Document 2JpYLdOXkwy8bvDjY3XExOgb6

VINYL CHLORIDE Supplement b A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INS". .TFT MENLO PARK. CALIFORNIA o Report No. 5B Supplement VINYL CHLORIDE by YU-REN CHIN and KENNETH E. LUNDE September 1975 t A private report by the PROCESS ECONOMICS PROGRAM [SBJD STANFORD RESEARCH INSTITUTE MENLO PARK. CALIFORNIA GGC 002502 CONTENTS 1 INTRODUCTION ............................................................................................................. 2 SUMMARY ...................................................................................................................... 3 INDUSTRY STATUS .................................................................................................... 4 LICENSED PROCESSES ............................................................................................... Balanced Ethylene Chlorination-Oxychlorination Processes . . The Chloe Balanced Chlorination-Oxychlorination Process . , The Kureha-Chiyoda Acetylene-Ethylene Process ............................. The Transcat Process .......................................................................................... 5 REVIEW OF PATENTS BY LICENSOR ................................................................... Review of Goodrich and Hoechst Patents ................................................ Ethylene Oxychlorination ............................................................................ Ethylene Chlorination ................................................................................. Ethylene Dichloride Pyrolysis ........................................................... Ethylene Dichloride Purification ......................................................... Vinyl Chloride Purification ................................................................... Hydrogen Chloride Purification... ................................................... Review of Imperial Chemical Industries, Ethyl Corporation, and Solvay Patents............................................................................................... Ethylene Oxychlorination ............................................................................ Ethylene Chlorination............................ Ethylene Dichloride Pyrolysis ........................................................... Ethylene Dichloride Purification . , ................................................ Vinyl Chloride Purification ................................................................... Review of Kureha Patents ................................................................................. Acetylene Hydrochlorination ................................................................... Ethylene Chlorination ................................................................................. Ethylene Dichloride Pyrolysis ........................................................... Review of Lummus Patents ................................................................................. Review of Mitsui Toatsu Patents ........................................................... Ethylene Oxychlorination ............................................................................ Ethylene Chlorination ................................................................................. Ethylene Dichloride Pyrolysis ........................................................... Vinyl Chloride Purification ................................................................... Review of Monsanto Patents ............................................................................ Ethylene Oxychlorination ............................................................................. Ethylene Chlorination ................................................................................. Ethylene Dichloride Pyrolysis ........................................................... Vinyl Chloride Purification ................................................................... 