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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.

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. Phenol Supp B. CALIFORNIA I .

the reader is referred to one of the SRI programs specializing in marketing research. In addition. . and plant for the United States and Western Europe. the SRI DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company.. 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. product. December 1977 For detailed marketing data and information. Phenol Supp B.

..... Hydrogenation of a-Methylstyrene to Cumene . 84 An Alternative Design with Recovery of Acetophenone as a By-Product ........ . 3 General Aspects ............ .... ........ ............ ...... ....... ..... ................. .......... ....... ..... ........................ ... 21 Process Description ..... 83 0 An Alternative Design with By-Production of a-Methylstyrene . . 66 Cost Estimates .... 39 Chemistry ............... 40 Oxidation of Cumene ...... ..... ... ....... .... . .... 1 0 2 SUMMARY ... .. Combination of Oxidation and Acid Cleavage .. 43 43 Treatment of Heavy Ends ..... . ... .......... 43 0 Distillation and Purification ... .. . .. 49 Process Description ....................... . . December 1977 0 CONTENTS 1 INTRODUCTION . . 39 Review of Processes ... 87 An Alternative Design.. . .... ....... Phenol Supp B....... 88 89 0 Vii ... .. . ............. . ......... ...... ....... 13 4 CUMENE MANUFACTURE .... 83 An Alternative Design Using Extraction for Phenol Purification .... 9 l 3 INDUSTRY STATUS .. 3 Technical Aspects .. ............ . 68 An Alternative Design Using a Sulfonated Olefin Polymer as a Cleavage Catalyst ...... ..................................... ........ Without Cracking .... 48 Licensors ...... ...... 29 Cost Estimates ............. . .................... ... .... ... ... ............ 24 Process Discussion .... ....... ...... .. ........ . .... 88 0 An Alternative Design with p-Cumyl Phenol Recovery ........ 48 Recovery and Removal of Phenol from Water to be Discharged .. 29 5 PHENOL BY CUMENE PROCESS ... ........ .................. 40 Cleavage ..... 52 Process Discussion ..... .............

.. .... 92 Process Discussion ... ........... ..... ... SULFONATION PROCESS.. 183 Economics of Processes Using Hydrogen Peroxide Produced In Situ ........... 178 Chlorination Process ............................................ 91 Review of Processes .. 173 Raschig Process ................... ... .. Propylene Oxide............... 151 Process Discussion ........ ......... 173 Sulfonation Process ... 119 Process Discussion .... . .. December 1977 CONTENTS PROCESSES SIMILAR TO THE CUMENE PROCESS ..... 163 Thorough Recovery of Copper and Magnesium .................. . 186 Economics of Oxidation by Molecular Oxygen in Liquid Phase ... ............... 104 Coproduction of Styrene........ ........ 91 The Ethylbenzene Process for Making Phenol .. and Acetaldehyde .............. .. 148 Process Description ............ 92 Process Description ........... 124 The Cyclohexylbenzene Process for Making Phenol . . .. 113 Alkylation of Benzene with Butene to Form Secondary Butylbenzene . AND CHLORINATIONPROCESS ............. . ............ ...... 183 Economics of Processes Using Hydrogen Peroxide Aqueous Solution ... .... ....... Phenol Supp B........ ... ...................................... .. .. .... ...... 114 The Cleavage of Secondary Butylbenzene Hydroperoxide ...... 147 Review of Processes .... ....... 163 Cost Estimates .... ...... 123 Cost Estimates ..... 113 Oxidation of Secondary Butylbenzene ...... 124 Integrated Production ..... .......... ..... .. ...... 143 PHENOL BY THE TOLUENE PROCESS ... ... 112 The Secondary Butylbenzene Process for Making Phenol ............. 172 RASCHIG PROCESS.......... ........ 147 Chemistry ....... ................. .... ... ............................. 104 Cost Estimates ....... 187 viii .. .. . . .. . 183 Review of Processes ..... ......... 117 Process Description . ...... 183 Chemistry ...... ..... ......... 186 Vapor-Phase Direct Oxidation Process Based on a Gulf Patent . 180 PHENOL BY DIRECT OXIDATION OF BENZENE .. ........ ....... Phenol..

