Report No. 79 l DIHYDROXYBENZENES by HAROLD W. SCHEELINE September 1972 0 A private report by the PROCESS ECONOMICS PROGRAM l , STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA I CONTENTS 1 INTRODUCTION..,. , . , . , . 1 2 SUMMARY ,,,..,..,,...,.,,..~ .I . 3 General Aspects . , . , . , , , , . , . , . , . 3 Resorcinol . , . , . , . 3 Hydroquinone . , . 4 Pyrocatechol , . , , , . , , . 4 Economics . , , . 5 Resorcinol by Benzene Sulfonation , . , . , . , 9 Hydroquinone by Aniline Oxidation . , , , , , . 9 Resorcinol or Hydroquinone by Hydroperoxidation . s . 10 Pyrocatechol by o-Chlorophenol Hydrolysis . , . 11 Pyrocatechol and Hydroquinone from Phenol . , , , . 11 Technical Aspects . , , . , . , . , . 12 Resorcinol by Benzene Sulfonation . , . 12 Hydroquinone by Aniline Oxidation . , . , . , . I , . 13 Diisopropylbenzenes . , . , . , . 13 Resorcinol or Hydroquinone by Hydroperoxidation . 14 Pyrocatechol by o-Chlorophenol Hydrolysis . , . m . 16 Pyrocatechol and Hydroquinone from Phenol . , . 16 Other Processes for Dihydroxybenzenes . , . l 17 3 INDUSTRY STATUS ...................... 19 Resorcinol ......................... 19 Hydroquinone ........................ 24 Pyrocatechol ........................ 27 4 RESORCINOL BY BENZENE SULFONATION PROCESS . , . , , . , . 31 Chemistry ......................... 31 Review of Processes .................... 35 Process Description .................... 40 Process Discussion ..................... 52 Cost Estimates ....................... 54 Capital Costs .......................................... 54 Production Cost: 55 V 5 HYDROQUINONE BY ANILINE PROCESS . , . 63 Chemistry,,,,,. , .,.., ., ,.., ., , . , . , . 63 Review of Processes , , . , . , . , , , . , , . , , , . 66 Process Description . , . 70 Process Discussion . 82 Cost Estimates , . , . , . , . , . , . 84 Capital Costs . , . , , . , . , . 84 Production Costs . , . 85 6 DIISOPROPYLBENZENES ..................... 91 Chemistry .......................... 91 Review of Processes ..................... 95 Process Description ..................... 98 Process Discussion ..................... 111 Cost Estimates ....................... 113 Capital Costs ....................... 113 Production Costs ..................... 114 7 RESORCINOL OR HYDROQUINONE BY HYDROPEROXIDE PROCESS . 119 Chemistry.......................... 119 Review of Processes . , . , . , . 124 Dihydroperoxide Recovery by Solvent Extraction . , . , . 129 Process Description . , . , . 129 Process Discussion . , . 142 Cost Estimates . , . 144 Dihydroperoxide Recovery by crystallization . , . , . 150 Process Description . , . 150 Process Discussion . , . , , . , . , . 159 Cost Estimates . , . , . 161 8 PYROCATECHOL BY HYDROLYSIS OF o-CHLOROPHENOL ........ 167 Chemistry .......................... 167 Review of Processes ..................... 168 Process Description ..................... 170 Cost Estimates ....................... 175 Capital Costs ....................... 175 Production Costs ..................... 175 vi CONTENTS 9 DIHYDROXYBENZENES BY OXIDATION OF PHENOL . 181 Oxidation of Phenol by Hydrogen Peroxide . , . , 181 Air Oxidation of Phenol . , . , . , 189 10 DIHYDROXYBENZENES BY OTHER PROCESSES . , . 195 Hydrolysis of m-Phenylenediamine , . , , . , . , . , . , 195 From Cyclohexane Derivatives . , . , . , . , 198 Electrolytic Oxidation of Benzene . , , . , , . 198 Electrolytic Oxidation of Phenol . , , , . , . , . 199 Carbonylation of Acetylene . , . 199 From Hydroxybenzaldehydes . , . , . , . 200 APPENDIX A DESIGN AND COST BASIS . , , . , . 201 APPENDIX B PHYSICAL DATA . 205 APPENDIX C PRODUCT SPECIFICATIONS . , , 211 APPENDIX D PRODUCT TOXICITY AND HANDLING . , , . , . 217 CITEDREFERENCES. , . 219 PATENT REFERENCES BY COMPANY, . , , , . , 239 vii ILLUSTRATIONS 4.1 Resorcinol by Benzene Sulfonation Process . , 45 4.2 Resorcinol by Benzene Sulfonation Process Effect of Operating Level and Plant Capacity on Production Cost . 60 4.3 Resorcinol by Benzene Sulfonation Process Effect on Sodium Sulfate Value on Resorcinol Production Cost . 61 5.1 Hydroquinone by Aniline Process . , , . 77 5.2 Hydroquinone by Aniline Process Effect of Operating Level and Plant Capacity on Production Cost . , . 89 6.1 Para-Diisopropylbenzene , . , . 105 6.2 Meta-Diisopropylbenzene . 109 6.3 Meta- or Para-Diisopropylbenzene Effect of Operating Level and Plant Capacity on Production Cost . , . 118 7.1 Resorcinol or Hydroquinone by Hydroperoxide Process (Dihydroperoxide Separation by Extraction) . 