1 3 13 27 27 29 30 30 33 33 33 34 34 36 38 38 38 38 39 40 41 41 42 42 42 43 43 45 45 46 46 47 47 47 48 48 49 vii GGC 002503 CONTENTS 5 (Continued) Review of PPG Patents............................................................................................. Ethylene Oxychlorination ....................................................................... Ethylene Dichloride Purification andRecovery ........................... Review of Rhone Progil Patents .............................................................. Chlorination-Oxychlorination Process .................................................. Ethylene Oxychlorination ............................................................................... Review of Stauffer Patents ............................................................................... Ethylene Oxychlorination ....................................................................... Ethylene Dichloride Purification andRecovery ........................... Review of Toa Gosei Patents............................................................................... Ethylene Oxychlorination ....................................................................... Ethylene Chlorination ................................................................................. Hydrogen Chloride and EthyleneDichlorideRecovery ... Ethylene Dichloride Pyrolysis .............................................................. Review of Tokuyama Soda Patents .............................................................. Ethylene Oxychlorination ....................................................................... Ethylene Chlorination ................................................................................. Review of Toya Soda Patents....................................................................... Ethylene Oxychlorination ....................................................................... Ethylene Dichloride Recovery .............................................................. Review of Vulcan and Union Carbide Patents ................................. 50 50 52 53 53 54 56 56 58 58 59 60 60 60 60 60 61 62 62 63 64 6 REVIEW OF PATENTS: NONLICENSED PROCESSES ...................................... 135 Ethylene Dichloride by Ethylene Chlorination ................................... Ethylene Dichloride by Ethylene Oxychlorination ............................... Ethylene Dichloride by Ammonium Chloride Oxychlorination .......................................................................................................... Ethylene Dichloride Purification ................................................................ Vinyl Chloride by Ethylene Dichloride Pyrolysis ......................... Vinyl Chloride by Ethylene Chlorination ............................................ Vinyl Chloride by Ethylene Oxychlorination ................................... Vinyl Chloride by Ethylene Dichloride by Ethane Oxychlorination .......................................................................................................... Vinyl Chloride by Acetylene Hydrochlorination ................................... Vinyl Chloride or Ethylene Dichloride by Nitrosyl Chloride Processes ................................................................................................. Vinyl Chloride by Ethylene Dichloride by Transhalogenation ...................................................................................................... 135 138 140 142 142 143 147 151 152 154 155 I viii ) GGC 002504 CONTENTS 7 VINYL CHLORIDE MONOMER BY A BALANCED ETHYLENE CHLORINATION-OXYCHLORINATION PROCESS .................................................... Process Description .......................................................................................... Process Discussion ............................................................................................... Cost Estimates........................................................................................................ 8 VINYL CHLORIDE MONOMER FROM CRUDE OIL ACETYLENE AND ETHYLENE............................................................................................................. Process Description .......................................................................................... Process Discussion ............................................................................................... Cost Estimates........................................................................................................ 9 VINYL CHLORIDE BY THE TRANSCAT PROCESS ................................................. APPENDIX A DESIGN AND COST BASIS,DEFINITIONS ....................................... APPENDIX B PHYSICAL DATA...................................................................................... APPENDIX C SAFETY......................................................................................................... CITED REFERENCES............................................................................................................. PATENT REFERENCES BY COMPANY ........................................................................... 