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TRANSCRIPT
STANFORD RESEARCH INSTITUTE l Menlo Park, California 94025
Abstract
Process Economics Program Report No. 22B
PHENOL
Among all the processes for making phenol, the cumene process is
the most economical. The by-production of acetone, unique to this
process for phenol, is not a serious constraint, at least in the United
States. If by-production of acetone has to be avoided, the best choices
are the toluene process and the oxychlorination process, with the former
having an economic advantage at present relative prices of toluene and
benzene. The economics of the sulfonation process depends heavily on
the market for a by-product useful only to pulp mills. The chlorination
process has a high production cost, and the by-products are not common
commodities.
Other processes (direct oxidation, phenyl acetate, and dealkylation)
were also evaluated. None of them has prospects of becoming commercial
with current technology.
Report No. 22B
PHENOL
Supplement B
by YEN-CHEN YEN
December 1977
A private report by the
PROCESS ECONOMICS PROGRAM
I STANFORD RESEARCH INSTITUTE
I MENLO PARK, CALIFORNIA
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 HYDROCARBONS Program covers major
hydrocarbons and their derivatives on a worldwide Basis. In
addition, the SRI DIRECTORY OF CHEMICAL PRODUCERS services
provide detailed lists of chemical producers by company,
product, and plant for the United States and Western Europe.
CONTENTS 0
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1 INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . 1
2 SUMMARY .......................... 3
General Aspects ...................... 3 Technical Aspects ..................... 9
3 INDUSTRY STATUS . . . . . . . . . . . . . . . . . . . . . . 13
4 CUMENE MANUFACTURE ..................... 21
Process Description .................... 24 Process Discussion ..................... 29 Cost Estimates ....................... 29
5 PHENOL BY CUMENE PROCESS . . . . . . . . . . . . . . . . . . 39
Chemistry ......................... Review of Processes ....................
Oxidation of Cumene ................... Cleavage ......................... Distillation and Purification .............. Hydrogenation of a-Methylstyrene to Cumene ........ Treatment of Heavy Ends ................. Recovery and Removal of Phenol from Water to be Discharged ....................... Licensors ........................
Process Description .................... Process Discussion ..................... Cost Estimates ....................... An Alternative Design Using a Sulfonated Olefin Polymer as a Cleavage Catalyst ..............
An Alternative Design Using Extraction for Phenol Purification ....................
An Alternative Design with By-Production of a-Methylstyrene ......................
An Alternative Design with Recovery of Acetophenone as a By-Product ......................
An Alternative Design, Without Cracking .......... An Alternative Design with p-Cumyl Phenol Recovery ..... Combination of Oxidation and Acid Cleavage .........
39 40 40 43 43 43 48
48 49 52 66 68
83
83
84
87 88 88 89
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CONTENTS
PROCESSES SIMILAR TO THE CUMENE PROCESS .
The Ethylbenzene Process for Making Phenol Review of Processes . . . . . . . . . . Process Description . . . . . . . . . . Process Discussion . . . . . . . . . . . Cost Estimates . . . . . . . . . . . . .
.........
.........
.........
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......... Coproduction of Styrene, Propylene Oxide, Phenol, and Acetaldehyde ....................
The Secondary Butylbenzene Process for Making Phenol .... Alkylation of Benzene with Butene to Form Secondary Butylbenzene .................
Oxidation of Secondary Butylbenzene ...........
The Cleavage of Secondary Butylbenzene Hydroperoxide , . , Process Description ...................
Process Discussion .................... Cost Estimates ...................... Integrated Production ..................
The Cyclohexylbenzene Process for Making Phenol ......
PHENOL BY THE TOLUENE PROCESS ...............
Chemistry ......................... Review of Processes .................... Process Description .................... Process Discussion ..................... Cost Estimates ....................... Thorough Recovery of Copper and Magnesium .........
RASCHIG PROCESS, SULFONATION PROCESS, AND CHLORINATIONPROCESS ...................
Raschig Process ...................... Sulfonation Process .................... Chlorination Process ....................
PHENOL BY DIRECT OXIDATION OF BENZENE ...........
Chemistry .............. . .......... Review of Processes .................... Economics of Processes Using Hydrogen Peroxide
Aqueous Solution ..................... Economics of Processes Using Hydrogen Peroxide Produced In Situ .....................
