PROCESS ECONOMICS PROGRAM ..-. SRI INTERNATIONAL Mm10 Park, California Abstract 9402E

Process Economics Program Report No. 11C

METHACRYLIC ACID AND METHACRYLIC ESTERS

(September 1984)

For the last fifteen years, processes have been developed to supplant the established process for making methyl methacrylate from acetone, hydrogen cyanide, and methanol. The acetone cyanohydrin route suffers from production of acidic wastes; the newer processes avoid these wastes and offer lower costs.

Since our most recent previous report on the subject (Report LlB, issued in July 1980), a methyl methacrylate process based on a C4 feed- stock has been commercialized in Japan. This process oxidizes a t-butanol feed to methacrolein and methacrylic acid in two stages, then esterifies the acid to methyl methacrylate.

We have evaluated this process and several variations, including the alternative use of isobutane feed and the supplementary use of isobutyraldehyde (by-product from 0x0 alcohol plants). We have also evaluated an attractive process based on propylene hydrocarboxylation to isobutyric acid, followed by dehydrogenation to methacrylic acid.

We have updated some of the processes evaluated in Report llB, including the acetone cyanohydrin process. For a newly constructed plant, and at market prices for HCN and acetone, the acetone cyanohydrin process is more expensive than several of the newer processes.

PEP'83 RHS - ReportNo. 11C

a METHACRYLIC ACID AND ESTERS

SUPPLEMENT C

by ROBERT H. SCHWAAR ETSUO MATSUNAGA SHOICHI KIKUCHI a- and WATARU NISHIMOTO

September 1984

- Cl a A private report by the PROCESS ECONOMICS PROGRAM a m Menlo Park, California 94025 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 PETROCHEMICALS Program covers major hydrocarbons and their derivatives on a worldwide basis. In addition, the SRI DIRECTOKY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, prod- uct, and plant for the United States and Western Europe.

ii CONTENTS

1 INTRODUCTION...... 1

2 SUMMARY ...... 3 General Aspects ...... 3 Economic Aspects ...... 4 Technical Aspects ...... 9 t-Butanol Oxidation ...... 9 Isobutane Dehydrogenation ...... 10 Dehydrogenation of Isobutyraldehyde ...... 11 Dehydrogenation of Isobutyric Acid ...... 12 Oxidation of Isobutyraldehyde ...... 13 Other Processes for Making Methyl Methacrylate ...... 13 Isobutylene Oxidation ...... 14 Mixed Butylenes Oxidation ...... 14 Methyl Propionate Route from Ethylene ...... 14 Acetone Cyanohydrin Route ...... 14 Hydroformylation of Ally1 Acetate ...... 15 Liquid-Phase Oxidation of Methacrolein to Methyl Methacrylate ...... 15

3 INDUSTRY STATUS ...... 17 United States ...... 18 Western Europe ...... 21 Japan ...... 23 Asahi Chemical ...... 23 Mitsubishi Rayon ...... 25 Japan Methacryl Monomer ...... 25

4 ROUTES TO METHYL METHACRYLATE AND METHACRYLIC ACID .... 29 Isobutylene Routes ...... 29 Propylene Routes ...... 32 Ethylene Routes ...... 34

5 METHYL MRTHACRYLATE PROM t-BUTANOL VIA METHACROLEIN . . . . 37 Review of Patents ...... 37 Oxidation of t-Butanol or Isobutylene to Methacrolein . . 37 Catalyst Preparation . . . . . , ...... 38 a iii CONTENTS -