195 195 198 200 217 217 222 224 243 249 253 255 257 275 ix GGC 002505 ILLUSTRATIONS 6.1 Reaction Rates in Ammonium Chloride Oxychlorination .... 6.2 Reaction in Ethylene Oxychlorination ................................................ 7.1 Vinyl Chloride Monomer by a Balanced Ethylene Chlorination and Oxychlorination Process ...................................... 7.2 Vinyl Chloride Monomer by a Balanced Ethylene Chlorination and Oxychlorination Process Effect of Operating Level and Plant Capacity on Production Cost.......................................................................................... 8.1 Vinyl Chloride Monomer from Crude Oil Acetylene and Ethylene........................................................................................................ 8.2 Vinyl Chloride Monomer from Crude Oil Acetylene and Ethylene Effect of Operating Level and Plant Capacity on Production Cost.......................................................................................... 192 193 283 215 287 242 xi OGC 02506 TABLES 2.1 Vinyl Chloride Monomer Manufacture Comparison of Process Economics ............................................................. 6 3.1 Vinyl Chloride Monomer Plant Capacities North America.............................................................................................................. 16 3.2 Vinyl Chloride Monomer Plant Capacities Latin America.............................................................................................................. 17 3.3 Vinyl Chloride Monomer and Ethylene Dichloride Plant Capacities Western Europe ......................................................................................................... 18 3.4 Vinyl Chloride Monomer and Ethylene Dichloride Plant Capacities Asia and Oceania..................................................................................................... 21 3.5 Vinyl Chloride Monomer Plant Capacities Eastern Europe, Middle East,and Africa .................................................... 24 5.1 Vinyl Chloride Monomer Process Patent Summary: Goodrich and Hoechst ............................................... 68 5.2 Vinyl Chloride Monomer Process Patent Summary: ICI, Ethyl Corporation, Solvay & Cie ... 74 5.3 Vinyl Chloride Monomer Process Patent Summary: Kureha Chemical Industries ................................. 82 5.4 Vinyl Chloride Monomer Process Patent Summary: Lummus ................................................................................ 86 5.5 Vinyl Chloride Monomer Process Patent Summary: Mitsui Toatsu Chemicals ..................................... 88 5.6 Vinyl Chloride Monomer Process Patent Summary: Monsanto ........................................................................... 98 5.7 Vinyl Chloride Monomer Process Patent Summary: PPG..................................................................................... 102 5.8 Vinyl Chloride Monomer Process Patent Summary: Rhone Progil .................................................................. 110 5.9 Vinyl Chloride Monomer Process Patent Summary: Stauffer Chemical Company ................................. 116 5.10 Vinyl Chloride Monomer Process Patent Summary: Toa Gosei Chemical Industry ............................ 120 xiii OGC 00250? TABLES 5.11 Vinyl Chloride Monomer Process Patent Summary: Tokuyama Soda .............................................................. 5.12 Vinyl Chloride Monomer Process Patent Summary: Toya Soda........................................... 5.13 Vinyl Chloride Monomer Process Patent Summary: Vulcan andUnion Carbide . ................................ 6.1 Ethylene Dichloride by Ethylene Chlorination Patent Summary ................................................................................................... 6.2. Ethylene Dichloride by Ethylene Oxychlorination Patent Summary ................................................................................................... 6.3 Ethylene Dichloride by Ammonium Chloride Oxychlorination Patent Summary ................................................................................................... 6.4 Vinyl Chloride by Ethylene Dichloride Pyrolysis Patent Summary........................................................................... 6.5 Vinyl Chloride by Ethylene Chlorination Patent Summary.......................................................................... 6.6 Vinyl Chloride by Ethylene Oxychlorination Patent Summary........................................................................... 