Phenol, April 1967
Report No. 22
PHENOL
by YEN-CHEN
YEN
April 1967
A private report by the
PROCESS
STANFORD
ECONOMICS
RESEARCH
INSTITUTE
PROGRAM
I
MENLO
I
PARK,
CALIFORNIA
Phenol, April 1967
CONTENTS
INTRODUCXION.
-
SUMMARY
1.
I
1
.........................
3
............................
3
8
General Aspects
........................
Technical Aspects
.......................
INDUSTRY STATUS
15
........................
8
CHEMISTRY
8-
8
8
8
1
8I
8
8
t-
8
...........................
23
..........
Manufacture of Phenol by the Cumene Process
Oxidation of Cumene to Hydroperoxide .............
Cleavage of Hydroperoxide
..................
Manufacture of Phenol by Raschig Process ............
Chlorination of Benzene by Hydrochloric Acid and Air .....
Hydrolysis of Chlorobenzene
.................
Manufacture of Phenol by Toluene Process ............
Oxidation of Toluene to Benzoic Acid .............
Conversion of Benzoic Acid to Phenol .............
Manufacture of Phenol from Benzene Through Cyclohexane
Oxidation ...........................
...........
Hydrogenation of Benzene to Cyclohexane
Oxidation of Cyclohexane to Cyclohexanol and Cyclohexanone . .
........
Dehydrogenation of Cyclohexanol/Cyclohexanone
.........
Manufacture of Phenol by Chlorination Process
Chlorination of Benzene
...................
Conversion of Chlorobenzene to Phenol
............
Manufacture of Phenol by Sulfonation Process ..........
Sulfonation
.........................
Conversion of Benzenesulfonic Acid to Phenol ..........
Manufacture of Phenol by Direct Oxidation of Benzene ......
Manufacture of Phenol by Other Processes ............
23
23
23
25
25
26
28
28
31
MANUFACTURE OF PHENOL BY CUMENE PROCESS
47
............
Review of Processes
......................
Oxidation of Cumene to Hydroperoxide .............
Temperature
........................
Pressure ..........................
OxygenorAir
.......................
Promoters
.........................
Phase
...........................
Reactors ..........................
iii
34
34
36
37
38
38
39
40
40
42
43
46
47
47
47
47
53
53
53
53
Phenol, April 1967
CONTENTS
5
6
7
(continued)
Concentration of Hydroperoxide ................
..................
Cleavage of Hydroperoxide
Neutralization of the Cleavage Product .............
...............
Distillation of Cleavage Products
.....................
Purification of Phenol
Treatment of the Residue ....................
......................
Process Description
.......................
Process Discussion
Cost Estimates .........................
54
54
55
55
57
58
59
74
76
PHENOLBY
87
RASCHIG PROCESS
. . . . . . . . . . . . .. . . . . . .
......................
Review of Processes
The Catalyst for Oxychlorination ...............
The Catalysts for Hydrolysis .................
.................
The Oxychlorination Reactor
....................
The Hydrolysis Reactor
The Recovery System .....................
......................
Process Description
ProcessDiscussion
.......................
Cost Estimates .........................
87
87
88
88
89
89
90
93
103
PHENOLBY
113
TOLUENE PROCESS
. . . . . . . . o . . . . . . . . . .
......................
Review of Processes
Oxidation of Toluene to Benzoic Acid ..............
Conversion of Benzoic Acid to Phenol ..............
A Process Based on Standard Oil and Montecatini Patents
.....................
Process Description
Process Discussion ......................
........................
Cost Estimate
A Process Based on Dow Patents .................
.....................
Process Description
Process Discussion ......................
........................
Cost Estimate
8
PHENOLBY
CYCIGHEXANE PROCESS
.................
......................
Review of Processes
...........
Hydrogenation of Benzene to Cyclohexane
...................
Oxidation of Cyclohexane
........
Dehydrogenation of Cyclohexanol/Cyclohexanone
iv
....
113
113
118
124
124
137
139
148
148
158
158
165
165
165
172
175
Phenol, April 1967
CONTENTS
8
9
10
(continued)
Process Description
......................
Process Discussion .......................
Cost Estimate
.........................
176
193
195
PHENOL BY CHLORINATION PROCESS .................
205
Review of Processes
.....................
Chlorination to ChlorLbenzeAe
...........................
Conversion of Chlorobenzene to Phinol'
Process Description
......................
Process Discussion .......................
Cost Estimate
.........................
205
205
206
207
222
223
PHENOL BY SULFONATION PROCESS
235
.................
Review of Processes
......................
Sulfonation
..........................
Conversion of Benzenesulfonate to Phenol ............
Process Description
......................
Process Discussion .......................
Cost Estimate
.........................
11
12
PHENOL FRC#l OXIDATION OF BENZENE BY MOLECULAR OXYGEN . 9
235
235
238
239
252
253
l
l
.
l
267
Review of Processes
. ...
