Report No. 49 CRESOLS AND CRESYLICACIDS by YEN-CHEN YEN March 1969 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA I CONTENTS 1 INTRODUCTION . 1 2 SUMMARY........................... 3 3 INDUSTRY STATUS . 4 CRESOLS AND CRESYLIC ACIDS FROM COAL TAR AND PETROLEUM REFINERYWASTE . 29 Review of Processes ..................... 29 Recovery of Phenols from Coal Tar Oil ............ 51 Process Description .................... 51 Process Discussion .................... 61 Cost Estimates ...................... 62 Phenols from Petroleum Refinery Waste ............ 67 Process Description .................... 67 Process Discussion .................... 77 Cost Estimates ...................... 77 5 ALKYLATION OF PHENOL BY METHANOL .............. 85 Chemistry .......................... 85 Review of Processes ..................... 86 VaporPhase ........................ 86 Liquid Phase ....................... 89 Alkylation of Phenol by Methanol in Vapor Phase ....... 90 Process Description .................... 90 Process Discussion .................... 99 Cost Estimates ...................... 100 Brief Evaluation of Process Variations ........... 111 6 CRESOLS BY SULFONATION PROCESS ............... 115 Chemistry .......................... 115 Sulfonation ........................ 115 Caustic Fusion ...................... 116 Process Description ..................... 116 Process Discussion ...................... 118 Cost Estimates ....................... 123 iii CONTENTS - 7 CRESOLS BY CYMENE PROCESS .................. 133 Chemistry .......................... 133 Propylation of Toluene .................. 133 Oxidation of Cymene .................... 134 Review of Processes ..................... 135 Manufacture of Cresols by Cymene Process .......... 138 a Process Description .................... 138 Process Discussion .................... 149 Cost Estimates ...................... 149 Alternative Processes .................... 158 8 OTHER PROCESSES ....................... 161 Xylene Process ....................... 161 Chlorination Process .................... 162 Methylcyclohexane Process .................. 162 Raschig Process ....................... 163 Direct Oxygen Oxidation Processes .............. 164 Peroxide Processes ..................... 164 Iodotoluene Process ..................... 166 Ditolylethane Process .................... 166 Cyclohexane Process ..................... 167 Chlorotoluene and Ammonia Process .............. 168 Diazonium Salt Process ................... 168 Cyclization Processes .................... 169 The Coproduction of Nitrile and Hydrocyanic Acid ...... 169 Ortho-Cresol from 2-Chloro-Orthocresol ........... 170 Cracking, Dealkylation, and Transalkylation Processes .... 170 Isomerization of Cresols .................. 171 9 SEPARATION OF META-CRESOL AND PARA-CRESOL .......... 173 Review of Processes ..................... 173 Azeotropic Distillation .................. 173 0 Freezing and Crystallization ............... 173 Adsorption ........................ 173 Selective Resinification .................. 174 Other Chemical Processes ................. 174 Process Using Additives of Cresols ............ 174 Solvent Extraction Process ................ 176 Butylation Process .................... 176 iv CONTENTS 9 (Continued) Preparation of Ditertiary Butyl p-Cresol from m,p-Cresol with Simultaneous Production of m-Cresol .......... 177 Process Description .................... 177 Process Discussion .................... 187 Cost Estimates ...................... 189 Alternative Process Using C-4 Refinery Gas ......... 201 APPENDIX A DESIGN AND COST BASIS . 203 APPENDIX B SPECIFICATIONS OF PRODUCTS . 209 APPENDIX C PHYSICAL DATA . 211 APPENDIX D TREAl'%lENTOF PHENOLIC WASTE WATER . 215 APPENDIX E XYLENOLS...................... 221 CITEDREFERENCES . 223 PATENT REFERENCES BY COMPANY . 253 V ILLUSTRATIONS 4.1 Cresols and Cresylic Acids from Coal Carbonization . 31 4.2 Cresols and Cresylic Acids from Petroleum Refinery Waste . 33 4.3 Cresols from Na-Phenolates by Carbonation Scheme A of Figure 4.1 . , . 35 4.4 Treatment of Ammoniacal Liquor Scheme B of Figure 4.1 . 37 4.5 Extraction of Tar Acid from a Dilute Solution Scheme C of Figure 4.1 . 38 4.6 Treatment of Ammoniacal Liquor Scheme D of Figure 4.1 . 39 4.7 Recovery of Phenols by Extraction Scheme E of Figure 4.1 . 41 4.8 Extraction of Carbolic Acid by Pressurized Water Scheme F of Figure 4.1 . 