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PROCESS ECONOMICS PROGRAM

SRI INTERNATIONAL Menlo Park, California Abstract 94025

Process Economics Program Report No. 2D

ETHYLENE OXIDE/PROPYLENE OXIDE

(February 1985)

Ethylene oxide (EO) is exclusively made from ethylene by direct oxidation, using oxygen or air. This report establishes that using oxygen is more economical than using air. Existing EO plants are integrated with ethylene glycol (EG) production, with part or all EO processed into EG in situ. Plants can also be designed to produce essentially only marketable EO. All of these variations are evaluated.

Propylene oxide (PO) is made either by the chlorohydrin process or the hydroperoxide process. The chlorohydrin process needs lime or cell liquor for neutralization; in the latter case, the PO plant is virtual- ly integrated with a chlorine plant. The hydroperoxide process uses or to coproduce t-butyl alcohol or . All of these processes, with variations in the methods of treatment of the recycle in the case of chlorohydrin process and in the amount of coproduction in the case of isobutane hydroperoxide process, are evalu- ated in this report.

The numerous noncommercial processes briefly evaluated include: a chlorohydrin process involving tert butyl hypochlorite; another chloro- hydrin process using ally1 chloride; several hydroperoxide processes using isobutane, cumene, or cyclohexene; a glycol acetate process; and a peracid process. Given the present s.tateof the art and trade, none of them is viable. The most economical process for making PO remains the hydroperoxide process, with coproduction of grade t-butyl alcohol; next are the hydroperoxide process with coproduction of styrene and the chlorohydrin process using lime or cell liquor.

PEP'84 YCY CSL Report No. 2D

ETHYLENE OXIDE/PROPYLENE OXIDE

SUPPLEMENT D

by YEN-CHEN YEN with contributions by CHUN-SAN LIU

February 1985

A private report by the PROCESS ECONOMICS PROGRAM

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 Program covers major hydrocarbons and their derivatives on a worldwide basis. In addition, the SRI DIRECTORY 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 Technical Aspects ...... 9 Conventional Chlorohydrin Process ...... 9 Chlorohydrin Process Using Cell Liquor ...... 9 Tertiary Butyl Hypochlorite Process ...... 9 Ally1 Chloride Process ...... 10 Hydroperoxide Process Using Isobutane ...... 10 Hydroperoxide Process Using Ethylbenzene ...... 10 Peracid Process ...... 10 Glycolacetate Process ...... 11

3 INDUSTRY STATUS ...... 13 Ethylene Oxide ...... 13 Propylene Oxide ...... 14

4 ETHYLENE OXIDE...... 25 Chemistry ...... 25 Review of Processes ...... 26 Catalyst ...... 26 Gas Composition ...... 30 Reactors ...... 32 Recovery of Ed ...... 32 Wastes ...... 32 Processes ...... 33 Making EO by the Oxygen Process ...... 34 Process Description ...... 34 Process Discussion ...... 43 Cost Estimates ...... 47 Making EO by the Air Process ...... 59 Process Description ...... 59 Cost Estimates ...... 65

5 PROPYLENE OXIDE BY THE CHLOROHYDRIN PROCESS ...... 75 Review of the Processes ...... 75 Evaluation of a Conventional Chlorohydrin Process ...... 80 Process Description ...... 80 Process Discussion ...... 82

iii CONTENTS

5 PROPYLENE OXIDE BY THE CHLOROHYDRIN PROCESS (continued) Cost Estimates ...... 83 Evaluation of a Chlorohydrin Process Using Cell Liquor for Saponification ...... 90 Process Description ...... 90 Process Discussion ...... 95 CostEstimates ...... 96 The Lummus Chlorohydrin Process for Making Propylene Oxide ...... 104 Process Description ...... 104 Process Discussion ...... 112 Cost Estimates ...... 112 Naphtachimie Process ...... 118 Comparison of the Processes ...... 123

