Preparing By Oxyhalogenation Patents (Class 570/243)
  • Patent number: 5243111
    Abstract: Hydrocarbons, e.g., ethylene, are steady-state catalytically oxychlorinated into chlorocarbons, e.g., 1,2-dichloroethane, by fluidizing a fluidizable charge by directing a gaseous feedstream containing a hydrocarbon therethrough and therein oxychlorinating such hydrocarbon, the gaseous feedstream further comprising an oxygen-containing gas and gaseous hydrochloric acid and the fluidizable charge comprising immixture of a catalytically effective amount of an oxychlorination catalyst and particles of a catalytically and chemically inert solid substance, and which further comprises introducing a solution or suspension of a catalytically active copper compound into such fluidized charge during the oxychlorination reaction.
    Type: Grant
    Filed: December 14, 1992
    Date of Patent: September 7, 1993
    Assignee: Atochem
    Inventors: Alain Petit, Roland Bachelard, Rene Clair, Yves Correia
  • Patent number: 5227549
    Abstract: A major amount of 1,2-dichloroethane (D12) and lesser amounts of trichloroethane and tetrachloroethane are prepared by contacting carbon tetrachloride, ethylene and oxygen (or an oxygen-containing gas, notably air) with an oxychlorination catalyst at a temperature sufficient to produce D12, and thereafter separating such D12 from the products of reaction.
    Type: Grant
    Filed: February 18, 1992
    Date of Patent: July 13, 1993
    Assignee: Elf Atochem S.A.
    Inventors: Yves Correia, Gerard Chastel
  • Patent number: 5227548
    Abstract: A process for the oxychlorination of ethylene to 1,2-dichloroethane using an oxychlorination catalyst composition comprising a mixture of copper chloride, magnesium chloride and potassium chloride carried on a support therefor.
    Type: Grant
    Filed: January 16, 1991
    Date of Patent: July 13, 1993
    Assignee: Imperial Chemical Industries PLC
    Inventor: John D. Scott
  • Patent number: 5202511
    Abstract: Alumina is used as a support for the CuCl2 catalyst and as a diluent in the oxychlorination of ethylene. When a low surface area alumina, e.g. high purity alpha-alumina, is used as diluent for the reaction, reduced oxidation and less chlorinated by-products are achieved. Alternatively, the alumina used as the catalyst support, e.g. a gamma-alumina which has a high surface area and higher amounts of impurities, can be used as diluent if it is impregnated with an alkali metal ion, e.g K+ ion, which is usually employed as a salt.
    Type: Grant
    Filed: August 16, 1989
    Date of Patent: April 13, 1993
    Assignee: The Dow Chemical Company
    Inventors: Leopoldo Salinas, III, Thomas E. Morris, Arnold D. Harley
  • Patent number: 5200376
    Abstract: Catalysts for the oxyhydrochlorination of methane into methyl chloride, comprising a chemical compound of great specific surface area of the zeolite type which is partially exchanged at least with divalent metallic cations, preferably Cu.sup.++ cations, the catalysts being applicable in particular to the formation of monochlorinated products usable as such or as intermediate chemical agents.
    Type: Grant
    Filed: April 24, 1991
    Date of Patent: April 6, 1993
    Assignee: Gaz De France
    Inventors: Jacques Saint Just, Yaounes B. Taarit, Meyer C. Naccache, Michel Dufaux
  • Patent number: 5185479
    Abstract: An improved method of producing methyl alcohol (methanol) from methane is provided using two reaction steps operated in tandem. In the first reaction step two chemical reactions occur simultaneously: a) perchloroethylene (CCl.sub.2 CCl.sub.2) is oxychlorinated with hydrogen chloride and oxygen to obtain hexachlorethane (CCL.sub.3 CCL.sub.3) and water, and b) methyl chloride (CH.sub.3 Cl) is hydrolyzed with water to give methyl alcohol and hydrogen chloride. In the second reaction step methane is chlorinated with hexachlorethane to produce methyl chloride, hydrogen chloride and perchloroethylene. By recycling the methyl chloride, hydrogen chloride, and regenerated perchloroethylene produced in the second step to the first step the process can be operated in a balanced mode whereby the internal consumption of hydrogen chloride is equal to its formation.
    Type: Grant
    Filed: April 21, 1992
    Date of Patent: February 9, 1993
    Inventor: John E. Stauffer
  • Patent number: 5179215
    Abstract: An improved process is provided for the production of a petrochemical by the vapor phase reaction of a hydrocarbon with an oxygen-containing gas in the presence of a suitable catalyst to produce a flammable gaseous product stream comprising the desired petrochemical, unreacted hydrocarbon, oxygen, carbon monoxide and carbon dioxide. In the improved process, a cooled or liquefied inert gas is injected as a quench fluid into the gaseous product stream exiting the hydrocarbon oxidation reactor, thereby cooling the stream to a temperature below the autoignition temperature of the flammable components of the stream, the petrochemical is recovered from the gaseous product and unreacted hydrocarbon is removed from the gaseous product and recycled to the reactor.