5 METHYL METHACRYLATE FROM t-BUTANOL VIA METHACROLEIN (continued) Liquid-Phase Process for Methacrolein ...... 38 Methacrolein Recovery ...... 39 0- Oxidation of Methacrolein to Methacrylic Acid ...... 40 Liquid-Phase Processes ...... 1 41 Methacrylic Acid Recovery ...... 42 Esterification of Methacrylic Acid with Methanol ...... 43 t-Butanol Feedstock ...... 45 Process Description ...... 47 Oxidation of t-Butanol to Methacrolein (Section 100) L ... 47 Oxidation of Methacrolein to Methacrylic Acid (Section 200) . 50 Esterification of Methacrylic Acid with Methanol (Section 300) ...... 51 Process Discussion ...... 61 Oxidation of t-Butanol to Methacrolein ...... 61 Recovery of Methacrolein ...... 63 a- Oxidation of Methacrolein to Methacrylic Acid ...... 64 Recovery of Methacrylic Acid ...... 64 Esterification ...... 66 Waste Streams ...... 66 Materials of Cohstruction ...... 67 Cost Estimates ...... 69 Capital Costs ...... 69 Production Costs ...... 70

6 VARIATIONS OF THE t-BUTANOL PROCESS ...... 81 Other C4 Feedstocks ...... 82 Isobutylene Feed...... 82 Mixed C4 Olefin Feed ...... 83 a- MIBEFeed...... 8 4 Isobutane Feed ...... 84 Isobutyraldehyde Feed ...... 87 Isobutane Process Description ...... 88 Dehydrogenation of Isobutane to Isobutylene (Section 100) . . 89 Oxidation of Isobutylene to Methacrolein (Section 200) ... 91 a- Oxidation of Methacrolein to Methacrylic Acid (Section 300) Esterification and MMA Refining (Section 400) ...... 92 a iv CONTENTS

6 VARIATIONS OF THE t-BDTANOL PROCESS (continued) Isobutane Process Discussion ...... 98 - Dehydrogenation of Isobutane to Isobutylene ...... 98 Oxidation of Isobutylene to Methacrolein ...... 98 Waste Streams ...... 99 Materials of Construction ...... 99 Isobutane Process Cost Estimates ...... 102 Capital Costs ...... 102 Production Costs ...... 102 Isobutyraldehyde Process Description ...... 112 Oxidation of Isobutyraldehyde to Methacrylic Acid (Section 400) ...... 112 Oxidation of t-Butanol to Methacrolein (Section 100) Oxidation of Methacrolein to Methacrylic Acid (Section 200) Esterification of Methacrylic Acid with Methanol (Section 300) ...... 114 a- Isobutyraldehyde Process Discussion ...... 123 Isobutyraldehyde Process Cost Estimates ...... 123 Capital Costs ...... 123 Production Costs...... 126 Other Process Variations ...... 136 Methacrolein Isolation Omitted ...... 136 Methacrylic Acid from t-Butanol or Isobutylene in a Single Step ...... 137 Methyl Methacrylate from Isobutylene in a Single Step . . 137 Methyl Methacrylate by Esterification of Methacrolein . . 138 Methyl Methacrylate from Isobutylene via Methacrylonitrile ...... 141 Methacrylic Acid from Methacrylonitrile ...... 142 a Methyl Methacrylate from Methacrylonitrile ...... 142

7 METHYL METEACRYLATE FROM PROPYLENE VIA ISOBDTYRIC ACID ... 143 Review of Patents ...... 143 Production of Isobutyric Acid from Propylene ...... 143 Dehydrogenation of Isobutyric Acid to Methacrylic Acid . . 144 a Recovery and Purification of Methacrylic Acid ...... 145 Esterification of Methacrylic Acid with Methanol ..... 146 Purification of Methyl Methacrylate...... 148