6.7 Vinyl Chloride or Ethylene Dichloride by Ethane Oxychlorin Oxychlorination Patent Summary ................................................................................................... 6.8 Vinyl Chloride by Acetylene Hydrochlorination Patent Summary ................................................................................................... 7.1 Vinyl Chloride Monomer by a Balanced Ethylene ChlorinationOxychlorination Process Summary of Operating Conditions ......................................................... 7.2 Vinyl Chloride Monomer by a Balanced Ethylene Chlorination-Oxychlorination Process Major Process Equipment and Utilities Summary ........................ 7.3 Vinyl Chloride Monomer by a Balanced Ethylene Chlorination-Oxychlorination Process Stream Flows ........................................................................................................ 7.4 Vinyl Chloride Monomer by a Balanced Ethylene Chlorination and Oxychlorination Process Total Capital Investment ............................................................................ 126 128 132 158 164 170 172 176 182 188 190 196 202 206 210 xiv GGC 002508 TABLES 7.5 7.6 7.7 8.1 8.2 8.3 8 .4 8.5 8.6 8.7 9.1 9.2 Vinyl Chloride Monomer by a Balanced Ethylene Chlorination and Oxychlorination Process Capital Investment by Process Section ........................ . .. . Vinyl Chloride Monomer by a Balanced Ethylene Chlorination-Oxychlorination Process Production Costs ...................................................................................... . Vinyl Chloride Monomer by a Balanced Ethylene and Oxychlorination Process Production Costs by Process Section .......................................... . . Vinyl Chloride Monomer from Crude Oil Acetylene and Ethylene Summary of Operating Conditions ................................................ . . Vinyl Chloride Monomer from Crude Oil Acetylene and Ethylene Major Process Equipment and Utilities Summary .................... . Vinyl Chloride Monomer from Crude Oil Acetylene and Ethylene Stream Flows .......................................................................................... ,. . Vinyl Chloride Monomer from Crude Oil Acetylene and Ethylene Total Capital Investment .............................................................. .. . Vinyl Chloride Monomer from Crude Oil Acetylene and Ethylene Capital Investment by Process Section ....................................... . Vinyl Chloride Monomer from Crude Oil Acetylene and Ethylene Production Costs ..................................................................................... . . Vinyl Chloride Monomer from Crude Oil Acetylene and Ethylene Production Costs by Process Section ............................................ . Vinyl Chloride Monomer by the Transcat Process Total Capital Investment .............................................................. ,, . Vinyl Chloride Monomer by the Transcat Process Production Costs ..................................................................................... 211 213 214 218 226 230 237 238 240 241 244 xv GGC 002509 2 SUMMARY General Aspects The worldwide plant capacity for vinyl chloride monomer was approxi mately 12 million metric tons per year in 1974. About 17% of this capac ity was new in 1974. Capacity additions in the United States, Western Europe, and Japan in 1974 amounted to only about 10% of the total for that year. Major future additions to vinyl chloride capacity have been an nounced for all parts of the world, with the notable exception of the United States. The largest percentage expansion is to take place in Eastern Europe, where announced future new capacity will be double the 1974 capacity of 700,000 metric tons per year. Also some of the major petrochemical complexes being planned in OPEC countries will include production of vinyl chloride. With all the new capacity and a slowing of demand for polyvinyl chloride, the supply of vinyl chloride monomer will probably be ample at least for the immediate future. The incidence of a form of liver cancer (angiosarcoma) in workers exposed to vinyl chloride monomer has resulted in severe restrictions in the United States and Sweden on maximum allowable concentrations of vinyl chloride in the work area. The problem is much less serious in monomer plants than in polymer plants because most of a monomer plant is out-ofdoors and nearly all streams are enclosed. The principal sources of emissions from a monomer plant are tank car loading, vents, and leaks from pumps and flanges. The U.S. Environmental Protection Agancy (EPA) has estimated that, in the past, total emissions from a