    Type: Grant
    Filed: February 27, 1991
    Date of Patent: January 12, 1993
    Assignee: The BOC Group, Inc.
    Inventors: Ramakrishnan Ramachandran, Donald L. MacLean
  • Patent number: 5157174
    Abstract: Hydrocarbons are oxychlorinated by reaction with gaseous HCl and an oxygen-containing gas, in the presence of a catalytically effective amount of a ternary copper/molybdenum chalcogenide having the formula:Cu.sub.x Mo.sub.6 Ch.sub.8wherein x is a number ranging up to 4 and Ch is sulfur, selenium or tellurium, advantageously, in the added presence of a known oxychlorination catalyst and, optionally, a proportion of inert particulate solids; the ternary molybdenum chalcogenides of the formula M.sub.x Mo.sub.6 S.sub.8 are also prepared, wherein M is a metal, advantageously by the hydrogen gas reduction of intimate admixture of MoS.sub.2 and metal M, or precursors thereof.
    Type: Grant
    Filed: October 2, 1991
    Date of Patent: October 20, 1992
    Assignee: Atochem
    Inventors: Murielle Rabiller-Baudry, Annick Faure, Jean Lesparre, Marcel Sergent, Roger Chevrel
  • Patent number: 5099085
    Abstract: The use of hitherto known supported catalysts in chlorination processes and oxychlorination processes leads to high pressure drops and to the formation of hot spot temperatures in the reactor. When honeycomb monolithic catalyst supports provided with a multiplicity of channels open at both ends and parallel to the longitudinal axis are used, both the heat dissipation is improved and the pressure drops across the reactor are lowered drastically. This leads ultimately to an increase in the selectivity of the reaction and to a minimization of the combustion rate.
    Type: Grant
    Filed: March 1, 1991
    Date of Patent: March 24, 1992
    Assignees: Wacker Chemie GmbH, Degussa AG
    Inventors: Rudolf Strasser, Ludwig Schmidhammer, Klaus Deller, Helmfried Krause
  • Patent number: 5053567
    Abstract: Chlorinated hydrocarbons, e.g., 1,2-dichloroethane, are prepared by heterogenously oxychlorinating a hydrocarbon with an oxygen-containing gas and gaseous hydrochloric acid in a fluidized bed containing admixture of (i) a catalytically effective amount of an oxychlorination catalyst, (ii) diluent particles of at least one catalytically and chemically inert solid material, and (iii) copper powder or a powdered copper compound.
    Type: Grant
    Filed: December 21, 1989
    Date of Patent: October 1, 1991
    Assignee: Atochem
    Inventors: Yves Correia, Jean Lesparre, Alain Petit
  • Patent number: 5047209
    Abstract: The operation of a fluid-bed reactor in which the catalyst has a proclivity to stickiness deleterious to efficiently carrying out a reaction of the gaseous components fed to the reactor, is controlled by monitoring the fluctuations in temperature at various locations in the bed, and computing the standard deviation of temperature at predetermined intervals of time. When the fluid-bed consists essentially of a supported catalyst performing at peak efficiency, near which it has a proclivity to "stickiness", slight fluctuations, less than 1.degree. F., of operating temperature are correlatable to the quality of fluidization and the risk of an uncontrollable upset in the reactor.
    Type: Grant
    Filed: February 16, 1988
    Date of Patent: September 10, 1991
    Assignee: The B. F. Goodrich Company
    Inventor: John P. Lenczyk
  • Patent number: 4910354
    Abstract: The invention relates to a process for the oxychlorination of ethylene by means of a catalyst composition comprising an alumina support impregnated with cupric chloride, magnesium chloride and a chloride of an alkali metal chosen from sodium and lithium. The oxychlorination performed in this manner makes it possible to obtain an excellent yield without the reactor being corroded by the catalyst composition employed.