6 PROPYLENE OXIDE BY HYDROPEROXIDE PROCESSES ...... 125 Review of Processes ...... 125 Hydroperoxide Preparation ...... 125 Epoxidation ...... 126 Recovery of TBA ...... 127 Recovery of Styrene ...... 128 Evaluation of a Process for Making Propylene Oxide from Isobutane ...... 128 Process Description ...... 128 Process Discussion ...... 137 Isobutane Feed ...... 137 Propylene Feed ...... 137 Epoxidation ...... 137 Flexibility of Coproduction ...... 138 Cost Estimates ...... 141 Evaluation of a Process for Making Propylene Oxide from Ethylbenzene Using a Homogeneous Catalyst ...... 151 Process Description ...... 151 Process Discussion ...... 161 Cost Estimates ...... 161 Ethylbenzene Process Using a Heterogeneous Catalyst ..... 167 General Discussion of the Hydroperoxide Process and Prospects for Using Other Hydrocarbons for Making Hydroperoxide .... 167 A Process Based on Isopentane with Coproduction of t-Amy1 Alcohol ...... 168 Process Based on Cumene with the Coproduction of alpha-Methylstyrene ...... 169

iv CONTENTS

6 PROPYLENE OXIDE BY HYDROPEROXIDE PROCESSES (continued) A Process Based on Ethyltoluene, with Coproduction of p-Methylstyrene ...... 170 A Process Based on Cyclohexane with Coproduction ofPhenol ...... 172 A Process Based on Cyclohexane with Coproduction of Caprolactam ...... ; ...... 172

7 OTHER PROCESSES FOR MAKING PROPYLENE OXIDE ...... 175 Propylene Oxide by Epoxidation of Propylene with Hydrogen Peroxide ...... 175 Propylene Oxide by Peracid Made from Hydrogen Peroxide . . . . 176 Propylene Oxide by Peracid Made from Aldehydes ...... 181 Propylene Oxide by Direct Oxidation with Molecular Oxygen. . . 181 Propylene Oxide by Monoacetate Pyrolysis . . 182 Propylene Oxide from ...... 183 Fermentation Process ...... 186

APPENDIX HEALTH HAZARD ...... 189

PATENT SUMMARY TABLES ...... 191

CITED REFERENCES ...... 241

PATENT REFERENCES ...... 259

V ILLUSTRATIONS

4.1 Effect of Promoters in a Silver Catalyst ...... 28 4.2 Effect of Co-Promoters on Potassium-Promoted Silver Catalyst ...... 29 4.3 Flammability of Gas Mixture (C2H4-021nerts) ...... 31 a 4.4 Ethylene Oxide by Oxygen Process Flow Sheet ...... 267 4.5 Recovery of Ethylene Oxide for a Plant Making Marketable Ethylene Oxide Only ...... 45 4.6 Recovery of Ethylene Oxide for a Plant Producing EO for Ethylene Glycol Only ...... 46 4.7 Ethylene Oxide by Air Process Flow Sheet ...... 271 5.1 Propylene Oxide by Chlorohydrin Process with Saline Water Discharged to Brine Wells ...... 78 5.2 Propylene Oxide by Conventional Chlorohydrin Process Flow Sheet ...... 273 5.3 Propylene Oxide by Chlorohydrin Process Using Cell Liquor Flow Sheet ...... 277 5.4 Propylene Oxide by Chlorohydrin Process Via Tert-Butyl Hypochloride Flow Sheet ...... 281 5.5 Propylene Oxide from Ally1 Chloride Flow Sheet ...... 285 6.1 Propylene Oxide by the Isobutane Process with Butyl Alcohol Coproduction a Flow Sheet ...... 287 6.2 Flexibility of Coproduction ...... 140 6.3 Propylene Oxide by the Isobutane Process Effect of Operation and Plant Capacity on Production Cost ...... 148 6.4 Effect of Oxinol and Methanol Prices on Propylene Oxide Product Value ...... 150 6.5 Propylene Oxide by Ethylbenzene Process Flow Sheet ...... 291

Vii ILLUSTRATIONS

6.6 Propylene Oxide by the Ethylbenzene Process Effect of Operating Level and Plant Capacity on Production Cost ...... 166 7.1 Propylene Oxide by Propylene Glycol Monoacetate Pyrolysis Flow Sheet ...... 297