....................
Phenol from Benzene--Ax;dit;on with IrradiatiAn'
267
272
OTBERPROCESSES
285
........................
Oxidation by a Peroxide, Peracid, or Hydroperoxide .......
Phenol from Acid Cleavage of Cyclohexylbenzenehydroperoxide
Hydrodealkylation of Cresol
..................
Oxidation by Cupric Sulfate and Water
.............
Pyrolysis of Ortho-Benzoic Acid ................
APPENDIX A
DESIGN AND COST BASIS
APPENDIX B
PHYSICALDATA
APPENDIX C
RAW MATERIALS AND PRODUCT SPECIFICATIONS
285
286
286
287
287
291
.................
.....................
V
, .
299
........
305
Phenol, April 1967
CONTENTS
CITEDREFERENCES ..........................
311
SUPPLEMENTALREFERENCES ......................
335
I
8
I
8
I
I
I
8
1
vi
8
I
Phenol, April 1967
ILLUSTRATIONS
5.1
Phenol by Cumene Process ..................
61
5.2
Relationship of Production Costs of Phenol and
Acetone by Cumene Process .................
83
Phenol by Cumene Process
Production Cost for Varying Annual Production
Acetone Credited at 4C/lb, Acetophenone Credited
at209,Qb
.........................
85
6.1
Phenol by Raschig Process
95
6.2
Phenol by Raschig Process
Production Cost for Varying Annual Production
5.3
.................
.......
111
Effect of Conversion on Process Unit Investment
and Production Cost ....................
112
7.1
Conversion and Selectivity of Phenol from Benzoic Acid . . ,
122
7.2
Phenol by Toluene Process Based on Standard Oil and
Montecatini Patents
....................
129
Phenol by Toluene Process Based on Standard Oil and
Montecatini Patents
Production Cost for Varying Annual Production
.......
147
7.4
Phenol by Toluene Process Based on Dow Patents .......
151
7.5
Phenol by Toluene Process Based on Dow Patents
Production Cost for Varying Annual Production
.......
164
8.1
Phenol by Cyclohexane Process
179
8.2
Phenol by Cyclohexane Process
Production Cost for Varying Annual Production
6.3
7.3
...............
9.1
Phenol by Chlorination Process ...............
9.2
Phenol by Chlorination Process
Production Cost for Varying Annual Production
.......
204
209
.......
232
Effect of Diphenyl Ether Production on Production
Cost of Phenol .......................
233
10.1
Phenol by Sulfonation Process
241
10.2
Relationship of Production Costs of Phenol and
Sodium Sulfite by the Sulfonation Process
(100 Million lb/gr Phenol) . . . . . . . . . . . . . . . . .
9.3
vii
...............
261
Phenol, April 1967
ILLUSTRATIONS
10.3
11.1
Phenol
by Sulfonation
Process
Production Cost for Varying Production . . . . . . . . . . .
263
Phenol by Direct Oxidation Process . . . . . . . . . . . . .
277
viii
8
I
8
8
I8
8
1
I
8
8
1
8
8
8
8
8
I
8
8
8
8
8
8
8
8
8
8
8
8
8
8
I
8
8
8
8
8
Phenol, April 1967
TABLES
2.1
2.2
Evaluation of Processes for Producing 100 Million
lb/yr of Phenol
. . . . . . . . . . . . . . . . . . . . . .
5
Summary of Technical Data of Processes for Manufacture
ofPhenol
. . . . . . . . . . . . . . . . . . . . . . . . .
9
3.1
Synthetic Phenol Plants in North and South America
3.2
Synthetic Phenol Plants in Europe
3.3
Synthetic Phenol Plants in Asia and Australia
. . . . . . .
20
5.1
Oxidation of Cumene to Hydroperoxide
Summary of Patents . . . . . . . . . . . . . . . . . . . . .
49
Phenol by Cumene Process
Major Process Equipment and Utilities Summary
. . . . . . .
60
Phenol by Cumene Process
Stream Flows . . . . . . . . . . . . . . . . . . . . . . . .
65
Phenol by Cumene Process
Process Unit and Utilities Investment
. . . . . . . . . . .
77
Phenol by Cumene Process
Total Capital Investment . . . . . . . . . . . . . . . . . .
79
Phenol by Cumene Process
Production Costs . . . . . . . . . . . . . . . . . . . . . .
81
Phenol by Raschig Process
Major Process Equipment and Utilities Summary
. . . . . . .
94
Phenol by Raschig Process
Stream Flows . . . . . . . . . . . . . . . . . . . . . . . .
99
5.2
5.3
5.4
5.5
5.6
6.1
6.2
6.3
6.4
6.5
7.1
7.2
. . . . .
18
. . . . . . . . . . . . .
19
Phenol by Raschig Process
Process Unit and Utilities Investment
. . . . . . . . . . .