V CONTENTS

7 METHYL METHACRYLATE FROM PROPYLENE VIA ISOBUTYRIC ACID (Continued) Chemistry ...... 149 Hydrocarboqlation of Propylene to Isobutyric Acid .... 149 Hydrolysis of By-Products ...... 150 Carboxylation of Isopropanol to Isobutyric Acid ...... 150 Process Description ...... 151 Hydrocarboxylation of Propylene to Isobutyric Acid (Section 100) ...... 151 Dehydrogenation of Isobutyric Acid to Methacrylic Acid (Section 200) ...... 155 Esterification of Methacrylic Acid with Methanol (Section 300) ...... 156 Process Discussion ...... 166 Hydrocarboqlation of Propylene to Isobutyric Acid .... 166 Isopropanol Formation and Handling ...... 167 2-Fluoropropane Formation and Handling ...... 167 Removal of Light By-Products from Isobutyric Acid .... 168 Dehydrogenation of Isobutyric Acid to Methacrylic Acid . . 169 Recovery of Methacrylic Acid ...... 169 Esterification of Methacrylic Acid ...... 170 Waste Streams ...... 170 Materials of Construction ...... 170 Cost Estimates ...... 173 Capital Costs ...... ; 173 Production Costs ...... 173

8 SUPPLEMENTARY PRODUCTION OF ISOBUTYRIC ACID FROM ISOBUTYRALDEHYDE ...... 185 Review of Patents ...... 185 a Process Description ...... 186 Oxidation of Isobutyraldehyde to Isobutyric Acid (Section 400) ...... 187 Hydrocarboxylation of Propylene to Isobutyric Acid (Section 100) ...... 189 Dehydrogenation of Isobutyric Acid to Methacrylic Acid (Section 200) ...... Esterification of Methacrylic Acid to Methyl Methacrylate (Section 300) ...... 189

Vi CONTENTS

8 SUPPLEMENTARY PRODUCTION OF ISOBUNRIC ACID PROM ISOBUNRALDEHYDE (Continued) Process Discussion ...... 199 Cost Estimates...... 202 Capital Costs ...... 202 Production Costs ...... 202

APPENDIX A DESIGN AND COST BASES ...... 213

APPENDIX B CONVERSION, SELECTIVITY, AND YIELD ...... 221

APPENDIX C AZEOTROPES ...... 223

PATENTSUMMARYTABLES .:...... 225

CITEDREFERENCES ...... 257

PATENTREFERENCES ...... 271

Vii ILLUSTRATIONS

2.1 Manufacture of Methyl Methacrylate Effect of Plant Capacity on Total Fixed Capital ...... 5 4.1 Routes to Methyl Methacrylate and Methacrylic Acid from C4 Fraction ...... 30 4.2 Routes to Methyl Methacrylate and Methacrylic Acid from Propylene ...... 33 4.3 Routes to Methyl Methacrylate and Methacrylic Acid fromEthylene...... 35

METHYL MgTHACRYLATE FROM t-BUTANOL VIA METHACROLEIN 5.1 Process Flow Magram ...... 277 5.2 Effect of Raw Material Prices on Production Cost ...... 78 5.3 Effect of Operating Level and Plant Capacity on Production Cost and Product Value ...... 79

METHYL METHACRYLATE FROM ISOBDTANE VIA ISOBDTYLENE 6.1 process Flow Magram ...... 283 6.2 Effect of Raw Material Prices on Production Cost ...... 110 6.3 Effect of Operating Level and Plant Capacity on Production Cost and Product Value ...... 111

METHYL METHACRYLATE FROM t-BDTANOL AND ISOBUTYRALDEHYDE VIA METHACROLEIN 6.4 Process Flow Diagram ...... 287 6.5 Effect of Raw Material Prices on Production Cost ...... 134 6.6 Effect of Operating Level and Plant Capacity on Production Cost and Product Value ...... 135

METHYL METHACRYLATE FROM PROPYLENE VIA ISOBDTYRIC ACID 7.1 Process Flow Magram ...... 289 7.2 Effect of Raw Material Prices on Production Cost ...... 182 7.3 Effect of Operating Level and Plant Capacity on Production Cost and Product Value ...... 183