137 7.2 Resorcinol or Hydroquinone by Hydroperoxide Process, Including Manufacture of DIPB Feedstock Effect of Operating Level and Plant Capacity on Production Cost . , . , . , , . 149 7.3 Resorcinol or Hydroquinone by Hydroperoxide Process (Dihydroperoxide Separation by Crystallization) . , . 155 8.1 Pyrocatechol by o-Chlorophenol Hydrolysis . , . 173 8.2 Pyrocatechol by Hydrolysis of o-Chlorophenol Effect of o-Chlorophenol Price on Pyrocatechol Production Cost . , . 179 9.1 Pyrocatechol and Hydroquinone by Oxidation of Phenol with Hydrogen Peroxide . 187 9.2 Pyrocatechol and Hydroquinone by Air Oxidation of Phenol . 193 ix TABLES 2.1 Dihydroxybenzenes Summary of Economics , . 7 3.1 Dihydroxybenzene Plants--United States , . , . , . , . , . 20 3.2 Dihydroxybenzene Plants--Europe . , . , . , . , 22 3.3 Dihydroxybenzene Plants--Japan , . , . 22 4.1 Resorcinol by Benzene Sulfonation Process Patent Summary. , . , . , . 36 4.2 Resorcinol by Benzene Sulfonation Process Major Process Equipment and Utilities Summary . , . , , 45 4.3 Resorcinol by Benzene Sulfonation Process Stream Flows . , . 49 4.4 Resorcinol by Benzene Sulfonation Process Summary of Waste Products , . , . , 51 4.5 Resorcinol by Benzene Sulfonation Process Total Capital Investment . , . , . , . , . , . , , , 57 4.6 Resorcinol by Benzene Sulfonation Process Production Costs , . , . , . , . , , . , . 59 5.1 Hydroquinone by Aniline Process Patent Summary.................. , ., . 67 5.2 Hydroquinone by Aniline Process Major Process Equipment and Utilities Summary , . 75 5.3 Hydroquinone by Aniline Process Stream Flows . , . 79 5.4 Hydroquinone by Aniline Process Summary of Waste Products . , . , . , . , , . , . 81 5.5 Hydroquinone by Aniline Process Total Capital Investment . , . 87 5.6 Hydroquinone by Aniline Process Production Costs . , . 88 6.1 Diisopropylbenzenes a Patent Summary. , . , . , 97 6.2 Meta- or Para-Diisopropylbenzene Major Process Equipment and Utilities Summary . 103 l Xi . TABLES 6.3 Para-Diisopropylbenzene Stream Flows . , . , . , . 107 6.4 Meta-Diisopropylbenzene Stream Flows , . , . , , . , , . , 109 6.5 Meta- or Para-Diisopropylbenzene Total Capital Investment . , , . 116 6.6 Meta- or Para-Diisopropylbenzene Production Costs . , . 117 7.1 Resorcinol or Hydroquinone by Hydroperoxide Process Patent Summary...................... 125 7.2 Resorcinol or Hydroquinone by Hydroperoxide Process (DRP Extraction) Major Process Equipment and Utilities Summary , . , , 135 7.3 Resorcinol or Hydroquinone by Hydroperoxide Process (DHP Extraction) Stream Flows . '. , . , . 139 7.4 Resorcinol or Hydroquinone by Hydroperoxide Process (DHP Extraction) Summary of Waste Products . , . 141 7.5 Resorcinol or Hydroquinone by Hydroperoxide Process (DHP Extraction) Total Capital Investment . , . , . , . , . , . , . 147 7.6 Resorcinol or Hydroquinone by Hydroperoxide Process (DHP Extraction) Production Costs . , . , . , . , , . 148 7.7 Resorcinol or Hydroquinone by Hydroperoxide Process (DIG Crystallization) Major Process Equipment and Utilities Summary , , , . 153 0- 7.8 Resorcinol or Hydroquinone by Hydroperoxide Process (DHP Crystallization) Stream Flows....................... 157 7.9 Resorcinol or Hydroquinone by Hydroperoxide Process (DHP Crystallization) 0- Total Capital Investment , , . , . , . 164 7.10 Resorcinol or Hydroquinone by Hydroperoxide Process (DHP Crystallization) Production Costs . , . , , . , . , . .'. 165 0 xii TABLES 8.1 Dihydroxybenzenes by Hydrolysis of Halogenated Compounds Patent Summary. , . , . , . 169 8.2 Pyrocatechol by Hydrolysis of o-Chlorophenol Stream Flows....................... 173 8.3 Pyrocatechol by o-Chlorophenol Hydrolysis Total Capital Investment , . , . 177 8.4 Pyrocatechol by o-Chlorophenol Hydrolysis Production Costs . , , . , . , . , . 178 9.1 Dihydroxybenzenes by Oxidation of Phenol Patent Summary..........,........... 182 9.2 Pyrocatechol and Hydroquinone by Oxidation of Phenol with Hydrogen Peroxide Stream Flows . , . , . , . , . 187 9.3 Pyrocatechol and Hydroquinone by Air Oxidation of Phenol Stream Flows........ , . , . 193 10,l Other Processes for Dihydroxybenzenes Patent Summary..........,........... 196 B.l Physical Data on Dihydroxybenzenes , . , . , . , . 207 B.2 Other Properties of Resorcinol , , , . , . 208 B.3 Properties of Diisopropylbenzenes , , , . , . 209 C.l Resorcinol Specifications , , . , . 213 C.2 Hydroquinone Specifications and Typical Properties , . 214 C.3 Pyrocatechol Specifications , . , . , , . 215 l 0 Xiii .