . . . .
Market Distribution of Aniline in the United States . . . .
Chemicals Made from Aniline . . , . . . . . . . . . . . . .
Chemicals Made from Nitrobenzene. . . . . . . . . . . . . .
U.S. Production of Aniline and Some Alkylanilines . . . . .
Nitrobenzene Patent Summary . . . . . . . . . . . . . . . . . . . . . .
Nitrobenzene by Conventional Nitration Process Design Bases and Assumptions. . . . . . . . . . . . . . . .
Nitrobenzene Production by Conventional Nitration Process Stream Flows .,.....................
Nitrobenzene Production by Conventional Nitration Process Major Equipment . . . . . . . . . . . . . . . . . . . . . .
Nitrobenzene Production by Conventional Nitration Process Utilities Summary . . . . . . . . . . . . . . . . . . . . .
Nitrobenzene Production by Conventional Nitration Process Total Capital Investment. . l . . . . . , . . . . . . . . .
Nitrobenzene Production by Conventional Nitration Process Production Costs . . . . . . . . . . . . . . . . . , . . .
Nitrobenzene by Adiabatic Nitration Process Design Bases and Assumptions. . . . . . . . . . . . . . . .
iX
4
32
5
7
14
15
17
19
21
22
27
29
34
36
39
40
43
TABLES
4.9 Nitrobenzene Production by Adiabatic Nitration Process Stream Flows. . . . . . . . . . . . . . q . . . . . . . . . . 44
4.10 Nitrobenzene Production by Adiabatic Nitration 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
5.9 Aniline by Vapor-Phase Catalytic Reduction of Nitrobenzene Production Costs . . . , . . . . . . . . . , . . . . . . . . 70
5.10 Aniline Production frczn Benzene via Nitrobenzene (Conventional Process) Total Capital Investment. . . . , . . . . . . . . . . . . . . 72
5.11 Aniline Production from Benzene via Nitrobenzene (Conventional Process) Production Costs . . . . . . . . . . . . . . . . . . . . . . 73
-
0 -
0
X
5.12
5.13
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
7.1
7.2
7.3
7.4
7.5
7.6
7.7
TABLES
Aniline Production fra Benzene via Nitrobenzene (Adiabatic Process) Total Capital Investment. . . . . . . , . . . . . . . . . . .
Aniline Production from Benzene via Nitrobenzene (Adiabatic Process) Production Costs . . . . . . . . , . . . . . . . . . . . . .
Aniline from Ammonolysis of Phenol Patent Summary . . . . . . . . , . . . . . . . . . . . . . .
Aniline by Ammonolysis of Phenol Design Bases and Assumptions. . . , . . . . . , . . . . . . .
Aniline by Ammonolysis of Phenol Stream Flows . . . . . . . . . . . . . . . . . . . . . . . .
Aniline by Ammonolysis of Phenol Major Equipment . . . . . . . . . . . . . . . . . . . . . . .
Aniline by Ammonolysis of Phenol Utilities Summary . . . . . . . . . . . . . . . . . . . . . .
Aniline by Ammonolysis of Phenol Total Capital Investment. . . . . . , . . . . . . . . . . . .
Aniline by Ammonolysis of Phenol Production Costs . . . . . . , . . . . . . . . . . . . . . .
Comparison of Product Value of Aniline Made via Nitrobenzene and Aniline Made from Phenol . . . . . . . . . .
Aniline by Bechamp Reduction of Nitrobenzene Patent Summary . . . . . , .., . . . . . . . . . . . . . .
Aniline by Bechamp Reduction of Nitrobenzene Design Bases and Assumptions. . . . . . . . . . . . . . . . .
Aniline by Bechamp Reduction of Nitrobenzene Stream Flows . . . . . . . . . . . . . . . . . . . . . . . .
Aniline by Bechamp Reduction of Nitrobenzene Major Equipment . . . . . . . . . . . . . . . . . . . . . . .
Aniline by Bechamp Reduction of Nitrobenzene Utilities Summary . . . . . . . . . . . . . . . . . . . . . .
Aniline by Bechamp Reduction of Nitrobenzene Total Capital Investment. . . . . . . . , . . . . . . . . . .
Aniline by Bechamp Reduction of Nitrobenzene Production Costs . . . . . . . . . . . . . . . . . . . . . .
xi
75
76
80
82
86
88
90
93
94
97
101
102
105
107
109
112
113
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 Alcohol in 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
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 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
0
0
xii
9.15A
9.15B
0 9.16
9.17
10.1
10.2
10.3
a 10.4
10.5
10.6
10.7A
10.7B
10.8
10.9
10.10
11.1
11.2
TABLES
N-Ethylaniline and N,N-Diethylaniline by Vapor Phase Ethylation of Aniline Total Capital Investment. . . . . . . . . . . . . . . . . . . 150
N-Ethylaniline and N,N-Diethylaniline by Vapor Phase Ethylation of Aniline Capital Investment by Section . . . . . . . . , . . . . . . . 151
N-Ethylaniline by Vapor Phase Ethylation of Aniline Production Costs . . . . ; . . . . . . . . . , . . . . . . . 152
N,N-Diethylaniline by Vapor Phase Ethylation of Aniline Production Costs . . . . . . . . . . . . . . . . . . . . . . 155
Ring Alkylated Aniline by Olefin Alkylation Patent Summary . . . . . . . . . . . . . . . . . . . . . . . 161
Ring Alkylated Aniline by Other Processes Patent Summary . . . . . . . . . . . . . . . . . . . . . . . 164
o-Ethylaniline and 2,6-Diethylaniline Manufacture Design Bases and Assumptions. . . . . . . . . . . . . . . . . 166
o-Ethylaniline Manufacture StreamFlows......................... 168
2,6-Diethylaniline Manufacture StreamFlows. . . . . . . . . . . . . . . . . . . . . . . . . 169
o-Ethylaniline and 2,6-Diethylaniline Manufacture Major Equipment . . . . . . . . . . . . . . . . . . . . . . . 170
o-Ethylaniline Manufacture Utilities Summary . . . . . . . . . . . . . . . . . . . . . . 171
2,6-Diethylaniline Manufacture Utilities Summary . . . . . . . . . . . . . . . . . . . . . . 172
o-Ethylaniline and 2,6-Diethylaniline Manufacture Total Capital Investment . . . . . . . . . . . . . . . . . . 175
o-Ethylaniline Manufacture Production Costs. . . . . . . . . . . . . . . . . . . . . . . 176
2,6-Diethylaniline Manufacture Production Costs. . . . . . . . . . . . . . . . . . . . . . . 178
Diphenylaminine by Liquid Phase Condensation of Aniline Total Capital Investment. . . . . . . . . . . . . . . . . . . 184
Diphenylaminine by Liquid Phase Condensation of Aniline Production Costs. . . . . . . . . . . . . . . . . . . . . . . 185
Xiii