Economics of Oxidation by Molecular Oxygen in Liquid Phase .......................
Vapor-Phase Direct Oxidation Process Based on a Gulf Patent ........................
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91 92 92
104 104
112 113
113 114 117 119
123 124
124 143
147
147 148 151 163 163 172
173
173 178 180
183 183 183
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PHENOL BY PHENYL ACETATE PROCESS , ............. 193
Process Description .................... 193 Process Discussion ..................... 201 Cost Estimates ....................... 201
PHENOL BY DEALKYLATION OF CRESOLS ............. 207
Chemistry ......................... 207 Process Description .................... 208 Process Discussion ..................... 215 Cost Estimates ....................... 215
OTHER PROCESSES ......................
Cyclohexane Process .................... Cyclohexane Dehydration Process .............. Electrolytic Oxidation Processes .............. Toluene Oxidation to Phenol by Titanium Dioxide and Ultraviolet Light as Catalysts. .............. Processes of Theoretical Interest Only ...........
223
223 223 224
225 225
CITED REFERENCES ........................ 227
PATENT REFERENCES BY COMPANY .................. 241
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4:1
4.2
5.1
5.2
5.3
5.4
5.5
5.6
5.7
6.1
6.2
6.3
6.4
7.1
7.2
ILLUSTRATIONS
Cumene Production Flow sheet........................ 245
Cumene Production Effect of Operating Level and Plant Capacity on Production Cost . . . . . . . . . . . . . . . . . . . . . 37
Phenol by Cumene Process Flow Sheet........................ 247
Phenol by Cumene Process Effect of Operating Level and Plant Capacity on Production Cost . . . . . . . . . . . . . . . . . . . . . 81
Phenol by Cumene Process, from Benzene and Propylene Effect of Operating Level and Plant Capacity on Production Cost . . . . . . . . . . . . . . . . . . . . . 82
Purification by Extraction, Phenol by Cumene Process Flow Sheet........................ 251
cr-Methylstyrene Recovery, Phenol by Cumene Process
Flow Sheet........................ 86
Acetophenone Recovery, Phenol by Cumene Process Flow Sheet........................ 253
para-Cumyl Phenol Recovery, Phenol by Cumene Process
Flow Sheet........................ 255
Phenol by Ethylbenzene Process Flow Sheet........................ 257
Phenol by Ethylbenzene Process Effect of Operating Level and Plant Capacity on Production Cost . . . . . . . . . . . . . . . . . . . . . 111
sec-Butylbenzene from Benzene and Mixed Butenes Flow Sheet........................ 261
Phenol by sec-Butylbenzene Process Flow sheet........................ 263
Phenol by Toluene Process Flow sheet........................ 265
Phenol by Toluene Process Effect of Operating Level and Plant Capacity on Production Cost . . . . . . . . . . . . . . . . . . . . . 171
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ILLUSTRATIONS
7.3
10.1
11.1
11.2
Recovery of Copper and Magnesium, Phenol by Toluene Process
Flow sheet........................ 269
Phenol by Phenyl Acetate Process
Flow Sheet........................ 271
Phenol by Dealkylation of Cresols Flow sheet........................ 273
Phenol by Dealkylation of Cresols Relationship Between Value of Phenol and Value of Cresol . . . . . . . . . . . . . . . . . . . . . 222