monomer plant could have amounted to as much as 0.17. of the production. Ten companies or groups of companies offer basically similar bal anced ethylene chlorination-oxychlorination processes for license. No one licensor has a patent structure covering all parts of any one overall 3 GGC 002510 process; much of the technology seems to be based on know-how. As far as can be discerned from the patent and trade literature, the most dis tinguishing difference among the various processes is the use of fixed or fluid bed reactors in the oxychlorination step. iSeveral licensors use chlorination to recover unreacted ethylene in oxychlorination off gases. Also, oxygen rather than air is used for oxychlorination in some processes; the greatly reduced volume of offgases would be a signi ficant advantage if the offgases have to be incinerated for hydrocarbon pollution abatement. A few of the licensed processes are distinctly different. The Rhone-Progil process is a balanced ethylene chlorination and oxychlori nation process, but employs nonselective chlorination; chlorinated sol vents are coproducts. The Lummus Transcat process is also basically a balanced chlorination and oxychlorination process, but it uses a molten salt as the catalyst and ethane as the hydrocarbon feedstock. Chlori nated by-products can be recovered as chlorinated solvents, or they can be burned in the process along with other by-products to recover their chlorine values. The Transcat process has not yet been commercialized for vinyl chloride, but the process will be used for chloromethane pro duction in a plant now under construction. The only extant process based on hydrochlorination and chlorination of ethylene-acetylene streams is offered by Kureha-Chiyoda, The process uses high-temperature cracking of crude oil or naphtha to produce an equimolar mixture of ethylene and acetylene. There are no new processes starting from ethylene that seem likely to challenge the conventional balanced ethylene chlorination and oxy chlorination process. However, it is possible that feedstock prices and availability as well as increased investment costs could alter the eco nomics among processes using different feedstocks. Hence in this report, costs have been estimated for the balanced ethylene chlorination and oxy chlorination process and for acetylene-ethylene hydrochlorination and chlorination, with crude oil as the feedstock. These costs and the 4 GGC 002511 updated costs for ethane chlorination-oxychlorination by the Transcat process are compared in Table 2,1. The capital investment needed for vinyl chloride production from crude oil acetylene-ethylene is much greater than that for ethylene chlo rination-oxychlorination because the former includes the investment in crude oil cracking and cracked gas purification. The allocated battery limits investment for ethylene production from gas oil amounts to about $35 million. Thus the total battery limits investment for vinyl chloride production with gas oil cracking and balanced ethylene chlorinationoxychlorination amounts to about $54 million. This investment is signi ficantly greater than that for the crude oil acetylene-ethylene process and is more than double that for ethane chlorination-oxychlorination. On this more comparable basis, both the crude oil acetylene-ethylene pro cess and the ethane chlorination and oxychlorination process seem attrac tive . Hydrocarbon feedstock costs are one of the most important elements in vinyl chloride production costs. Those indicated above are on a mu tually consistent basis for U.S. conditions and are derived from SRI's energy studies (see Process Economics Reviews, Report X-l). Some advan tage is indicated in net operating costs for the crude oil acetyleneethylene process over those for the ethylene chlorination and oxychlori nation process. However, this advantage is greatly dependent on the value of the oil by-products obtained from crude oil cracking. The values assigned are mainly fuel values less desulfurization costs, it might also be noted that in parts of the world where crude oil prices are higher than they are in the United States, the crude oil acetyleneethylene process would probably be less favorable. Feedstock costs for this process are directly proportional to crude oil price. Ethylene costs and prices also would be higher, but not in direct proportion to crude oil price. The production cost estimates indicate a greater than 2c/lb differ ential in favor of ethane oxychlorination as compared with ethylene oxy chlorination. However, according to SRI's projections, future world 5 GGC 