PROCESS ECONOMICS PROGRAM SRI INTERNATIONAL mnlo Puk, cdifomim

Abstract

Process Economics Program Report No. 126

Cl CHLORINATEDHYDROCARBONS -

This report reviews the technology, economics and market status of the Cl chlorinated solvents. Methylene chloride is emphasized because of its emerging dominance on the market place over other chlorinated solvents and fluorocarbons which are beset by problems arising from stricter environmental pollution standards.

A detailed analysis is made of two major commercial processes for producing Cl chlorinated solvents: one using methane as the organic l feed, and the other using methanol. Methylene chloride is maximized as a product in relation to chloroform and carbon tetrachloride coprod- ucts. The methanol process is preferred because of a recycle use of by-product hydrogen chloride.

Methyl chloride is an intermediate and is recycled to extinction in both processes. Otherwise it is largely a captive intermediate in making silicones and tetramethyl lead.

The technology and economics of a methane oxychlorination process are reviewed briefly. As yet, there is no known commercial application of this process.

Two commercial carbon tetrachloride processes are reviewed: the chlorination of carbon disulfide, and the Coproduction of carbon tetra- chloride and perchloroethylene from Cl-C3 hydrocarbons and chlorinated derivatives. A third process, the severe chlorinolysis of waste chlorinated residues, is also included. - Report No. 126

*e C1 CHLORINATED HYDROCARBONS

by LEONARD A. WASSELLE

cl August 1978 a A private report by the m 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 CHEMICALECONOMICS HANDBOOK Program covers most major chemicals and chemical products produced in the United States and the WORLDPETROCHEMICALS Program covers major hydrocarbons and their derivatives on a worldwide basis. In addition, the SRI DIRECTORYOF CHEMICALPRODUCERS 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 Markets ...... 3 Methylene Chloride...... , . 3 Chloroform...... 4 Carbon Tetrachloride...... 4 Methyl Chloride ...... 5 International ...... 6 Economic Aspects...... 8 Methylene Chloride from Methane or Methanol ...... 8 Methylene Chloride by Oxychlorination of Methane. . . . . 11 Carbon Tetrachloride...... 13 Technical Aspects ...... 14 Methane Chlorination...... , . 19 Methanol Hydrochlorination...... 22 Oxychlorination of Methane...... 22 Carbon Tetrachloride from Carbon Disulfide...... 23 Carbon Tetrachloride and Perchloroethylene from Propylene ...... 23 Chlorinolysis of Chlorinated Residues to Carbon Tetrachloride ...... 24 Licensing ...... 25

3 INDUSTRY STATUS ...... 27 Methylene Chloride...... 27 Chloroform...... 30 Carbon Tetrachloride...... 32 Methyl Chloride ...... 35 Worldwide Production...... 41

4 CHLOROMETHANES BY THERMAL CHLORINATION OF METHANE ..... 49 Introduction...... 49 Chemistry ...... 50 Review of Processes ...... 60 Process Description ...... 71 Process Discussion...... 83 Cost Estimates...... 88 Capital Costs ...... 88 Production Costs...... 89

ix CONTENTS

5 CHLOROMETHANES FROM METHANOL AND CHLORINE ...... 97 - Introduction...... 97 Chemistry...... 100 Hydrochlorination of Methyl Alcohol ...... 100 Chlorination of Methyl Chloride ...... 102 Review of Processes ...... 106 Process Description ...... 118 . a- Process Discussion...... 131 Cost Estimates...... 133 Capital Costs ...... 133 Production Costs...... 134

6 CARBON TETRACHLORIDE BY CHLORINATION OF CARBON DISULFIDE ...... 143 Chemistry ...... 143 Review of Processes ...... 144 Process Description ...... 147 Cost Estimates...... 152

7 CARBON TETRACHLORIDE AND PERCHLOROETHYLENE BY PERCHLORINATION OF 1-3 CARBON HYDROCARBONS...... 157 Chemistry ...... 157 Review of Processes ...... 160 Process Description ...... 168 Cost Estimates...... 170

8 CARBON TETRACHLORIDE BY CHLORINOLYSIS OF CHLORINATED HYDROCARBON RESIDUES...... 175 Chemistry ...... 176 Review of Processes ...... 177 Process Description ...... 180 Cost Estimates...... 183

9 CHLOROMETHANES BY OXYCHLORINATION OF METHANE...... 189 Chemistry ...... 189 Review of Processes ...... 195 Process Description ...... 196 Cost Estimates...... 201

