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Methycryolic Acid and Esters, Supp. A Report No. 11 A METHACRYLIC ACID METHACRYLIC ESTERS Supplement A by DONALD C. THOMAS Contributions by Brij M. Sood and Leslie A. Carmichael May 1974 A private report by the PROCESS ECONOMICS PROGRAM I STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA I - - CONTENTS 1 INTRODUCTION . 1 2 SUMMARY................,.......... 3 Methyl Methacrylate via Acetone Cyanohydrin . 5 Methyl Methacrylate from Isobutylene via Methacrylonitrile . 6 Methyl Methacrylate from Isobutylene via Methacrylic Acid . 7 3 COMPARISON OF PROCESSES . 9 4 INDUSTRY STATUS . 15 5 METHYL METHACRYLATE VIA ACETONE CYANOHYDRIN ......... 19 Review of Processes ..................... 19 Hydrogen Cyanide Production ................ 19 Acetone Cyanohydrin Production .............. 21 Hydrolysis and Esterification ............... 24 Recovery of Methyl Methacrylate .............. 25 Handling and Disposition of Ammonium Bisulfate ...... 26 Process Description ..................... 29 Hydrogen Cyanide Production ................ 29 Acetone Cyanohydrin Production .............. 32 Hydrolysis and Esterification ............... 33 Purification ....................... 34 Sulfuric Acid Regeneration ................ 34 Process Discussion ..................... 49 Waste Treatment ....................... 50 Cost Estimates ....................... 52 6 METHYL METHACRYLATE FROM ISOBUTYLENE VIA METHACRYLONITRILE ...................... 61 Review of Processes ..................... 61 Methacrylonitrile Production ............... 61 Treatment of Ammoxidation By-Products ........... 65 Hydrolysis and Esterification ............... 65 Process Description ..................... 66 Methacrylonitrile Production ............... 66 Acetone Cyanohydrin Production .............. 84 Hydrolysis, Esterification, Purification, and Sulfuric Acid Regeneration ................ 84 Process Discussion ..................... 85 Cost Estimates ....................... 86 Vii - CONTENTS 7 METHYL METHACRYLATE FROM ISOBUTYLENE VIA METHACRYLIC ACID . 95 Review of Processes .............. 95 Oxidation of Isobutylene to Methacrolein and Methacrylic Acid .............. ....... 96 Oxidation of Methacrolein to Methacrylic Acid ....... 115 Recovery and Purification of Methacrylic Acid ....... 115 Esterification of Methacrylic Acid ..... ....... 121 Process Description .............. ....... 121 Methacrylic Acid Synthesis ......... ....... 128 Methacrylic Acid Recovery and Refining ... ....... 129 Esterification ............... ....... 130 Process Discussion .............. ....... 140 Methacrolein Synthesis ........... ....... 140 Methacrylic Acid Synthesis ......... ....... 141 Methacrylic Acid Extraction ......... ....... 141 Esterification ............... ....... 143 Data Needed ................. ....... 143 Possible Areas of Improvement ........ ....... 143 Cost Estimates ................ ....... 144 Capital Costs ................ ....... 144 Production Costs .............. ....... 144 a MISCELLANEOUS PROCESSES FOR METHACRYLIC ACID AND METHYLMETHACRYLATE................... 155 Methyl Methacrylate from Isobutyraldehyde . 155 Oxidative Dehydrogenation . 155 Oxyhalodehydrogenation . 156 Dehydrogenation with Sulfur . 157 Methacrylic Acid from Isobutylene by Oxidation with Nitrogen Tetroxide . 157 Methyl Methacrylate from Propylene, Isobutylene, or Propane via Methylacetylene . 161 Methylacetylene Production . 161 Methyl Methacrylate Production . 163 Methyl Methacrylate from Propylene by Oxidative Carbonylation . 164 Methacrylic Acid and Methyl Methacrylate by Other Processes.......................... 164 9 HEAVY ESTERS OF METHACRYLIC ACID . 167 Viii CONTENTS APPENDIX A DESIGN AND COST BASIS ............... 171 APPENDIX B PHYSICALDATA ................... 175 APPENDIX C PRODUCT SPECIFICATIONS ............... 179 CITED REFERENCES ........................ 181 PATENT REFERENCES BY COMPANY .................. 197 IX ILLUSTRATIONS 3.1 Manufacture of Methyl Methacrylate Comparison of Process Routes . 11 5.1 Acetone Cyanohydrin from Acetone and Hydrogen Cyanide Equilibrium Conversion of HCN as a Function of Temperature . 22 5.2 Acetone Cyanohydrin from Acetone and Hydrogen Cyanide Reaction Time as a Function of Temperature . 23 5.3 Methyl Methacrylate from Acetone, Ammonia, and Methane via Acetone Cyanohydrin Flow Sheet . 37 5.4 Methyl Methacrylate from Acetone, Ammonia, and Methane via Acetone Cyanohydrin Effect of Plant Capacity on Total Fixed Capital . 57 5.5 Methyl Methacrylate from Acetone, Ammonia, and Methane via Acetone Cyanohydrin Effect of Plant Capacity and Operating Level on Production Cost . 