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TABLES
2.1 Comparison of Economics of Commercial Processes for Making Phenol . . . . . . . . . . . . . . . . . . . .
2.2 Comparison of Economics of Noncommercial Processes for Making Phenol . . . . . . . . . . . . . . . . , . . .
2.3 Economics of Cumene and Secondary Butylbenzene Manufacture . . . . . . . . . . . . . . . . . . . . . . .
3.1 Synthetic Phenol Producers and Capacities . . . . . . . .
3.2 Cumene Producers and Capacities . . . . . . . . . . . . .
4.1 Cumene Preparation Patent Summary. . . . . . . . . . . . . . . . . . . . . .
4.2 Cumene Production Design Bases and Assumptions . . . . . , . . . . . . . . .
4.3 Cumene Production Stream Flows . . . . . . . . . . . . . . . . . . . . . . .
4.4 Cumene Production Major Equipment . . . . . . . . . . . . . . . . . . . . .
4.5 Cumene Production Utilities Summary . . . . . . . . . . . . . . . . . . . ,
4.6 Cumene Production Capital Investment . . . . . . . . . . . . . . . . . . . .
4.7 Cumene Production Production Costs . . . . . . . . . . . . . . . . . . . . .
5.1 Cumene Hydroperoxide Preparation Patent Summary. . . . . . . . . . . . . . . . . . . . . .
5.2 Cleavage of Cumene Hydroperoxide Patent Summary. . . . . . . . . . . . . . . . . . . . . .
5.3 Distillation of Cleavage Product Patent Summary. . . . . . . . . . . . . . . . . . . . . .
5.4 Phenol Purification Patent Summary. . . . . . . . . . . . . . . . . . . . . .
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5.5 Hydrogenation of o-Methylstyrene to Cumene Patent Summary. . . . . . . . . . . . . . . . . . . . . .
5.6 Treatment of Heavy Ends in Phenol Manufacture by Cumene Process Patent Summary . . . . . . . . . . . . . . . . . . . . . .
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TABLES
5.7 Treatment of Waste Water from Cumene Process for Making Phenol, and Similar Effluents
Patent Summary. . . . . . . . . . . . . . . . . . . . . . 50
5.8 Phenol by Cumene Process Design Bases and Assumptions . . . . . . . . . . . . . . . 52
5.9 Phenol by Cumene Process
Stream Flows . . . . . . . . . . . . . . . . . . . . . . . 57
5.10 Phenol by Cumene Process Major Equipment . . . . . . . . . . . . . . . . . . . . . 60
5.11 Phenol by Cumene Process Utilities Summary . . . . . . . . . . . . . . . . . . . . 65
5.12 Phenol by Cumene Process Capital Investment . . . . . . . . . . . . . . . . . . . . 70
5.13 Phenol by Cumene Process Production Costs . . . . . . . . . . . . . . . . . . . . . 72
5.14 Comparison of Estimates on Cumene Process . . . , . . . . 75
5.15 Phenol by Cumene Process, from Benzene and Propylene
Capital Investment . . . . . . . . . . . . . . . . . . . . 76
5.16 Phenol by Cumene Process, from Benzene and Propylene Production Costs . . . . . . . . . . . . . . .' . . . . . . 78
5.17 Comparison of Various Alternative Designs of Cumene Process . . . . . . . . . . . . . . . . . . . . . 85
6.1 Phenol from Ethylbenzene Hydroperoxide Patent Summary. . . . . . . . . . . . . . . . . . . . . . 93
6.2 Phenol by Ethylbenzene Process Design Bases and Assumptions . . . . . . . . . . . . . . . 94
6.3 Phenol by Ethylbenzene Process Stream Flows . . . . . . . . . . . . . . . . . . . . . . . 97
6.4 Phenol by Ethylbenzene Process Major Equipment . . . . . . . . . . . . . . . . . . . . . 99
6.5 Phenol by Ethylbenzene Process Utilities Summary . . . . . . . . . . . . . . . . . . . . 103
6.6 Phenol by Ethylbenzene Process Capital Investment . . . . . . . . . . . . . . . . . . . . 106
6.7 Phenol by Ethylbenzene Process Production Costs . . . . . . . . . . . . . . . . . l l l l 108
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TABLES
6.8 sec-Butylbenzene Manufacture Patent Summary. . . . . . . . . . . . . . . . . . . . . . 115
6.9 Phenol from sec-Butylbenzene Patent Summary. . . . . . . . . . . . . . . . . . . . . . 118
6.10 Phenol by sec-Butylbenzene Process Design Bases and Assumptions . . . . . . . . . . . . . . . 120
6.11 sec-Butylbenzene from Benzene and Mixed Butenes Capital Investment . . . . . . . . . . . . . . . . . . . . 126