Viii TABLES

2.1 Ethylene Oxide Processes Summary of Economics ...... 4 2.2 Commercial Processes for Making Propylene Oxide Summary of Economics ...... 6 2.3 Processes Under Development for Making Propylene Oxide Summary of Economics ...... 8 3.1 U.S. Producers of Ethylene Oxide ...... 15 3.2 Producers of Ethylene Oxide Outside the United States . . . 16 3.3 U.S. Producers of Propylene Oxide ...... 19 3.4 Producers of Propylene Oxide Outside the United States . . . 20 4.1 Catalysts for Making Ethylene Oxide Patentsummary...... 192 4.2 Ethylene Oxide Production Patent Summary...... 218 4.3 Ethylene Oxide by the Oxygen Process Design Bases and Assumptions ...... 35 4.4 Ethylene Oxide by the Oxygen Process (50% Marketable EO, 50% for EG) Stream Flows ...... 38 4.5 Ethylene Oxide by the Oxygen Process (50% Marketable EO, 50% for EG) Major Equipment ...... 40 4.6 Ethylene Oxide by the Oxygen Process (50% Marketable EO, 50% for EG) Utilities Summary ...... 42 4.7 Ethylene Oxide by the Oxygen Process (50% Marketable EO, 50% for EG) Total Capital Investment ...... 49 4.8 Ethylene Oxide by the Oxygen Process (50% Marketable EO, 50% for EG) Production Costs ...... 51 4.9 Ethylene Oxide by the Oxygen Process (All Marketable EO) Total Capital Investment ...... 53

iX TABLES

4.10 Ethylene Oxide by the Oxygen Process (All Marketable EO) Production Costs ...... 54 4.11 Ethylene Oxide by the Oxygen Process (All EO for EG) Total Capital Investment ...... 56 4.12 Ethylene Oxide by the Oxygen Process (All EO for EG) Production Costs ...... 57 4.13 Ethylene Oxide by the Air Process Design Bases and Assumptions ...... 60 4.14 Ethylene Oxide by the Air Process (50% Marketable EO, 50% for EG) StreamFlows...... 62 4.15 Ethylene Oxide by the Air Process (50% Marketable EO, 50% for EG) Major Equipment ...... 63 4.16 Ethylene Oxide by the Air Process (50% Marketable EO, 50% for EG) Utilities Summary ...... 64 4.17 Ethylene Oxide by the Air Process (50% Marketable EO, 50% for EG) Total Capital Investment ...... 66 4.18 Ethylene Oxide by the Air Process (50% Marketable EO, 50% for EG) Production Costs ...... 67 4.19 Ethylene Oxide by the Air Process (All Marketable EO) Total Capital Investment ...... 69 4.20 Ethylene Oxide by the Air Process (All Marketable EO) Production Costs ...... 70 4.21 Ethylene Oxide by the Air Process (All EO for EG) Total Capital Investment ...... 72 4.22 Ethylene Oxide by the Air Process (All EO for EG) Production Costs ...... 73

X TABLES

5.1 Propylene Oxide by the Conventional Chlorohydrin Process Patentsummary...... 220 5.2 Electrolytic Chlorohydrin Process for Making Propylene Oxide Patent Summary...... 222 5.3 Propylene Oxide by Lummus Chlorohydrin Process Patentsummary...... 223 5.4 Propylene Oxide by the Conventional Chlorohydrin Process Total Capital Investment ...... 85 5.5 Propylene Oxide by the Conventional Chlorohydrin Process Production Costs ...... 87 5.6 Improvements in the Conventional Chlorohydrin Process Economic Effects ...... 89 5.7 Propylene Oxide by the Chlorohydrin Process Using Cell Liquor Design Bases and Assumptions ...... 91 5.8 Propylene Oxide by the Chlorohydrin Process Using Cell Liquor Stream Flows ...... 92 5.9 Propylene Oxide by the Chlorohydrin Process Using Cell Liquor Neutralization Major Equipment ...... 93 5.10 Propylene Oxide by the Chlorohydrin Process Using Cell Liquor Neutralization Utilities Summary ...... 94 5.11 Propylene Oxide by the Chlorohydrin Process Using Cell Liquor Neutralization Total Capital Investment ...... 98 5.12 Propylene Oxide by the Chlorohydrin Process Using Cell Liquor Neutralization Production Costs ...... 100 5.13 Propylene Oxide by the Chlorohydrin Process Using Cell Liquor Neutralization and Saline Liquor for Dissolving Solid Salt Production Costs ...... 102