58 5.6 Methyl Methacrylate from Acetone, Ammonia, and Methane via Acetone Cyanohydrin Effect of Raw Material Costs on Production Cost . 59 6.1 Methyl Methacrylate from Isobutylene via Methacrylonitrile Flow Sheet . 71 6.2 Methyl Methacrylate from Isobutylene via Methacrylonitrile Effect of Plant Capacity on Total Fixed Capital . 89 6.3 Methyl Methacrylate from Isobutylene via Methacrylonitrile Effect of Plant Capacity, Operating Level, and Isobutylene Cost on Production Cost . 93 7.1 Methyl Methacrylate from Isobutylene via Methacrylic Acid Flow Sheet . 133 Xi ILLUSTRATIONS 7.2 Solvent Extraction of Methacrylic Acid from Water by Pentane Upper and Lower Layer Distribution Coefficient as a Function of Methacrylic Acid Content in the Lower Layer at 20°C . 142 7.3 Methyl Methacrylate from Isobutylene via Methacrylic Acid Effect of Plant Capacity on Total Fixed Capital . 149 7.4 Methyl Methacrylate from Isobutylene via Methacrylic Acid Effect of Isobutylene Cost on Production Cost . 153 7.5 Methyl Methacrylate from Isobutylene via Methacrylic Acid Effect of Plant Capacity and Operating Level on Production Cost . 154 8.1 Pyrolysis of Propylene . 162 xii TABLES 2.1 Methyl Methacrylate Manufacture Summary of Economics . 4 4.1 Methyl Methacrylate Manufacture Plant Capacities . , . , . 16 5.1 Methyl Methacrylate from Acetone, Ammonia, and Methane via Acetone Cyanohydrin Bases and Assumptions . 30 5.2 Methyl Methacrylate from Acetone, Ammonia, and Methane via Acetone Cyanohydrin Major Process Equipment and Utilities Summary . 37 5.3 Methyl Methacrylate from Acetone, Ammonia, and Methane via Acetone Cyanohydrin Stream Flows . 43 5.4 Methyl Methacrylate from Acetone, Ammonia, and Methane via Acetone Cyanohydrin Waste Stream Summary . 51 5.5 Methyl Methacrylate from Acetone, Ammonia, and Methane via Acetone Cyanohydrin Total Capital Investment . 53 5.6 Methyl Methacrylate from Acetone, Ammonia, and Methane via Acetone Cyanohydrin Production Costs . 55 6.1 Methacrylonitrile from Isobutylene Patent Summary . 63 6.2 Methyl Methacrylate from Isobutylene via Methacrylonitrile Bases and Assumptions . 67 6.3 Methyl Methacrylate from Isobutylene via Methacrylonitrile Major Process Equipment and Utilities Summary . 71 6.4 Methyl Methacrylate from Isobutylene via Methacrylonitrile Stream Flows....................... 77 6.5 Methyl Methacrylate from Isobutylene via Methacrylonitrile Waste Stream Summary . 83 Xiii TABLES 6.6 Methyl Methacrylate from Isobutylene via Methacrylonitrile Total Capital Investment . 87 6.7 Methyl Methacrylate from Isobutylene via Methacrylonitrile Production Costs . 91 7.1 Methacrolein by Vapor Phase Oxidation of Isobutylene, Molybdenum-Bismuth Catalyst Patent Summary . 97 7.2 Methacrolein and Methacrylic Acid by Vapor Phase Oxidation of Isobutylene, Molybdenum-Bismuth Catalyst Patent Summary. 101 7.3 Methacrolein by Vapor Phase Oxidation of Isobutylene, Molybdenum Catalyst Not Containing Bismuth Patent Summary. 103 7.4 Methacrolein by Vapor Phase Oxidation of Isobutylene, Catalyst Not Containing Molybdenum l- Patent Summary. 109 7.5 Methacrolein and Methacrylic Acid by Vapor Phase Oxidation of Isobutylene, Catalyst Not Containing Molybdenum Patent Summary. 113 7.6 Methacrylic Acid by Vapor Phase Oxidation of Methacrolein Patent Summary . 117 7.7 Extraction of Methacrylic Acid from its Aqueous Solution Patent Summary. 123 7.8 Methyl Methacrylate from Methacrylic Acid Patent Summary . ._ . 125 7.9 Methyl Methacrylate from Isobutylene via Methacrylic Acid Bases and Assumptions . 126 7.10 Methyl Methacrylate from Isobutylene via Methacrylic Acid Major Process Equipment and Utilities Summary . 132 xiv TABLES 7.11 Methyl Methacrylate from Isobutylene via Methacrylic Acid Stream Flows....................... 137 7.12 Methyl Methacrylate from Isobutylene via Methacrylic Acid Waste Stream Summary . , . 139 7.13 Methyl Methacrylate from Isobutylene via Methacrylic Acid Total Capital Investment . 147 7.14 Methyl Methacrylate from Isobutylene via Methacrylic Acid Production Costs . 151 8.1 Dehydration of o-Hydroxyisobutyric Acid or Methyl o-Hydroxyisobutyrate Patent Summary. 159 9.1 Butyl Methacrylate by Liquid Phase Transesterification of Methyl Methacrylate Patent Summary . -. 169 B.l Typical Properties of Methacrylate Monomers . 176 B.2 Distribution of Methacrylic Acid Between Water and Certain Organic Solvents at Room Temperature . 177 B.3 Liquid-Liquid Equilibria in the System Methacrylic Acid, Water, and Diethyl Ether at 15'C . 177 c.1 Shipping Specifications for Methacrylate Monomers . 179 xv .
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