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Report No. 6B

ACRYLIC ACID AND ACRYLIC ESTERS

Supplement B

by DONALD C. THOMAS

Contributions by Kaiji Yokokawa and Harold W. Soheeline

September 1074

A private report by the

PROCESS ECONOMICS PROGRAM a STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA CONTENTS

1 INTRODUCTION ...... 1

2 SUMMARY ...... 3

3 INDUSTRY STATUS...... , ...... 7

4 CHEMISTRY ...... 19 Acrolein from Propylene ...... 19 Acrylic Acid from Acrolein ...... 19

5 MANUFACTURE OF ACRYLIC ACID ...... 21 Vapor Phase Oxidation of Propylene ...... 21 Review of Processes ...... 21 Process Description ...... 100 Process Discussion ...... 114 Cost Estimates ...... 116 Liquid Phase Oxidation of Propylene or Acrolein ...... 122 Catalytic Acetylene Process: Update of Economics . . . . . 123 Other Processes ...... 130 Oxidative Carbonylation ...... 130 Carbonylation ...... 131 Decarboxylation of Maleic Acid ...... 131 Ethylene Cyanohydrin Process ...... 131 B-Propiolactone Process ...... 132 Acrylonitrile Process ...... 132 Isopropanol Process ...... 133 Acetic Acid-Formaldehyde Process ...... , . 133

6 MANUFACTURE OF LOWER ACRYLIC ESTERS ...... 135 Acrylic Acid Esterification ...... 135 Review of Processes ...... ; .... 135 Process Description ...... 141 Process Discussion ...... 153 Cost Estimates ...... 154 Other Processes ...... 159 Saturated Ester Process ...... 159 Decarboxylation ...... 159 Ethylene Cyanohydrin Process ...... 160 Acrylonitrile Process ...... 160 Carbonylation ...... 161 Acrolein Process ...... 161

vii CONTENTS

(Continued)

Acetylene Process ...... 161 B-Propiolactone Process ...... 162 Production of Chlorinated Acrylates ...... 162

MANUFACTURE OF HIGHER ACRYLIC ESTERS BY TRANSESTERIFICATION ...... 163

ENVIRONMENTAL CONSIDERATIONS IN ACRYLIC ESTERS MANUFACTURE ...... 165 Odor Control ...... 165 Waste Water Control ...... 166 Residue Disposal ...... 166

APPENDIX A DESIGN AND COST BASIS ...... 169

APPENDIX B PHYSICAL PROPERTIES ...... 173

APPENDIX C SPECIFICATIONS ...... 175

CITED REFERENCES ...... 177

PATENT REFERENCES BY COMPANY ...... 209 .

viii ILLUSTRATIONS

3.1 Growth of Acrylic Ester Industry in the United States . . 8 3.2 Growth of Acrylic Ester Industry in Japan ...... 10 5.1 Vapor Phase Oxidation of Propylene or Acrolein Schemes for Recovery of Acrylic Acid ...... 93

5.2 Acrylic Acid by Two-Step Vapor Phase Oxidation of Propylene ...... 109 5.3 Acrylic Acid by Two-Step Vapor Phase Oxidation of Propylene Effect of Plant Capacity on Total Fixed Capital . . . . . 118 5.4 Acrylic Acid by Two-Step Vapor Phase Oxidation of Propylene Effect of Operating Level and Plant Capacity on Production Cost ...... 121 5.5 Acrylic Acid by Catalytic Acetylene Process Effect of Plant Capacity on Total Fixed Capital . . . . . 127 5.6 Acrylic Acid by Catalytic Acetylene Process Effect of Operating Level and Plant Capacity on Production Cost ...... 129 6.1 Ethyl Acrylate by Acrylic Acid Esterification ...... 147

ix TABLES

2.1 Acrylic Acid Manufacture Summary of Economics ...... 5 2.2 Methyl or Ethyl Acrylate Manufacture by Esterification of Acrylic Acid Summary of Economics . . . . . , ...... 6 3.1 Acrylic Acid and Esters Production in the United States ...... 9 3.2 Distribution of Acrylate Usage in the United States . . 9 3.3 Plant Capacities for Producing Acrylic Acid and Esters...... 11 3.4 List Prices of Acrylic Acid and Esters in the United States ...... 17 5.1 Acrolein by Propylene Oxidation Patent Summary...... 23 5.2 Acrylic Acid by Acrolein Oxidation Patent Summary...... 55 5.3 Acrylic Acid by Propylene Oxidation Patent Summary. . , ...... , 73 5.4 Propylene Oxidation Examples of Small Quantity By-Products . . . . , . . . . 91

5.5 Extractants for Recovery of Acrylic Acid from Aqueous Solutions . , ...... 95

5.6 Polymerization Inhibitors ...... 101 5.7 Acrylic Acid by Two-Step Vapor Phase Oxidation of Propylene Design Bases ...... 103 5.6 Acrylic Acid by Two-Step Vapor Phase Oxidation of Propylene Major Process Equipment and Utilities Summary . . . . . 107 5.9 Acrylic Acid by Two-Step Vapor Phase Oxidation of Propylene Stream Flows ...... 111 5.10 Acrylic Acid by Two-Step Vapor Phase Oxidation of Propylene Waste Stream Summary ...... 113

xi TABLES

5.11 Acrylic Acid by Two-Step Vapor Phase Oxidation of Propylene Total Capital Investment ...... 117 5.12 Acrylic Acid by Two-Step Vapor Phase Oxidation of Propylene Production Costs ...... 119 5.13 Acrylic Acid by Catalytic Acetylene Process Total Capital Investment ...... 125 5.14 Acrylic Acid by Catalytic Acetylene Process Production Costs ...... 128 6.1 Methyl or Ethyl Acrylate by Acrylic Acid Esterification Patent Summary ...... 137 6.2 Methyl or Ethyl Acrylate by Acrylic Acid Esterification Design Bases ...... 142 6.3 Methyl or Ethyl Acrylate by Acrylic Acid 0- Esterification Major Process Equipment and Utilities Summary . , . . . 147

6.4 Methyl or Ethyl Acrylate by Acrylic Acid Esterification Stream Flows ...... 149

6.5 Methyl or Ethyl Acrylate by Acrylic Acid Esterification Total Capital Investment ...... 156 6.6 Methyl or Ethyl Acrylate by Acrylic Acid Esterification Production Costs ...... 157 a- B.l Distribution Coefficients for Solvent Extraction of Acrylic Acid and Acetic Acid from Water ...... 173 B.2 Acrylic Acid Liquid-Liquid Distribution Coefficients and Solvent Solubility Relationships ...... 174 c.1 Typical Specifications for Acrylic Acid 0- and Acrylic Esters ...... , ...... 175

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