X CONTENTS

10 CHLOROMETHANES BY OTHER PROCESSES AND TECHNOLOGY...... 207 Carbon Tetrachloride from Phosgene...... 207 Electrolytic Preparation of Chloromethanes...... 210 Chloromethanes by Radiation Chlorination...... 210 Carbon Tetrachloride by Chlorination of Carbon...... 211 Miscellaneous Reactions ...... 212

11 STABILIZERS FOR CHLOROMETHANES...... 213

12 MATERIALS OF CONSTRUCTION IN CHLOROMETHANES PLANT DESIGNS ...... 219

APPENDIXA DESIGN AND COST BASIS ...... 223

APPENDIX B PHYSICAL DATA ...... 227

APPENDIX C PRODUCT SPECIFICATIONS AND ANALYSES ...... 237

APPENDIX D HANDLING AND HEALTHHAZARDS...... 241

APPENDIX E REPORT ON REGULATIONS BANNING AEROSOL PROPELLANT USES ...... 249

CITED REFERENCES...... 251

PATENT REFERENCES BY COMPANY ...... 265

Xi ILLUSTRATIONS

2.1 World Production of Cl Chlorocarbons ...... 7 - 3.1 Cl Chlorocarbons--U.S. Market, 1975...... 42

CHLOROMETHANES BY THERMAL CHLORINATION OF METHANE 4.1 Schematic Flow Diagram ...... 51 a- 4.2 Product Distribution--Hass and McBee ...... 58 4.3 Product Distribution--Dow...... 59 4.4 Partial Methane Chlorination--Mol Fraction Product CHxCly vs. Mol Ratio of Reactants at 475°C ...... 62 4.5 Partial Methane Chlorination--Mols Recycle vs. Mol Ratio of Reactants at 475“C...... 63 4.6 Methylene Chloride, Chloroform, and Carbon Tetrachloride by Chlorination of Methane Flow Diagram...... 271 4.7 Schematic Flow Diagram of Multiple Series Reactor system...... 87 a 4.8 Effect of Plant Capacity on Total Fixed Capital...... 94 4.9 Effect of Operating Level and Plant Capacity on Production Cost...... 95 4.10 Effect of Raw Material Prices on Net Production Cost . . . 96

CHLOROMETHANES FROM METHANOL AND CHLORINE 5.1 Schematic Flow Diagram ...... 99 5.2 Effect on Product Distribution by Varying Chlorine inFeed...... 107 5.3 Methyl Chloride from Methanol with Scrubbing System Schematic Flow Diagram ...... 110 5.4 Dry Methyl Chloride by Non-Catalytic Liquid Phase Hydrochlorination of Methanol Schematic Flow Diagram ...... 112 5.5 Methyl Chloride, Chloroform, and Carbon Tetrachloride from Methanol and Chlorine FlowDiagram...... 275 5.6 Effect of Plant Capacity on Total Fixed Capital...... 138

xiii ILLUSTRATIONS

5.7 Effect of Operating Level and Plant Capacity on Production Cost...... 140 5.0 Effect of Raw Material Prices on Net Production Cost . . . 141

CARBON TETRACHLORIDE BY CHLORINATION OF CARBON DISULFIDE

6.1 Stauffer Process Block Flow Diagram ...... 146 6.2 Flow Diagram...... 150 6.3 Effect of Plant Capacity on Total Fixed Capital...... 154 6.4 Effect of Operating Level and Plant Capacity on Production Cost...... 156

CARBON TETRACHLORIDE AND PERCHLOROETHYLENE BY PERCHLORINATION OF l-3 CARBON HYDROCARBONS 7.1 Flow Diagram...... 169 7.2 Effect of Plant Capacity on Total Fixed Capital...... 173 7.3 Effect o.fOperating Level and Plant Capacity on Production Cost...... 174

CARBON TETRACHLORIDE BY CHLORINOLYSIS OF CHLORINATED HYDROCARBON RESIDUES 8.1 Hoechst Process for the Chlorinolysis of Chlorinated Residues Flow Diagram...... 181 8.2 Effect of Plant Capacity on Total Fixed Capital...... 185 8.3 Effect of Operating Level and Plant Capacity on Production Cost...... 187

CHLOROMETHANES BY OXYCHLORINATION OF METHANE 9.1 Basic Transcat@ Process for Oxychlorination of Methane Block Flow Diagram . , ...... 197 9.2 Transcat@ Molten Salt Chlor/Oxy and Oxidation Reactor System Schematic Flow,Diagram ...... 198 9.3 Effect of Plant Capacity on Total Fixed Capital...... 203 9.4 Effect of Operating Level and Plant Capacity on Production Cost...... 205 . xiv l ILLUSTRATIONS

