PROCESS ECONOMICS PROGRAM
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PROCESS ECONOMICS PROGRAM SRI INTERNATIONAL mnlo Puk, cdifomim Abstract Process Economics Program Report No. 126 Cl CHLORINATED HYDROCARBONS 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 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.
Transcript of PROCESS ECONOMICS PROGRAM
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PROCESS ECONOMICS
PROGRAM SRI INTERNATIONAL
mnlo Puk, cdifomim
Abstract
Process Economics Program Report No. 126
Cl CHLORINATED HYDROCARBONS
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
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.
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Report No. 126
C1 CHLORINATED HYDROCARBONS
by LEONARD A. WASSELLE
a cl m
August 1978
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 PETROCHEMICALS 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.
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CONTENTS
1 INTRODUCTION. . . . . . . . . . . . . . . . . . . . . . . . 1
2 SUMMARY.......................,,.
Markets ...................... Methylene Chloride. ...............
Chloroform. ...................
Carbon Tetrachloride. ..............
Methyl Chloride .................
International ..................
Economic Aspects. .................
Methylene Chloride from Methane or Methanol ...
Methylene Chloride by Oxychlorination of Methane. Carbon Tetrachloride. ..............
Technical Aspects .................
Methane Chlorination. .............. Methanol Hydrochlorination. ...........
Oxychlorination of Methane. ...........
Carbon Tetrachloride from Carbon Disulfide. ...
Carbon Tetrachloride and Perchloroethylene from Propylene ....................
Chlorinolysis of Chlorinated Residues to Carbon Tetrachloride ..................
Licensing ....................
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3 INDUSTRY STATUS ......................
Methylene Chloride. ....................
Chloroform. ........................
Carbon Tetrachloride. ...................
Methyl Chloride ......................
Worldwide Production. ...................
4 CHLOROMETHANES BY THERMAL CHLORINATION OF METHANE .....
Introduction. .......................
Chemistry .........................
Review of Processes ....................
Process Description ....................
Process Discussion. ....................
Cost Estimates. ......................
Capital Costs ......................
Production Costs. ....................
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3 3 4 4 5 6 8 8 11 13 14 19 22 22 23
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27 30 32 35 41
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49 50 60 71 83 88 88 89
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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
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
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CONTENTS
CHLOROMETHANES BY OTHER PROCESSES AND TECHNOLOGY. .....
Carbon Tetrachloride from Phosgene. ............ Electrolytic Preparation of Chloromethanes. ........
Chloromethanes by Radiation Chlorination. .........
Carbon Tetrachloride by Chlorination of Carbon. ......
Miscellaneous Reactions ..................
STABILIZERS FOR CHLOROMETHANES. ..............
MATERIALS OF CONSTRUCTION IN CHLOROMETHANES PLANT DESIGNS ..........................
APPENDIXA DESIGN AND COST BASIS ..............
APPENDIX B PHYSICAL DATA ..................
APPENDIX C PRODUCT SPECIFICATIONS AND ANALYSES ......
APPENDIX D HANDLING AND HEALTHHAZARDS. ..........
APPENDIX E REPORT ON REGULATIONS BANNING AEROSOL PROPELLANT USES .................
CITED REFERENCES. .......................
PATENT REFERENCES BY COMPANY ..................
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207 210
210 211
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ILLUSTRATIONS
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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
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
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
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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.f Operating 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
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ILLUSTRATIONS
B.l Vapor Pressures of Chloromethanes, Perchloroethylene, and Hexachloroethane ................... 228
B.2 Latent Heat of Liquids .................. 229
B.3 Specific Heat of Liquids ................. 230
B.4 Specific Heat of Vapors. ................. 231
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
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2.1
2.2
2.3
2.4
2.5
3.1
3.2
3.3
3.4
3.5
3.6
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3.9
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4.1
4.2
4.3
4.4
4.5
4.6
4.7
4.8
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TABLES
Summary of Capital and Production Costs for Methylene Chloride and Coproducts. .................
Chloromethanes by Oxychlorination Capital Investment and Production Costs. .........
Summary of Capital and Production Costs for Carbon Tetrachloride Processes. .................
Technical Summary of Methylene Chloride Processes. ....
Technical Suuunary of Carbon Tetrachloride Processes. ...
Methylene Chloride--U.S. Production and Related Data ...
Methylene Chloride--Major End Use Markets, ........
Methylene Chloride --U.S. Producers and Capacities. ....
Chloroform--U.S. Production and Sales. ..........
Chloroform--U.S. Producers and Capacities. ........
Carbon Tetrachloride--U.S. Production, Sales, Imports, and Consumption .................
Carbon Tetrachloride--U.S. Producers and Capacities. ...
Methyl Chloride--U.S. Production .............
Methyl Chloride --U.S. Producers and Capacities ......
Cl Chlorocarbons--Producers and Capacities Outside the United States. ....................
CHLOROMETBANES BY THERMAL CRLORINATION OF METHANE
Product Distribution with Varying Molar Ratios of Chlorine to Methane. ...................
Product Distribution with Varying Feed and Recycle Conditions ........................
PatentSummary ......................
Bases and Assumptions. ..................
Major Equipment and Utilities Summary. ..........
StreamFlows .......................
Total Capital Investment .................
Working Capital. .....................
Production Costs .....................
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TABLES
CHLOROMETHANES FROM METHANOL AND CHLORINE
PatentSummary ...................... 114
Bases and Assumptions. .................. 119
Major Equipment and Utilities Summary. .......... 126
Stream Flows ....................... 129
Comparison of Maximum Methylene Chloride Product Distributions. ...................... 132
Total Capital Investment ................. 136
Working Capital. ...................... 137
Production Costs ..................... 139
5.1
5.2
5.3
5.4
5.5
5.6
5.7
5.8
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
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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
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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