...... 215 12 OTHER PROCESSES ... Phenol Supp B... ....... 215 Cost Estimates ........ 223 Cyclohexane Dehydration Process ..... .... 225 Processes of Theoretical Interest Only ................... 223 Cyclohexane Process .......................... 201 Cost Estimates ..................................... 193 Process Description ... 223 Electrolytic Oxidation Processes ..... 241 ix ........... 207 207 Process Description ................................................ 225 l CITED REFERENCES ........... ............ 201 0 11 PHENOL BY DEALKYLATION OF CRESOLS Chemistry . 224 Toluene Oxidation to Phenol by Titanium Dioxide and Ultraviolet Light as Catalysts........................................ December 1977 CONTENTS 10 PHENOL BY PHENYL ACETATE PROCESS . 227 PATENT REFERENCES BY COMPANY ................................................................ 208 Process Discussion ... 193 Process Discussion ....

Phenol by Cumene Process Flow Sheet.2 Cumene Production Effect of Operating Level and Plant Capacity on Production Cost .......3 Phenol by Cumene Process.. ..... 263 7...1 Phenol by Cumene Process Flow Sheet....... ..... from Benzene and Propylene Effect of Operating Level and Plant Capacity on Production Cost .... .. . ..4 Phenol by sec-Butylbenzene Process Flow sheet. 86 5. .... 111 6....... .. Phenol Supp B.. ...2 Phenol by Toluene Process Effect of Operating Level and Plant Capacity on Production Cost .... .. .. .. ....... .. . .. .. .. ... ..... . .... ... . .. ..1 Phenol by Ethylbenzene Process Flow Sheet. 255 6.. 81 5. . Phenol by Cumene Process Flow Sheet.......... ... . .. . ... .. . .. .3 sec-Butylbenzene from Benzene and Mixed Butenes Flow Sheet....1 Phenol by Toluene Process Flow sheet... .... .. 247 5...... . ... . ........ ..... . .... .. ........... .. ... .. .. ..... ......... .. 82 5.. ..... 261 6. .... . . .. . .... ... . 171 xi .... . ..2 Phenol by Ethylbenzene Process Effect of Operating Level and Plant Capacity on Production Cost . ..... . ... ... ....7 para-Cumyl Phenol Recovery. 245 4. ....2 Phenol by Cumene Process Effect of Operating Level and Plant Capacity on Production Cost . .. . .. 251 5...... 257 6... . 265 7..... .. Phenol by Cumene Process Flow Sheet.. . .... . . ... . ..... . ... . . Phenol by Cumene Process Flow Sheet.... .. ..... 37 5.. .. .6 Acetophenone Recovery.5 cr-Methylstyrene Recovery. .... December 1977 ILLUSTRATIONS 4:1 Cumene Production Flow sheet... . .... .4 Purification by Extraction...... 253 5. .. . .. . . ...

. .. Phenol Supp B.3 Recovery of Copper and Magnesium. ..... . . ......... 273 11....... ... ... .......1 Phenol by Phenyl Acetate Process Flow Sheet.. .2 Phenol by Dealkylation of Cresols Relationship Between Value of Phenol and Value of Cresol . December 1977 ILLUSTRATIONS 7... .1 Phenol by Dealkylation of Cresols Flow sheet.. .... 271 11... 269 10.. Phenol by Toluene Process Flow sheet. ....... .... .. .. 222 xii .......... . ..... .... .. ...