43 4.9 Pressure-Soda Process 0- Scheme G of Figure 4.1 . 44 4.10 Extraction of Carbolic Oil by Methanol Scheme H of Figure 4.1 . , . 45 4.11 Treatment of Petroleum Refinery Waste Scheme J of Figure 4.2 . 47 4.12 Treatment of Petroleum Refinery Waste Scheme K of Figure 4.2 . 49 4.13 Recovery of Phenol, Cresols, and Cresylic Acid from Coal Taroil............................ 55 4.14 Phenol, Cresols, Cresylic Acid from Petroleum Refinery Waste........................... 69 0- 5.1 Alkylation of Phenol by Methanol . 93 5.2 Alkylation of Phenol by Methanol Effect of Operating Level and Plant Capacity on Production cost . 109 5.3 Mutual Interdependence of Costs of o-Cresol and 2,6-Xylenol 0 Made by Alkylation of Phenol by Methanol . 110 6.1 Cresols by Sulfonation Process . 121 6.2 Cresols by Sulfonation Process Effect of Production Scale on Production Cost . 131 0 vii ILLUSTRATIONS 6.3 Interdependence of Production Costs of p,m-Cresol and - o-Cresol Made by Sulfonation Process . 132 7.1 Cresols by Cymene Process . 141 7.2 Cresols by Cymene Process Effect of Production Scale on Production Cost . , . 157 0 9.1 Ditertiary Butyl p-Cresol and m-Cresol from m,p-Cresol . 179 9.2 Ditertiary Butyl p-Cresol and m-Cresol from m,p-Cresol Mutual Dependence of Production Costs of Ditertiary Butyl p-Cresol and m-Cresol . 192 9.3 Ditertiary Butyl p-Cresol and m-Cresol from m,p-Cresol Production Costs at Different Production Levels . , . 193 c.1 Normal Boiling Points of Phenol, Cresols, Xylenols, and Neighboring Boiling Alkylphenols . 212 viii TABLES 2.1 Comparison of Processes for Producing Cresols and Related Products . 5 2.2 Processes for Various Cresols, Xylenols, and Cresylic Acid . 11 3.1 U.S. Production of Cresols and Cresylic Acids . 20 3.2 Petroleum and Coal Tar Cresols and Cresylic Acids Producers in the United States . 25 3.3 Synthetic Cresols Producers Plant Capacities . 27 4.1 Purification of Cresols Summary of Processes . 50 4.2 Phenol, Cresols, and Cresylic Acid from Coal Tar Oil Major Process Equipment and Utilities Summary . 54 4.3 Phenol, Cresols, and Cresylic Acid from Coal Tar Oil Stream Flows . 59 4.4 Phenol, Cresols, and Cresylic Acid from Coal Tar Oil Fixed Capital Investment . 63 4.5 Phenol, Cresols, and Cresylic Acid from Coal Tar Oil Total Capital Investment . 64 4.6 Recovery of Phenol, Cresols, and Cresylic Acid from Coal Tar Oil Production Costs . 65 4.7 Phenol, Cresols, and Cresylic Acid from Petroleum Refinery Waste Major Process Equipment and Utilities Summary . 69 4.8 Phenol, Cresols, and Cresylic Acid from Petroleum Refinery Waste 0 Stream Flows . 75 4.9 Phenol, Cresols, and Cresylic Acid from Petroleum Refinery Waste Fixed Capital Investment . 79 4.10 Phenol, Cresols, and Cresylic Acid from Petroleum Refinery Waste Total Capital Investment . 81 4.11 Phenol, Cresols, and Cresylic Acid from Petroleum Refinery Waste Production Costs . 83 ix TABLES 5.1 Alkylation of Phenol by Methanol Summary of Patents . 87 5.2 Alkylation of Phenol by Methanol Major Process Equipment and Utilities Summary , . , . 92 5.3 Alkylation of Phenol by Methanol Stream Flows . , . 97 5.4 Alkylation of Phenol by Methanol Fixed Capital Investment . 103 5.5 Alkylation of Phenol by Methanol Total Capital Investment . , . 105 5.6 Alkylation of Phenol by Methanol Production Costs . 107 6.1 Cresols by Sulfonation Process Major Process Equipment and Utilities Summary . , . 119 6.2 Cresols by Sulfonation Process Fixed Capital Investment . 125 6.3 Cresols by Sulfonation Process Total Capital Investment . 127 6.4 Cresols by Sulfonation Process Production Costs . 129 7.1 Oxidation of Cymene to Hydroperoxide Summary of Processes . 137 7.2 Cresol by Cymene Process Major Process Equipment and Utilities Summary . 141 7.3 Cresols by Cymene Process Stream Flows . 147 7.4 Cresols by Cymene Process Fixed Capital Investment . 151 7.5 Cresols by Cymene Process Total Capital Investment . 153 7.6 Cresols by Cymene Process Production Costs . 155 9.1 Ditertiary Butyl p-Cresol and m-Cresol from m,p-Cresol Major Process Equipment and Utilities Summary . 179 TABLES 9.2 Ditertiary Butyl p-Cresol and m-Cresol from m,p-Cresol Stream Flows . 185 9.3 Ditertiary Butyl p-Cresol and m-Cresol from m,p-Cresol Fixed Capital Investment . 195 9.4 Ditertiary Butyl p-Cresol and m-Cresol from m,p-Cresol Total Capital Investment , . , . 197 9.5 Ditertiary Butyl p-Cresol and m-Cresol from m,p-Cresol Production Costs . 199 xi .