Phenol Supp B.

, December 1977

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.
 Phenol Supp B., December 1977

Report No. 22B

PHENOL
Supplement B

by YEN-CHEN YEN

December 1977

A private report by the

PROCESS ECONOMICS PROGRAM

I
STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA
I
 Phenol Supp B., December 1977

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 HYDROCARBONSProgram 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.
 Phenol Supp B., December 1977

0 CONTENTS

1 INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . 1

0 2 SUMMARY .......................... 3
General Aspects ...................... 3
Technical Aspects ..................... 9
l 3 INDUSTRY STATUS . . . . . . . . . . . . . . . . . . . . . . 13

4 CUMENE MANUFACTURE ..................... 21

Process Description .................... 24
Process Discussion ..................... 29
Cost Estimates ....................... 29

5 PHENOL BY CUMENE PROCESS . . . . . . . . . . . . . . . . . . 39

Chemistry ......................... 39
Review of Processes .................... 40
Oxidation of Cumene ................... 40
Cleavage ......................... 43
0 Distillation and Purification ..............
Hydrogenation of a-Methylstyrene to Cumene ........
43
43
Treatment of Heavy Ends ................. 48
Recovery and Removal of Phenol from Water to be
Discharged ....................... 48
Licensors ........................ 49
Process Description .................... 52
Process Discussion ..................... 66
Cost Estimates ....................... 68
An Alternative Design Using a Sulfonated Olefin
Polymer as a Cleavage Catalyst .............. 83
An Alternative Design Using Extraction for
Phenol Purification .................... 83

0 An Alternative Design with By-Production of

a-Methylstyrene ...................... 84
An Alternative Design with Recovery of Acetophenone
as a By-Product ...................... 87
An Alternative Design, Without Cracking .......... 88
0 An Alternative Design with p-Cumyl Phenol Recovery .....
Combination of Oxidation and Acid Cleavage .........
88
89

0
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 Phenol Supp B., December 1977

CONTENTS

PROCESSES SIMILAR TO THE CUMENE PROCESS . ......... 91

The Ethylbenzene Process for Making Phenol ......... 91

Review of Processes . . . . . . . . . . ......... 92
Process Description . . . . . . . . . . ......... 92
Process Discussion . . . . . . . . . . . ......... 104
Cost Estimates . . . . . . . . . . . . . ......... 104
Coproduction of Styrene, Propylene Oxide, Phenol,
and Acetaldehyde .................... 112
The Secondary Butylbenzene Process for Making Phenol .... 113
Alkylation of Benzene with Butene to Form
Secondary Butylbenzene ................. 113
Oxidation of Secondary Butylbenzene ........... 114
The Cleavage of Secondary Butylbenzene Hydroperoxide , . , 117
Process Description ................... 119
Process Discussion .................... 123
Cost Estimates ...................... 124
Integrated Production .................. 124
The Cyclohexylbenzene Process for Making Phenol ...... 143

PHENOL BY THE TOLUENE PROCESS ............... 147

Chemistry ......................... 147
Review of Processes .................... 148
Process Description .................... 151
Process Discussion ..................... 163
Cost Estimates ....................... 163
Thorough Recovery of Copper and Magnesium ......... 172

RASCHIG PROCESS, SULFONATION PROCESS, AND

CHLORINATIONPROCESS ................... 173
Raschig Process ...................... 173
Sulfonation Process .................... 178
Chlorination Process .................... 180

PHENOL BY DIRECT OXIDATION OF BENZENE ........... 183

Chemistry .............. . .......... 183
Review of Processes .................... 183
Economics of Processes Using Hydrogen Peroxide
Aqueous Solution ..................... 183
Economics of Processes Using Hydrogen Peroxide
Produced In Situ ..................... 186
Economics of Oxidation by Molecular Oxygen in
Liquid Phase ....................... 186
Vapor-Phase Direct Oxidation Process Based on a
Gulf Patent ........................ 187

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 Phenol Supp B., December 1977

CONTENTS

10 PHENOL BY PHENYL ACETATE PROCESS , ............. 193

Process Description .................... 193
Process Discussion ..................... 201
Cost Estimates ....................... 201

0 11 PHENOL BY DEALKYLATION OF CRESOLS

Chemistry .........................
............. 207

207
Process Description .................... 208
Process Discussion ..................... 215
Cost Estimates ....................... 215

12 OTHER PROCESSES ...................... 223

Cyclohexane Process .................... 223
Cyclohexane Dehydration Process .............. 223
Electrolytic Oxidation Processes .............. 224
Toluene Oxidation to Phenol by Titanium Dioxide and
Ultraviolet Light as Catalysts. .............. 225
Processes of Theoretical Interest Only ........... 225
l CITED REFERENCES ........................ 227

PATENT REFERENCES BY COMPANY .................. 241

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 Phenol Supp B., December 1977