B.l Vapor Pressures of Chloromethanes, Perchloroethylene, a and Hexachloroethane ...... 228 B.2 Latent Heat of Liquids ...... 229 B.3 Specific Heat of Liquids ...... 230 B.4 Specific Heat of Vapors...... 231 l B.5 Liquid Density ...... 232 B.6 Heat of Formation...... 233 D.l Chlorinated Solvents (M2, M3, and M4> Unloading and Storage Installation ...... 242 D.2 Storage Tanks Horizontal Tank...... 243 D.3 Storage Tanks Vertical Solvent Storage System...... 244

a

a I a xv TABLES

2.1 Summary of Capital and Production Costs for Methylene Chloride and Coproducts...... 10

2.2 Chloromethanes by Oxychlorination Capital Investment and Production Costs...... 12 2.3 Summary of Capital and Production Costs for Carbon Tetrachloride Processes...... 15 2.4 Technical Summary of Methylene Chloride Processes. .... 16 2.5 Technical Suuunary of Carbon Tetrachloride Processes. ... 20 3.1 Methylene Chloride--U.S. Production and Related Data ... 29 3.2 Methylene Chloride--Major End Use Markets, ...... 29 3.3 Methylene Chloride --U.S. Producers and Capacities. .... 31 3.4 Chloroform--U.S. Production and Sales...... 33 3.5 Chloroform--U.S. Producers and Capacities...... 34 3.6 Carbon Tetrachloride--U.S. Production, Sales, Imports, and Consumption ...... 36 3.7 Carbon Tetrachloride--U.S. Producers and Capacities. ... 37 3.8 Methyl Chloride--U.S. Production ...... 39 3.9 Methyl Chloride --U.S. Producers and Capacities ...... 40 3.10 Cl Chlorocarbons--Producers and Capacities Outside the United States...... 43

CHLOROMETBANES BY THERMAL CRLORINATION OF METHANE 4.1 Product Distribution with Varying Molar Ratios of Chlorine to Methane...... 57 4.2 Product Distribution with Varying Feed and Recycle Conditions ...... 61 4.3 PatentSummary ...... 65 4.4 Bases and Assumptions...... 72 4.5 Major Equipment and Utilities Summary...... 79 4.6 StreamFlows ...... 81 4.7 Total Capital Investment ...... ?1 4.8 Working Capital...... 92 4.9 Production Costs ...... 93

xvii TABLES

CHLOROMETHANES FROM METHANOL AND CHLORINE 5.1 PatentSummary ...... 114 5.2 Bases and Assumptions...... 119 5.3 Major Equipment and Utilities Summary...... 126 5.4 Stream Flows ...... 129 5.5 Comparison of Maximum Methylene Chloride Product Distributions...... 132 5.6 Total Capital Investment ...... 136 5.7 Working Capital...... 137 5.8 Production Costs ...... 139

CARBON TETRACHLORIDE BY CHLORINATION OF CARBON DISULFIDE 6.1 Patentsummary...... 148 6.2 Capital Investment and Production Costs...... 155

CARBON TETRACHLORIDE AND PERCHLOROETHYLENE BY PERCHLORINATION OF l-3 CARBON HYDROCARBONS 7.1 PatentSummaryI...... 162 7.2 Patent SummaryII...... 166 7.3 Capital Investment and Production Costs. , ...... 172

CARBON TETRACHLORIDE BY CHLORINOLYSIS OF CHLORINATED HYDROCARBON RESIDUES 8.1 Patentsummary..... ; ...... 178 a.2 Capital Investment and Production Costs...... 186

CHLOROMETHANES BY OXYCHLORINATION OF METHANE 9.1 Patentsummary...... 191 9.2 Capital Investment and Production Costs...... 204

CHLOROMETHANES BY OTHER PROCESSES AND TECHNOLOGY 10.1 Patent Summary...... 208

STABILIZERS FOR CHLOROMETHANES 11.1 Patentsmary...... 215

xviii TABLES

B.l Physical Properties of Methylene Chloride, Chloroform, - and Carbon Tetrachloride ...... 234 B.2 Azeotropic Mixtures of Methylene Choride, Chloroform, and Carbon Tetrachloride ...... 235 c.1 Typical Product Specifications and Analysis of Methylene Chloride ...... 238 a- c.2 Typical Product Specifications and Analysis of Chloroform...... 239 c.3 Typical Product Specifications and Analysis of Carbon Tetrachloride ...... 240

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