105
Phenol by Raschig Process
Total Capital Investment . . . . . . . . . . . . . . . . . .
107
Phenol by Raschig Process
Production Costs . . . . . . . . . . . . . . . . . . . . . .
109
Oxidation of Toluene by Air
SummaryofPatents.....................
115
Conversion of Benzoic Acid to Phenol
Summary of Patents . . . . . . . . . . . . . . . . . . . . .
119
ix
Phenol, April 1967
TABLES
7.3
7.4
7.5
7.6
7.7
7.8
7.9
7.10
7.11
7.12
8.1
8.2
8.3
8.4
8.5
Phenol by Toluene Process Based on Standard Oil and
Montecatini Patents
Major Process Equipment and Utilities Summary
. . . , . , , .
128
Phenol by Toluene Process Based on Standard Oil and
Montecatini Patents
Stream Flows . . . . . . . . . . . . . . . . . . . . . . . . .
133
Phenol by Toluene Process Based on Standard Oil and
Montecatini Patents
Process Unit and Utilities Investment
. . . . . . . . . . . .
141
Phenol by Toluene Process Based on Standard Oil and
Montecatini Patents
Total Capital Investment . . . . . . . . . . . . . . . . . . .
143
Phenol by Toluene Process Based on Standard Oil and
Montecatini Patents
Production Costs . . . . . . . . . . . . . . . . . . . . . . .
145
Phenol by Toluene Process Based on Dow Patents
Major Process and Utilities Summary . . , . . . . . . . . . .
149
Phenol by Toluene Process Based on Dow Patents
Stream Flows . . . . . . . . . . . . . . . . . . . . . . . . .
153
Phenol by Toluene Process Based on Dow Patents
Process Unit and Utilities Investment
. . . . . . . . . . . .
159
Phenol by Toluene Process Based on Dow Patents
Total Capital Investment . . . . . . . . . . . . . . . . . . .
160
Phenol by Toluene Process Based on Dow Patents
Production Costs . . . . . . . . . . . . . . . . . . . . . . .
161
Phenol by Cyclohexane Process
Summary of Patents on Hydrogenation of Benzene . . . . . . . .
167
Phenol by Cyclohexane Process
Summary of Recent Patents on Oxidation of Cyclohexane
. . . .
173
. . . . . . . .
177
Phenol by Cyclohexane Process
Composition of Stream Flows
. . . . . . . . . . . . . . . . .
185
Phenol by Cyclohexane Process
Process Unit and Utilities Investment
197
Phenol by Cyclohexane Process
Major Process Equipment and Utilities Summary
X
. . . . . . . . . . . .
8
1
8
8
8
4
8
I
8
8
8
8
8
8
8
1
8
8
8
Phenol, April 1967
TABLES
8.6
8.7
9.1
9.2
9.3
9.4
9.5
10.1
10.2
10.3
10.4
10.5
11.1
11.2
11.3
Phenol by Cyclohexane Process
Total Capital Investment . . . . . . . . . . . . . . . . . . .
199
Phenol by Cyclohexane Process
Production Costs . . . . . . . . . . . . . . . . . . . . . . .
201
Phenol by Chlorination Process
Major Process Equipment and Utilities Summary
. . . . . , . .
208
Phenol by Chlorination Process
Stream Flows . . . . . . . . . . . . . . . . . . . . . . . . .
213
Phenol by Chlorination Process
Process Unit and Utilities Investment
. . . . . . . . . . . .
225
Phenol by Chlorination Process
Total Capital Investment . . . . . . . . . . . . . . . . . . .
227
Phenol by Chlorination Process
Production Costs . . . . . . . . . . . . . . . . . . . . . . .
229
Phenol by Sulfonation Process
Major Process Equipment and Utilities Summary
. . . . . . . .
240
Phenol by Sulfonation Process
Stream Flows . . . . . . . . . . . . . . . . . . . . . . . . .
245
Phenol by Sulfonation Process
Process Unit and Utilities Investment
. . . . . . . . . . . .
255
Phenol by Sulfonation Process
Total Capital Investment . . . . . . . . . . . . . . . . . . .
257
Phenol by Sulfonation Process
Production Costs . . . . . . . . . . . . . . . . . . . . . . .
259
Direct Oxidation of Benzene by Molecular Oxygen
Summary of Patents . . . . . . . . . . . . . . . . . . . . . .
269
Phenol by Direct Oxidation Process
Major Process Equipment and Utilities
. . . . . . . .
275
. . . . . . . . . . . . . . . . .
279
Phenol by Irradiated Direct Oxidation Process
Total Capital Investment
. . . . . . . . . . . . . . . . . . .
282
Phenol by Direct Oxidation Process
Composition
11.4
11.5
Summary
Phenol
of Flow
by Irradiated
Streams
Oxidation
Process
Production Costs . . . . . . . . . . . . . . . . . . . . . . .
xi
283