ILLUSTRATIONS

4:1 Cumene Production

Flow sheet........................ 245

4.2 Cumene Production

Effect of Operating Level and Plant Capacity on
Production Cost . . . . . . . . . . . . . . . . . . . . . 37
5.1 Phenol by Cumene Process
Flow Sheet........................ 247
5.2 Phenol by Cumene Process
Effect of Operating Level and Plant Capacity on
Production Cost . . . . . . . . . . . . . . . . . . . . . 81
5.3 Phenol by Cumene Process, from Benzene and Propylene
Effect of Operating Level and Plant Capacity on
Production Cost . . . . . . . . . . . . . . . . . . . . . 82
5.4 Purification by Extraction, Phenol by Cumene Process
Flow Sheet........................ 251
5.5 cr-Methylstyrene Recovery, Phenol by Cumene Process
Flow Sheet........................ 86
5.6 Acetophenone Recovery, Phenol by Cumene Process
Flow Sheet........................ 253
5.7 para-Cumyl Phenol Recovery, Phenol by Cumene Process
Flow Sheet........................ 255
6.1 Phenol by Ethylbenzene Process
Flow Sheet........................ 257
6.2 Phenol by Ethylbenzene Process
Effect of Operating Level and Plant Capacity on
Production Cost . . . . . . . . . . . . . . . . . . . . . 111
6.3 sec-Butylbenzene from Benzene and Mixed Butenes
Flow Sheet........................ 261
6.4 Phenol by sec-Butylbenzene Process
Flow sheet........................ 263
7.1 Phenol by Toluene Process
Flow sheet........................ 265
7.2 Phenol by Toluene Process
Effect of Operating Level and Plant Capacity on
Production Cost . . . . . . . . . . . . . . . . . . . . . 171

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 Phenol Supp B., December 1977

ILLUSTRATIONS

7.3 Recovery of Copper and Magnesium, Phenol by

Toluene Process
Flow sheet........................ 269

10.1 Phenol by Phenyl Acetate Process

Flow Sheet........................ 271

11.1 Phenol by Dealkylation of Cresols

Flow sheet........................ 273
11.2 Phenol by Dealkylation of Cresols
Relationship Between Value of Phenol and
Value of Cresol . . . . . . . . . . . . . . . . . . . . . 222

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 i

Phenol Supp B., December 1977

TABLES

2.1 Comparison of Economics of Commercial Processes

for Making Phenol . . . . . . . . . . . . . . . . . . . . 6

2.2 Comparison of Economics of Noncommercial Processes

for Making Phenol . . . . . . . . . . . . . . . . , . . . 7

2.3 Economics of Cumene and Secondary Butylbenzene

Manufacture . . . . . . . . . . . . . . . . . . . . . . . 8

3.1 Synthetic Phenol Producers and Capacities . . . . . . . . 14

3.2 Cumene Producers and Capacities . . . . . . . . . . . . . 18

4.1 Cumene Preparation

Patent Summary. . . . . . . . . . . . . . . . . . . . . . 22

4.2 Cumene Production

Design Bases and Assumptions . . . . . , . . . . . . . . . 25

4.3 Cumene Production

Stream Flows . . . . . . . . . . . . . . . . . . . . . . . 26
4.4 Cumene Production
Major Equipment . . . . . . . . . . . . . . . . . . . . . 27

4.5 Cumene Production

Utilities Summary . . . . . . . . . . . . . . . . . . . , 28
4.6 Cumene Production
Capital Investment . . . . . . . . . . . . . . . . . . . . 32
4.7 Cumene Production
Production Costs . . . . . . . . . . . . . . . . . . . . . 34
5.1 Cumene Hydroperoxide Preparation
Patent Summary. . . . . . . . . . . . . . . . . . . . . . 41

5.2 Cleavage of Cumene Hydroperoxide

Patent Summary. . . . . . . . . . . . . . . . . . . . . . 44

5.3 Distillation of Cleavage Product

Patent Summary. . . . . . . . . . . . . . . . . . . . . . 45

5.4 Phenol Purification

Patent Summary. . . . . . . . . . . . . . . . . . . . . . 46

5.5 Hydrogenation of o-Methylstyrene to Cumene

Patent Summary. . . . . . . . . . . . . . . . . . . . . . 47
5.6 Treatment of Heavy Ends in Phenol Manufacture
by Cumene Process
Patent Summary . . . . . . . . . . . . . . . . . . . . . . 47

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 Phenol Supp B., December 1977

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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 Phenol Supp B., December 1977

TABLES

6.8 sec-Butylbenzene Manufacture

Patent Summary. . . . . . . . . . . . . . . . . . . . . . 115
0 6.9 Phenol from sec-Butylbenzene
Patent Summary. . . . . . . . . . . . . . . . . . . . . . 118

6.10 Phenol by sec-Butylbenzene Process

l 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

lo 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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 Phenol Supp B., December 1977

TABLES

8.1 Phenol by Oxychlorination and Hydrolysis (Raschig-Hooker)

Production Costs . . . . . . . . . . . . . . . . . . . . . 176
-
8.2 Phenol by Sulfonation Process
Production Costs . . . . . . . . . . . . . . . . . . . . . 179

l
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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 Phenol Supp B., December 1977

TABLES

11.1 Phenol by Dealkylation of Cresols

- 11.2
Design Bases and Assumptions . . . . . . . . . . . . . , .
Phenol by Dealkylation of Cresols
209

211
Stream Flows . . . . . . . . . . . . . . . . . . . . . , .

11.3 Phenol by Dealkylation of Cresols

a 11.4
Major Equipment . . . . . . . . . . . . . . . . . . . . .
Phenol by Dealkylation of Cresols
212

Utilities Summary . . . . . . . . . . . . . . . . . . . . 214

11.5 Phenol by Dealkylation of Cresols

Capital Investment . . . . . . . . . . . . . . . . . . . . 217

11.6 Phenol by Dealkylation of Cresols

Production Costs . . . . . . . . . . . . . . . . . . . , . 219

a-

a-
a

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