002512 Table 2.1 VINYL CHLORIDE MONOMER MANUFACTURE COMPARISON OF PROCESS ECONOMICS Plant Capacity: 600 Million lb/yr (272,000 metric tons/yr) at 0.9 Stream Factor CE Cost Index: 180 Capital investment at CE Cost Index=180 ($ million) Battery limits Fixed capital Total investment, less land Production costs (c/lb) Direct operating cost Labor Crude oil (at $7.46/bbl) Ethane at 2.84c/lb Ethylene at 7.9c/lb Chlorine at 5c/lb Other materials Utilities Total direct oper ating cost Indirect operating cost Total production cost By-product credit Recovered HC1 Cracking by-products Net production cost Confidence rating* Ethylene Oxvchlorination $19.1 32.4 48.3 0.20c 3.75 3.03 0.18 1.06 8.22c 1.21 9.43c -0.04 9.39c C Crude Oil Ethane Ethylene Oxychlorination $ 38.5 61.5 82.8 $23.4 37.8 53.6 0.34c 3.32 3.06 0.24 1.03 7.99c 2.16 10.15c -0.04 -1.01 9.10c C 0.22c 1.71 2.87 0.15 0.99 5.94c 1.38 7.32c 7.32c C Jc The confidence rating (A is the highest) is SRI's appraisal of the reliability of the technical and economic input for the evaluation. The bases for these ratings are explained in detail on pages D-7, 8 in the July 1974 Index for the Process Economics Program. crude oil prices (in constant dollars) will be lower than at present. This will be reflected in reduced ethylene prices, whereas ethane prices will steadily increase in the United States. On this basis, the differ ential would decrease to about 0.6q/lb by 1980. On the other hand, if the ethane were obtained as a by-product from steam cracking, its value should be proportional to that of ethylene, and a large differential could remain. An even larger differential would exist in regions that are rich in natural gas. The above costs do not include provisions for compliance with the new regulations on allowable ambient concentrations of vinyl chloride. According to one survey, the added investment to keep within a 10 ppm limit would be about $2.4 million for a 600 million lb/yr monomer plant, and operating costs would increase by about 0.3q/lb. Extrapolation of the survey results to the 5 ppm ceiling (1 ppm 8-hour average) now re quired in the United States and Sweden indicates an added capital invest ment of about $3.5 million and increased operating costs of 0.6c/lb or more. Technical Aspects Other than giving general process descriptions, this discussion of technical aspects is restricted to significant developments that have occurred since the previous reports were issued. Vinyl Chloride by Balanced Ethylene Chlorination-Oxychlorination In this process, ethylene dichloride is produced by addition of chlorine to ethylene in the liquid phase (ethylene dichloride) and in the presence of iron as a catalyst. Ethylene dichloride also is produced by the oxychlorination of ethylene over a copper-bearing catalyst. The streams from these steps are combined with recycled ethylene dichloride and purified by neutralization and distillation. The pure ethylene di chloride is then pyrolyzed to vinyl chloride. Hydrogen chloride pro duced in the pyrolysis is used in the oxychlorination step, and uncon verted ethylene dichloride is recycled to the purification section. 7 6GC 002514 Probably the most significant developments in ethylene chlorination are a number of new catalysts that appear to be superior to the usual iron catalysts. These include inorganic salts of metals such as lithium, tin, bismuth, and tellurium, as well as organic compounds such as sulf oxides and substituted phenols such as o-cresol. The substituted phenols in particular are claimed to give marked improvements in product purity and to reduce corrosion. Patents on ethylene oxychlorination do not reveal appreciable changes or improvements in technology since the previous reports were issued. However, one patent reported extraordinarily high selectivities (9970 and better, both on hydrogen chloride and ethylene) by use of a 1007,, excess of ethylene. Unconverted ethylene is recovered by chlorination. New chemical methods have been developed for treating ethylene di chloride to facilitate removal of troublesome impurities, such as chloroprene, trichloroethylene, benzene, and butadiene. Among these methods are hydrogenation, chlorination, and treatment with aluminum chloride. In ethylene dichloride pyrolysis, a selectivity to vinyl chloride of 99.7% at a conversion of 1004 is attained by use of a catalyst composed of active carbon impregnated with chromium salts. However the life of the catalyst is not indicated. Also, it has been found that the exclu sion of oxygen reduces coking (even though oxygen is specified as a py rolysis