. . 7 2. . .. . . . . . . . . . . . . 47 5. . . . 46 5. . . . . . . . . . . . . .6 Cumene Production Capital Investment . . 27 4. . . . . . . . . . . . . . . . . . . . . . . . . . . . .4 Cumene Production Major Equipment . . . . . . . . . . . . . . .6 Treatment of Heavy Ends in Phenol Manufacture by Cumene Process Patent Summary . . . . . . . . . . . . 41 5. . . . 18 4. . .2 Cleavage of Cumene Hydroperoxide Patent Summary. .3 Distillation of Cleavage Product Patent Summary. . . . . . . 8 3. . . .2 Comparison of Economics of Noncommercial Processes for Making Phenol . . . . . . .1 Comparison of Economics of Commercial Processes for Making Phenol .2 Cumene Production Design Bases and Assumptions . . . . . . . . . . . 6 2. . . . i Phenol Supp B. . . . . . . 28 4. 44 5. . . . . . . . 47 xiii . . . . . . . . . . . . . . .5 Hydrogenation of o-Methylstyrene to Cumene Patent Summary. . . . . . .7 Cumene Production Production Costs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45 5. . . . . 32 4.1 Cumene Preparation Patent Summary.1 Cumene Hydroperoxide Preparation Patent Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25 4. . . . . . . . . . . . . . . . . . . . . . . 26 4. . . . . . . . . . .4 Phenol Purification Patent Summary. . . 22 4.1 Synthetic Phenol Producers and Capacities . . . . . . . . 14 3. . . . 34 5. . . . . . . . . . . .3 Economics of Cumene and Secondary Butylbenzene Manufacture . . . . . . . . . . . . . .5 Cumene Production Utilities Summary . . . . . .2 Cumene Producers and Capacities . . . . . . . December 1977 TABLES 2. . . . . . . . . .3 Cumene Production Stream Flows . . . . . . . . . . . . . . .

. . . . . . . . . . . . .4 Phenol by Ethylbenzene Process Major Equipment . . . . . . . . . . . . . . . . . . . . . . . . 75 5. . . . . .12 Phenol by Cumene Process Capital Investment . . . . . . . .14 Comparison of Estimates on Cumene Process . 85 6. . . . . . . . . .8 Phenol by Cumene Process Design Bases and Assumptions . . . . .10 Phenol by Cumene Process Major Equipment . . . . 97 6. Phenol Supp B. . . . . . . . . . . . . . . . from Benzene and Propylene Capital Investment . . . . . . . 103 6. . . . . . . 65 5. . . . . . . . .7 Phenol by Ethylbenzene Process Production Costs . . . . 52 5. . . . . l l l l 108 xiv . . . . . . .9 Phenol by Cumene Process Stream Flows . . . . . . . . . 94 6.17 Comparison of Various Alternative Designs of Cumene Process . . . . . . . . . . . . . 76 5. .3 Phenol by Ethylbenzene Process Stream Flows . . . . . . . . . . . . . . 78 5. . . . . . . .2 Phenol by Ethylbenzene Process Design Bases and Assumptions . . . . . . . . . . . . 93 6. . . . .1 Phenol from Ethylbenzene Hydroperoxide Patent Summary. . .15 Phenol by Cumene Process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106 6. . . . . . . . . December 1977 TABLES 5. . . . . . . . . .6 Phenol by Ethylbenzene Process Capital Investment . . . . . . . . . . . . .. . . . . . . . .7 Treatment of Waste Water from Cumene Process for Making Phenol. . . 57 5. . . . . . . . . .' . . . . . . . . . . from Benzene and Propylene Production Costs . . . . and Similar Effluents Patent Summary. . . . . . . . . 60 5. . .11 Phenol by Cumene Process Utilities Summary . .13 Phenol by Cumene Process Production Costs . . . . . . .5 Phenol by Ethylbenzene Process Utilities Summary . 72 5. . . . . . . . . . . . . . . . . 99 6. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .16 Phenol by Cumene Process. 70 5. . . . . . . . . 50 5. . .

