PROCESS ECONOMICS PROGRAM

Transcription

1 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 coproducts. 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 tetrachloride and perchloroethylene from Cl-C3 hydrocarbons and chlorinated derivatives. A third process, the severe chlorinolysis of waste chlorinated residues, is also included.

2 Report No. 126 C1 CHLORINATED HYDROCARBONS by LEONARD A. WASSELLE a cl m A private report by the August 1978 PROCESS ECONOMICS PROGRAM Menlo Park, California 94025

3 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. ii

4 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... 3 INDUSTRY STATUS... Methylene Chloride.... Chloroform.... Carbon Tetrachloride.... Methyl Chloride... Worldwide Production......,..., CHLOROMETHANES BY THERMAL CHLORINATION OF METHANE... Introduction.... Chemistry... Review of Processes... Process Description... Process Discussion.... Cost Estimates.... Capital Costs... Production Costs ix

5 CONTENTS 5 CHLOROMETHANES FROM METHANOL AND CHLORINE Introduction Chemistry Hydrochlorination of Methyl Alcohol Chlorination of Methyl Chloride Review of Processes Process Description Process Discussion Cost Estimates Capital Costs Production Costs CARBON TETRACHLORIDE BY CHLORINATION OF CARBON DISULFIDE Chemistry Review of Processes Process Description Cost Estimates CARBON TETRACHLORIDE AND PERCHLOROETHYLENE BY PERCHLORINATION OF 1-3 CARBON HYDROCARBONS Chemistry Review of Processes Process Description Cost Estimates CARBON TETRACHLORIDE BY CHLORINOLYSIS OF CHLORINATED HYDROCARBON RESIDUES Chemistry Review of Processes Process Description Cost Estimates CHLOROMETHANES BY OXYCHLORINATION OF METHANE Chemistry Review of Processes Process Description Cost Estimates X

6 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 Xi

7 ILLUSTRATIONS 2.1 World Production of Cl Chlorocarbons Cl Chlorocarbons--U.S. Market, CHLOROMETHANES BY THERMAL CHLORINATION OF METHANE 4.1 Schematic Flow Diagram Product Distribution--Hass and McBee Product Distribution--Dow Partial Methane Chlorination--Mol Fraction Product CHxCly vs. Mol Ratio of Reactants at 475 C Partial Methane Chlorination--Mols Recycle vs. Mol Ratio of Reactants at 475 C Methylene Chloride, Chloroform, and Carbon Tetrachloride by Chlorination of Methane Flow Diagram Schematic Flow Diagram of Multiple Series Reactor system Effect of Plant Capacity on Total Fixed Capital Effect of Operating Level and Plant Capacity on Production Cost Effect of Raw Material Prices on Net Production Cost CHLOROMETHANES FROM METHANOL AND CHLORINE 5.1 Schematic Flow Diagram Effect on Product Distribution by Varying Chlorine infeed Methyl Chloride from Methanol with Scrubbing System Schematic Flow Diagram Dry Methyl Chloride by Non-Catalytic Liquid Phase Hydrochlorination of Methanol Schematic Flow Diagram Methyl Chloride, Chloroform, and Carbon Tetrachloride from Methanol and Chlorine FlowDiagram Effect of Plant Capacity on Total Fixed Capital xiii

8 ILLUSTRATIONS 5.7 Effect of Operating Level and Plant Capacity on Production Cost Effect of Raw Material Prices on Net Production Cost CARBON TETRACHLORIDE BY CHLORINATION OF CARBON DISULFIDE 6.1 Stauffer Process Block Flow Diagram Flow Diagram Effect of Plant Capacity on Total Fixed Capital Effect of Operating Level and Plant Capacity on Production Cost CARBON TETRACHLORIDE AND PERCHLOROETHYLENE BY PERCHLORINATION OF l-3 CARBON HYDROCARBONS 7.1 Flow Diagram Effect of Plant Capacity on Total Fixed Capital Effect o.f Operating Level and Plant Capacity on Production Cost CARBON TETRACHLORIDE BY CHLORINOLYSIS OF CHLORINATED HYDROCARBON RESIDUES 8.1 Hoechst Process for the Chlorinolysis of Chlorinated Residues Flow Diagram Effect of Plant Capacity on Total Fixed Capital Effect of Operating Level and Plant Capacity on Production Cost CHLOROMETHANES BY OXYCHLORINATION OF METHANE 9.1 Basic Process for Oxychlorination of Methane Block Flow Diagram., Molten Salt Chlor/Oxy and Oxidation Reactor System Schematic Flow,Diagram Effect of Plant Capacity on Total Fixed Capital Effect of Operating Level and Plant Capacity on Production Cost xiv

9 ILLUSTRATIONS B.l Vapor Pressures of Chloromethanes, Perchloroethylene, and Hexachloroethane B.2 Latent Heat of Liquids B.3 Specific Heat of Liquids B.4 Specific Heat of Vapors B.5 Liquid Density B.6 Heat of Formation D.l Chlorinated Solvents (M2, M3, and M4> Unloading and Storage Installation D.2 Storage Tanks Horizontal Tank D.3 Storage Tanks Vertical Solvent Storage System xv

10 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 ? xvii

11 TABLES CHLOROMETHANES FROM METHANOL AND CHLORINE PatentSummary Bases and Assumptions Major Equipment and Utilities Summary Stream Flows Comparison of Maximum Methylene Chloride Product Distributions Total Capital Investment Working Capital Production Costs CARBON TETRACHLORIDE BY CHLORINATION OF CARBON DISULFIDE 6.1 Patentsummary Capital Investment and Production Costs CARBON TETRACHLORIDE AND PERCHLOROETHYLENE BY PERCHLORINATION OF l-3 CARBON HYDROCARBONS 7.1 PatentSummaryI Patent SummaryII 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 CHLOROMETHANES BY OXYCHLORINATION OF METHANE 9.1 Patentsummary Capital Investment and Production Costs CHLOROMETHANES BY OTHER PROCESSES AND TECHNOLOGY 10.1 Patent Summary STABILIZERS FOR CHLOROMETHANES 11.1 Patentsmary xviii

12 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 c.3 Typical Product Specifications and Analysis of Carbon Tetrachloride xix