accelerator) and that the addition of nitric oxide to deoxygenated ethylene dichloride reduces coke formation still further. Vinyl Chloride from Acetylene and Mixed Acetylene-Ethylene Streams Vinyl chloride was originally produced by the hydrochlorination of acetylene derived from calcium carbide over a mercury catalyst. The pro cess is still in use today on a limited scale. The overall process has been modified by generating acetylene from hydrocarbons. A further modi fication has been to produce a mixed stream of ethylene and acetylene by cracking hydrocarbons followed by hydrochlorination of the contained acetylene and then chlorination of ethylene to ethylene dichloride. The 8 GGC 002515 Appendix C SAFETY All chlorinated hydrocarbons are toxic to some degree. In general, toxicity increases with increased halogentation, and saturated compounds are usually more toxic than their unsaturated analogs. Therefore, vinyl chloride and other toxic products such as tetrachloroethane and 1,1,2trichloroethane are present in vinyl chloride system. The threshold limit of vinyl chloride was at 500 ppm. It has been set at 50 ppm on a tempo rary 6-month emergency basis by Occupational Safety and Health Adminis tration since the January announcement by B.F. Goodrich Chemical Company of the deaths of several employees from angiosarcoma of the liver. A number of companies have observed physiological effects of vinyl chloride monomer at concentrations above 50 ppm in laboratory animals. A report by Biochemical Research Laboratory, Dow Chemical in 1961 indi cated (2019) that repeated exposure to vinyl chloride monomer caused liver and kidney injury. Repeated 7-hour exposure at 200 ppm for six months results in micropathological changes in the livers of rabbits and statistically significant increases in the average weight of the livers of male and female rats, but no detectable changes in dogs and guinea pigs. At 100 ppm, slight increases in the average weight of rat livers were observed. All species studied tolerated repeated, daily 7-hour exposures to 50 ppm for six months with no detectable injury. Recently, Professor Cesare Maltoni of Instituto di Oncologia, Bologna, Italy has experimentally created liver angiosarcoma in rats inhaling vinyl chloride down to 250 ppm level, but so far not at 50 ppm level (90549). He also found that vinyl chloride monomer administered to rats by inhalation results in zymbal gland carcinomas, kidney nephroblastomas, and skin carcinomas and probably hepatomas and neuroblastomas (90550). A pre liminary test at Industrial Bio-Test Laboratories, Inc. for the Manufacturing Chemists Association confirms the findings of Cesare Maltoni (90548). 255 0GC002516 Currently, OSHA has proposed a no-detectable level for exposure for monomer, polymer, and fabricating operations as determined by a sampling and analytical technique capable of detecting vinyl chloride concentra tion of 1 ppm with 50% accuracy, SPI, however, proposed a ceiling of 40 ppm for vinyl chloride monomer for 1974, 25 ppm in 1975 for polyvinyl chloride resin plants, and a ceiling of 25 ppm for vinyl chloride monomer this year, 10 ppm in 1975 for VCM plants. In addition to chlorinated compounds, an accidental release of hy drogen chloride or chlorine also could be hazardous to operating personnel. Highly inflammable gases such as acetylene, ethylene, and hydrogen are present in vinyl chloride operations, and vinyl chloride itself has a flash-point of 108.4F (-78C) with explosive limits in air of 4 to 227. (B-8). In common with many other monomers, accidental initiation of poly merization can result in a dangerous liberation of heat. The presence of water, acids, or air accelerates polymerization and the formulation of shock-sensitive peroxides (B-8) . 256 GGC 002517 CITED REFERENCES 289 2019 5 2279 5 2290 5 2291 5 2301 5 2315 2319 5 2347 5 2368 2382 5 2400 5 2401 5 2402 5 2404 5 2553 5 2554 5 2555 5 2558 5, 6 2571 Hlrsch, J. H,, et al., "Estimating Plant Investment Costs," Chem, Eng, Progr., 56, 12 (I960), 37-43 Torkelson, T. R,, et al., "The Toxicity of Vinyl Chloride as Determined by Repeated Exposure of Laboratory Animals," Ind. Hyg. Assoc. J,, 22 (1961), 354-61 Lee, D,, et al. (to ICI), "Production of Chlorinated Hydrocarbons," British 997,825 (July 7, 1965) Hirsh, D, H,, et al. (to Union Carbide), "Process for the Production of Ethylene Dichloride," US 3,042,728 (July 3, 1962) Keating, H. M,, et al. (to Monsanto Chemical), "Purification of Vinyl Chloride," US 3,125,607 (March 17, 1964) Solvay, "Process for Producing Vinyl Chloride," British 605,277 (July 20, 