. . . . . . . . . . . . . . . . . . . . 118 6. .8 Phenol by Toluene Process Production Costs . . .6 Phenol by Toluene Process Utilities Summary . . . . . . . . . . . . . 162 7. . . . . . . . . . . . . 152 lo 7. . . . . . . . . . . . . . . 126 6. from Butenes Production Costs . . . . . . . . . . .7 Phenol by Toluene Process Capital Investment . . . . . . . . . . . . . .8 sec-Butylbenzene Manufacture Patent Summary. . 168 xv . . . . . . . . . . . . . . . . 128 6. . . . . . 134 6. . . . . . . .1 Benzoic Acid from Toluene Oxidation Patent Summary. .11 sec-Butylbenzene from Benzene and Mixed Butenes Capital Investment . . . . . . . . . . . . . . . . 156 7. . . . . . . . 138 6. .10 Phenol by sec-Butylbenzene Process l Design Bases and Assumptions . . . 144 7. . . . . . . . . . . . . . . . . . . . . . . . . . . 159 7. . . . . . . 150 7. . . . . . . . . . . . . . . . . . . . . . . . 149 7. . . . . . . . . . . . . . . . . . . . . . . . . . .4 Phenol by Toluene Process Stream Flows . . . . . . .17 Phenol from Cyclohexylbenzene Patent Summary. . .15 Phenol by sec-Butylbenzene Process.16 Phenol by sec-Butylbenzene Process. . .14 Phenol by sec-Butylbenzene Process Production Costs . . from Butenes Capital Investment . . . .. . . . . . . . . . . 140 6. . . . . . . . . . . . . . . 166 7. . . . . . . . . . . . . . .5 Phenol by Toluene Process Major Equipment . . . . . . . . . . .9 Phenol from sec-Butylbenzene Patent Summary. . . . . . . .2 Phenol from Benzoic Acid Oxidation-Decarboxylation Patent Summary. . . 132 6. . . . . .13 Phenol by sec-Butylbenzene Process Capital Investment . . . Phenol Supp B. . . . . . . . . . . . . December 1977 TABLES 6. . . . . . . . . . . . .12 sec-Butylbenzene from Benzene and Mixed Butenes Production Costs . . . . . . 115 0 6. . . . . . . . . .3 Phenol by Toluene Process Design Bases and Assumptions . . . . . 120 6. . . . . . . . . . . .

. . . . . . . . . . . . . . . . .2 Phenol from Benzene by Direct Oxidation with Molecular Oxygen in Liquid Phase Patent Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3 Phenol from Benzene by Oxidation with Aqueous Hydrogen Peroxide Patent Summary.6 Phenol by Phenyl Acetate Process Total Capital Investment . . . . . . . . . . . . . . . .1 Phenyl Acetate from Benzene. . . . . . . December 1977 TABLES 8.1 Phenol from Benzene by Direct Oxidation with Molecular Oxygen in Vapor Phase Patent Summary. . . . . 176 - 8. .3 Phenol by Phenyl Acetate Process Stream Flows . . . .1 Phenol by Oxychlorination and Hydrolysis (Raschig-Hooker) Production Costs . . . . . . . . . . . . . . . . .. . . . . .7 Phenol by Phenyl Acetate Process Production Costs . . . . . . . . . . . . 198 10. 195 10. . . . . . . . . . . . . . . . . . . . . . . . . 185 9. Phenol Supp B. . . . . . . . . 181 9. . . 188 9. .2 Phenol by Sulfonation Process Production Costs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190 10. 196 10. . . . . .3 Phenol by Chlorination Process Production Costs . . . . . .. . . . . . . . . . . . . . . . . . 197 10. . . . 185 9. . . . .5 Phenol from Benzene by Direct Oxidation (Vapor Phase) Production Costs . . . . . . . . . . 184 9. . . . . . . .5 Phenol by Phenyl Acetate Process Utilities Summary . . . 204 xvi . . . 202 10. . . . . 200 10. . . . . . .4 Phenol by Phenyl Acetate Process Major Equipment . . . . . . . . . . . . . . .2 Phenol by Phenyl Acetate Process Design Bases and Assumptions . . . . . . . . . . . . . . . and its Conversion to Phenol Patent Summary. . . . . . . . . . . 179 l 8. . . . . . . . .4 Phenol from Benzene by Direct Oxidation Based on a Shell Patent Production Costs . . . . . .

. . . . . . . . . . . . . . . . . . . . . . . . . 214 11.4 Major Equipment . . . . . . . . . . . . . . . . . . . . . . . . . Phenol Supp B. . . Phenol by Dealkylation of Cresols 209 211 Stream Flows . .1 Phenol by Dealkylation of Cresols . . 11. . December 1977 TABLES 11. . . . . . . . . . . . . . . . . . . . . . . .6 Phenol by Dealkylation of Cresols Production Costs . . . . . . . . Phenol by Dealkylation of Cresols 212 Utilities Summary . . . . . . . . . .3 Phenol by Dealkylation of Cresols a 11. . . .. . . . .2 Design Bases and Assumptions . 11. . . . . . .5 Phenol by Dealkylation of Cresols Capital Investment . . . . . 219 a- a- a xvii . . . . 217 11. .