xi TABLES

5.14 Lummus Chlorohydrin Process for Making Propylene Oxide Design Bases and Assumptions ...... 105 5.15 Propylene Oxide by the Chlorohydrin Process Via Tert-Butyl Hypochlorite StreamFlows...... 108 5.16 Propylene Oxide by the Chlorohydrin Process Via Tert-Butyl Hypochlorite Major Equipment ...... 110 5.17 Propylene Oxide by the Chlorohydrin Process Via Tert-Butyl Hypochlorite Utilities Summary ...... 111 5.18 Propylene Oxide by the Chlorohydrin Process Via Tert-Butyl Hypochlorite Total Capital Investment ...... 114 5.19 Propylene Oxide by the Chlorohydrin Process Via Tert-Butyl Hypochlorite Production Costs ...... 116 5.20 Propylene Oxide from Ally1 Chloride Total Capital Investment ...... 120 5.21 Propylene Oxide from Ally1 Chloride Production Costs ...... 121 5.22 Comparison of Various Chlorohydrin Processes ...... 124 6.1 Hydroperoxide Preparation PatentSummary...... 225 6.2 Recovery of t-Butylhydroperoxide Patent Summary...... 227 6.3 t- Production from Isobutane Oxidation PatentSummary...... 227 6.4 Catalyst for Epoxidation by Hydroperoxide PatentSummary...... 228 6.5 Treatment after Epoxidation Patent Summary...... 230 6.6 TBA Coproduction in Making Propylene Oxide - by Isobutane Process Patent Summary...... 230 0 xii TABLES

Production of Styrene as a Coproduct of Propylene Oxide Patent Summary...... 231 6.8 Propylene Oxide by the Isobutane Process Design Bases and Assumptions ...... 129 6.9 Propylene Oxide by Isobutane Process with Tertiary Butyl Alcohol Coproduction ...... 132 6.10 Propylene Oxide by Isobutane Process with Butyl Alcohol Coproduction Major Equipment ...... 134 6.11 Propylene Oxide by the Isobutane Process with Butyl Alcohol Coproduction Utilities Summary ...... 136 6.12 Propylene Oxide by the Isobutane Process with Butyl Alcohol Coproduction Total Capital Investment ...... 144 6.13 Propylene Oxide by the Isobutane Process with Butyl Alcohol Coproduction Production Costs ...... 146 6.14 Isobutane Processes with Different Coproduction Ratio . . . 149 6.15 Propylene Oxide by the Ethylbenzene Process Using Homogeneous Catalyst Design Bases and Assumptions ...... 152 6.16 Propylene Oxide by the Ethylbenzene Process Using Homogeneous Catalyst Stream Flows ...... 155 6.17 Propylene Oxide by the Ethylbenzene Process Major Equipment ...... 157 6.18 Propylene Oxide by the Ethylbenzene Process Utilities Summary ...... 160 6.19 Propylene Oxide by the Ethylbenzene Process Total Capital Investment ...... 162 6.20 Propylene Oxide by the Ethylbenzene Process Production Costs ...... 164 6.21 Other Hydroperoxide Processes ...... 171

Xiii TABLES

7.1 Propylene Oxide by the Hydrogen Peroxide or Peracid Processes PatentSummary...... 232 7.2 Propylene Oxide by Perpropionic Acid Process Based on Bayer-Degussa Patents Total Capital Investment ...... 177 7.3 Propylene Oxide by Perpropionic Acid Process Based on Bayer-Degussa Patents Production Costs ...... 179 7.4 Propylene Oxide by Oxidation with Molecular Oxygen Patentsummary...... 235 7.5 Propylene Oxide by Propylene Glycol Monoacetate Patentsummary...... 237 7.6 Propylene Oxide by Propylene Glycol Monoacetate Pyrolysis Production Costs ...... 184 7.7 Propylene Oxide from Propylene Carbonate or Halogenated Propylene Carbonate Patent Summary...... 238 7.8 Propylene Oxide by Fermentation Patentsummary...... 239

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