IX ILLUSTRATIONS

METHYL MEXWACRYLATE FROM PROPYLENE AND ISOBUTYRALDEHYDE VIA ISOBUTYRIC ACID 8.1 Process Flow Diagram ...... 295 8.2 Effect of Raw Material Prices on Production Cost . . . . . 211 8.3 Effect of Operating Level and Plant Capacity on Production Cost and Product Value ...... 212

X TABLES

2.1 Summary of Cost Estimates for Methyl Methacrylate Manufacture...... 6 2.2 Summary of Cost Estimates for Methyl Methacrylate Manufacture Updates of Previous Evaluations ...... 8

METHYL METUACRYLATE PRODUCERS 3.1 United States ...... 19 3.2 Western Europe ...... 22 3.3 Japan ...... 24 3.4 Other Countries ...... 27

5.1 Vapor-Phase Oxidation of t-Butanol or Isobutylene to Methacrolein Summary of Selected Patents on Catalyst Composition . . . . 226 5.2 Methacrolein Recovery Patent Summary ...... 232 5.3 Vapor-Phase Oxidation of Methacrolein to Methacrylic Acid Summary of Selected Patents on Catalysts ...... 234 5.4 Methacrylic Acid Recovery PatentSummary ...... 238 5.5 Esterification of Methacrylic Acid with Methanol PatentSummary ...... 245

METBYL METUACRYLATE FROM t-BUTANOL VIA METBACROLEIN 5.6 Bases and Assumptions ...... 48 5.7 Major Equipment ...... 53 5.8 Utilities Summary ...... 56 5.9 Stream Flows ...... 57 5.10 Waste Streams ...... 68 5.11 Capital Investment ...... 72 5.12 Major Capital Equipment Costs ...... 74 5.13 Production Costs ...... 75

xi TABLES

6.1 Isobutyraldehyde Conversion to Methacrolein and Methacrylic Acid Patent Summary...... 249

METBYL METUACRYLATE FROM ISOBUTANE VIA ISOBUTYLENE 6.2 Bases and Assumptions ...... 90 6.3 Major Equipment ...... 93 6.4 Utilities Summary ...... 95 6.5 StreamFlows...... 96 6.6 Waste Streams ...... 100 6.7 Capital Investment ...... 104 6.8 Major Capital Equipment Costs ...... 106 6.9 Production Costs ...... 107

METHYL METHACRYLATE FROM t-BUTANOL AND ISOBUTYRALDEHYDE VIA METUACROLEIN 6.10 Bases and Assumptions ...... 113 6.11 Major Equipment ...... 115 6.12 Utilities Summary ...... 118 6.13 Stream Flows ...... 119 6.14 Waste Streams ...... 124 6.15 Capital Investment ...... 128 6.16 Major Capital Equipment Costs ...... 130 6.17 Production Costs ...... 131

7.1 Isobutyric Acid by Carbonylation of Propylene Patent Summary...... 250 7.2 Methacrylic Acid by Dehydrogenation of Isobutyric Acid Patent Summary...... 254

xii TABLES

METHYL METHACRYLATE FROM PROPYLENE VIA ISOBUTYRIC ACID 7.3 Bases and Assumptions ...... 152 7.4 Major Equipment ...... 158 7.5 Utilities Summary ...... 161 7.6 StreamFlows ...... 162 7.7 Waste Streams ...... 172 7.8 Capital Investment ...... 176 7.9 Major Capital Equipment Costs ...... 178 7.10 Production Costs ...... 179

METHYL METHACRYLATE FROM PROPYLENE AND ISOBUTYRALDEBYDE VIA ISOBUTYRIC ACID 8.1 Bases and Assumptions ...... 188 8.2 Major Equipment ...... 190 8.3 Utilities Summary ...... 194 8.4 Stream Flows ...... 195 8.5 Waste Streams ...... 201 8.6 Capital Investment ...... 206 8.7 Major Capital Equipment Costs ...... 207 8.8 Production Costs ...... 208

Xiii