6.12 sec-Butylbenzene from Benzene and Mixed Butenes Production Costs . . . . . . . . . . . . . . . . . . . . . 128
6.13 Phenol by sec-Butylbenzene Process Capital Investment . . . . . . . . . . . . . . . . . . . . 132
6.14 Phenol by sec-Butylbenzene Process Production Costs . . . . . . . . . . . . . . . . . . . . . 134
6.15 Phenol by sec-Butylbenzene Process, from Butenes Capital Investment . . . . . . . . . . . . . . . . . . . . 138
6.16 Phenol by sec-Butylbenzene Process, from Butenes Production Costs . . . . . . . . . . . , , . . . . . . . . 140
6.17 Phenol from Cyclohexylbenzene Patent Summary. . . . . . . . . . . . . . . . . . . . . . 144
7.1 Benzoic Acid from Toluene Oxidation Patent Summary. . . . . . . . . . . . . . . . . . . , . . 149
7.2 Phenol from Benzoic Acid Oxidation-Decarboxylation Patent Summary. . . . . . . . . . . . . , . . . . . . . . 150
7.3 Phenol by Toluene Process Design Bases and Assumptions . . . . . . . . . . . . . . . 152
7.4 Phenol by Toluene Process Stream Flows . . . . . . . . . . . . . . . . . . . . . . . 156
7.5 Phenol by Toluene Process Major Equipment . . . . . . . . . . . . . . . . . . . . . 159
7.6 Phenol by Toluene Process Utilities Summary . . . . . . . . . . . . . . . . . . . . 162
7.7 Phenol by Toluene Process Capital Investment . . . . . . . . . . . . . . . . . . . . 166
7.8 Phenol by Toluene Process Production Costs . . . . . . . . . . . . . . . . . . . . . 168
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TABLES
8.1 Phenol by Oxychlorination and Hydrolysis (Raschig-Hooker) Production Costs . . . . . . . . . . . . . . . . . . . . . 176
8.2 Phenol by Sulfonation Process Production Costs . . . . . . . . . . . . . . . . . . . . . 179
8.3 Phenol by Chlorination Process
Production Costs . . . . . . . . . . . . . . . . . . . . . 181
9.1 Phenol from Benzene by Direct Oxidation with Molecular Oxygen in Vapor Phase
Patent Summary. . . . . . . . . . . . . . . . . . . . . . 184
9.2 Phenol from Benzene by Direct Oxidation with Molecular Oxygen in Liquid Phase Patent Summary . . . . . . . . . . . . . . . . . . . . . . . 185
9.3 Phenol from Benzene by Oxidation with Aqueous Hydrogen Peroxide Patent Summary. . . . . . . . . . . . . . . . . . . . . . 185
9.4 Phenol from Benzene by Direct Oxidation Based on a Shell Patent
Production Costs . . . . . . . . . . . . . . . . . . . . . 188
9.5 Phenol from Benzene by Direct Oxidation (Vapor Phase) Production Costs . . . . . . . . . . . . . . . . . . . . . 190
10.1 Phenyl Acetate from Benzene, and its Conversion to Phenol
Patent Summary. . . . . . . . . . . . , . . . . . . . . . 195
10.2 Phenol by Phenyl Acetate Process Design Bases and Assumptions . . . . . . . . . . . . . , . 196
10.3 Phenol by Phenyl Acetate Process Stream Flows . . . . . . . . . . . . . . . . . . . . . . . 197
10.4 Phenol by Phenyl Acetate Process Major Equipment . . . . . . . . . . . . . . . . . . . . . 198
10.5 Phenol by Phenyl Acetate Process Utilities Summary . . . . . . . . . . . . . . . . . . . . 200
10.6 Phenol by Phenyl Acetate Process Total Capital Investment . . . . . . . . . . . . . . . . . 202
10.7 Phenol by Phenyl Acetate Process Production Costs . . . . . . . . . . , . . . . . . . . . . 204
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TABLES
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11.1 Phenol by Dealkylation of Cresols Design Bases and Assumptions . . . . . . . . . . . . . , . 209
11.2 Phenol by Dealkylation of Cresols Stream Flows . . . . . . . . . . . . . . . . . . . . . , . 211
11.3 Phenol by Dealkylation of Cresols Major Equipment . . . . . . . . . . . . . . . . . . . . . 212
11.4 Phenol by Dealkylation of Cresols Utilities Summary . . . . . . . . . . . . . . . . . . . . 214
11.5 Phenol by Dealkylation of Cresols Capital Investment . . . . . . . . . . . . . . . . . . . . 217
11.6 Phenol by Dealkylation of Cresols Production Costs . . . . . . . . . . . . . . . . . . . , . 219
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