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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.
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

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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 . . . . . . . . . . . . .

.........

.........

.........

.........

.........

......... 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

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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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4.2

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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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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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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