1948) B. F. Goodrich, "Preparation of Vinyl Chloride," British 938,824 (Oct. 9, 1963) Barton, D, H. R., et al*, "The Kinetics of Dehydrochlorinatian of Substituted Hydrocar bons. Part I. Induced Dehydrochlorination," J. Chem. Soc. (1949), 148-55; "Part II, The Mechanism of the Thermal Decomposition of 1:2 Dichloroethano," 155-64; "Part III, The Mechanism# of Thermal Decomposition of Ethyl Chloride and 1:1 Dichloroethane," 165-9 Rummert, G. (to Hoechst), "Vinyl Chloride by Thermal Decomposition of Ethylene Dichloride," German 1,100,616 (March 2, 1961) Benedict, D. (to Union Carbide), "Process for the Preparation of Olefin Dichlorides," US 2,929,852 (April 22, 1960) i Vaughan, W. E. , et al., "The High-Temperature Chlorination of Paraffin Hydrocarbons," J. Org. Chem., 5 (1940), 449-71 Pechiney Compagnie de Produits Chimiques et Electrometalluglques, "Chlorination of Hydrocarbons," British 959,244 (May 27, 1964) Hoechst, "Process for the Manufacture of 1,2-Dichloroethane by Oxychlorination of Ethylene," British 992,847 (May 26, 1965) Piester, L. W, (to Pittsburgh Plate Glass), "Gas Distributor," US 3,215,508 (Nov. 2, 1965) McGlnty, L,, et al, (to ICI), "Production of Chlorinated Hydrocarbons," British 967,936 (Aug. 26, 1964) Gause, E. H., et al. (to Monsanto), "Purification of Vinyl Chloride," US 3,142,709 (July 28, 1964) McDonald, D. W. (to Monsanto Chemical), "Purification of Vinyl Chloride," DS 3,125,608 (March 17, 1964) Jacklln, A. G. (to ICI), "Process for Purification of Vinyl Chloride," British 956,618 (April 29, 1964) Vulcan Materials, "Oxychlorination Process," British 980,983 (Jan, 20, 1965) Otsuka, E., et al. (to Toyo Koatsu Industries), "Process for Producing Vinyl Chloride," US 3,291,846 (Dec. 13, 1966) 257 GGC 002518 5 2586 5 2587 5 2588 5 2589 5 2590 5 2591 6 2610 5 16002 5 16004 5 16006 5 16010 5 16021 5 16022 5 16038 5, 8 16040 5 16041 5, 8 16042 16043 5 16051 5 16058 5 16069 5 16084 5 16088 Price, J, L. (to Monsanto Chemical), "Catalyst Preparation," US 3,010,913 (Nov. 28, 1961) ' ICI of Australia & New Zealand, "Manufacture of Chlorinated Hydrocarbons," British 987,529 (March 31, 1965) Bohl, L. E. , et al, (to Pittsburgh Plate Glass), "Process of Oxychlorination of Hydro carbons in a Fluidized Bed," French 1,355,886 (Feb, 10, 1964) Carlson, G. A., et al, (to Pittsburgh Plate Glass), "Process of Production of 1,2Dichloroethane Derived from Ethylene," French 1,323,939 (March 4, 1963) Bohl, L. E., et al. (to Pittsburgh Plate Glass), "Heat Transfer in Oxychlorination Reactions," US 3,256,352 (June 14, 1966) Pechiney-Compagnie de Produits Chimiques et Electrometallurgiques, "improvements In or Relating to Catalytic Oxychlorination Processes," British 993,939 (June 2, 1965) Wacker-Chemie, "Process for the Manufacture of Vinyl Chloride by the Catalytic Split ting of 1:2-Dichloroethane," British 979,309 (Jan. 1, 1965) Onoe, Y., et al. (to Tokuyama Soda), "Production of Ethane Dichloride," Japanese 41-3168 (Feb. 25, 1966) Ethyl, "A Process for the Production of Vinyl Chloride," British 1,031,006 (May 25, 1966) Leach, H, S., et al. (to Monsanto), "Production of Vinyl Chloride," US 3,222,407 (Dec. 7, 1965) Bohl, L. E. , et al. (to Pittsburgh Plate Glass), "Production of Chlorinated Hydrocar bons," British 1,027,277 (April 27, 1966) Ethyl, "Chlorinated Hydrocarbons," French 1,409,695 (Sept. 29, 1964) Laine, F., et al., "process for the Oxychlorination of Aliphatic Hydrocarbons," US 3,240,827 (March 15, 1966) Solvay, "Process for the Manufacture of Halogenated Hydrocarbons," British 1,016,485 (Jan. 12, 1966) Ito, K. (to Kureha Chemical Industry), "Manufacturing Process of Vinyl Chloride and Dichloroethane from Cracked Gases Containing Acetylene, Ethylene, etc. Obtained from Hydrocarbons," Japanese 39-28305 (Dec. 8, 1964) Kureha Chemical Industry, "Process for the Production of Dichloroethane," Netherlands 65,04088 (March 31, 1965) Kureha Chemical Industry, "A Process for the Manufacture of Vinyl Chloride," British 1,068,793 (May 17, 1967) Balasubramanian, S. N,, et al,, "Film Model for Ethylene Dichloride Formation," Ind. Eng, Chem., Fundamentals, 5, 2 (1966), 184-8 Produits Chimiques Pechiney-Saint-Gobain, "Indirectly Heated Reactor," French 1,411,183 (Aug. 5, 1964) Piaster, L. W. , et al, (to Pittsburgh Plate Glass), "Production of Chlorinated Hydro carbons," British 1,049,213 (Nov. 23, 1966) Hoechst, "1,2-Dlchloroethane," US 3,475,505 (Oct. 28, 1967) Wofford, G. L, (to Monsanto), "Purification of Vinyl Chloride," US 3,244,755 (April 5, 1966) B. F. Goodrich, "1,2-Dlchloroethane," Belgian 680,413 (May 3, 1966) (Abstract) 258 GGC0025J9