    Type: Grant
    Filed: June 26, 1987
    Date of Patent: March 20, 1990
    Assignee: Solvay & Cie (Societe Anonyme)
    Inventors: Helmut Derleth, Robert Walter, Gunter Weidenbach, Michel Strebelle
  • Patent number: 4849562
    Abstract: The oxychlorination process for producing ethylene dichloride is carried out by reacting ethylene with hydrogen chloride and oxygen in an oxychlorination reactor. Thereby, ethyl chloride and perhaps vinyl chloride are produced as by-products. The effluent from the reactor is at least fractionated into an ethylene dichloride-rich fraction (I) and an ethyl chloride-rich fraction (II) so that fraction (I) contains less than 50 percent of the total weight of ethyl chloride produced in step (a) and the sum of the weight of ethylene dichloride and vinyl chloride in fraction (II) is less than 30 percent of the weight of ethyl chloride in fraction (II). The ethyl chloride-rich fraction (II) is subjected to a cracking reaction in the presence or absence of an inert diluent wherein ethyl chloride is converted into ethylene and hydrogen chloride in the presence of a catalyst.
    Type: Grant
    Filed: August 26, 1988
    Date of Patent: July 18, 1989
    Assignee: The Dow Chemical Company
    Inventors: Christoph Buhs, Eberhard Dreher, Garnet E. McConchie
  • Patent number: 4814527
    Abstract: Monosubstituted saturated lower hydrocarbons are oxyhalogenated selectively to saturated dihalohydrocarbons at 180.degree.-350.degree. C. in the presence of a catalyst which is formed by depositing a variable valence metal compound on a zeolitic support in such a manner that the catalyst can be employed to selectively produce ethylene dichloride and ethylene from ethyl chloride.
    Type: Grant
    Filed: June 25, 1987
    Date of Patent: March 21, 1989
    Assignee: The Dow Chemical Company
    Inventor: Ronald W. Diesen
  • Patent number: 4788359
    Abstract: 1,2-dichloroethane is continuously and completely removed and recovered from the off-gas obtained during the production of 1,2-dichloroethane by subjecting ethylene to an oxychlorination reaction with hydrogen chloride and oxygen. The off-gas is initially contacted with active carbon, then incinerated at temperatures higher than 900.degree. C. and ultimately freed from hydrogen chloride and chlorine, and the active carbon is freed from 1,2-dichloroethane and regenerated by treating it with hot steam. More particularly, the off-gas loaded with the 1,2-dichloroethane and having a temperature of 1.degree. C. to 10.degree. C. is heated to a temperature at least 20.degree. C. higher than the respective dew point of water and contacted with the active carbon.
    Type: Grant
    Filed: July 27, 1987
    Date of Patent: November 29, 1988
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Kurt Schuchardt, Harald Scholz, Erich Niehus, Harald Adam
  • Patent number: 4788358
    Abstract: A process for the manufacture of 1,2-dichloroethane from ethylene by reaction with hydrogen chloride and inert gases containing oxygen, and also by reaction with chlorine, is described. The two chlorination reactions are carried out successively at 180.degree. to 360.degree. C. and under a pressure of 0.09 to 1.1 MPa in a common reaction space containing fluidized catalyst particles. A stoichiometric excess of ethylene is employed for the first chlorination reaction. The heat formed in the reaction space is removed by indirect cooling. The process is simple in terms of apparatus and permits a better re-use of the total heat of reaction of the chlorination of ethylene.
    Type: Grant
    Filed: August 5, 1985
    Date of Patent: November 29, 1988
    Assignee: Bayer Aktiengesellschaft
    Inventors: Josef Riedl, Wenzel Kuhn, Peter Widmann
  • Patent number: 4760207
    Abstract: In a process for producing 1,2-dichloroethane or ethylene dichloride ("EDC") in a high temperature direct chlorination ("HTDC") reactor in which ethylene is reacted with wet chlorine having a water content more than 100 ppm but no more than 1% by wt of the chlorine, the water leaves the reactor with the EDC product draw-off, either in the vapor overhead (if the HTDC is a boiling reactor), or, as a liquid sidestream (if the HTDC is a non-boiling reactor). In a subsequent step, the EDC draw-off is distilled in a product distillation column in which the water leaves in the overhead which is condensed to remove condensables in a first stage, and vent a non-condensable vent streams. The vent stream is corrosive due to the presence of minor amounts of chlorine, HCl and water, along with oxygen which is injected into the HTDC to improve selectivity of the reaction. The vent gases from the first stage are further cooled to a temperature in the range from about -30.degree. C. to about 0.degree. C.
    Type: Grant
    Filed: September 18, 1986
    Date of Patent: July 26, 1988
    Assignee: B.F. Goodrich Company
    Inventor: Joseph A. Cowfer
  • Patent number: 4754088
    Abstract: In a process for preparation of 1,2-dichloroethane by chlorination of ethylene-containing reaction vent gases from the oxychlorination of ethylene in the presence of a catalyst carrier impregnated with metal compounds wherein the waste from the oxychlorination stage are chlorinated, the improvement comprising preheating the ethylene-containing waste gases to at least 50.degree. C. and then chlorinating the ethylene at 100.degree. to 300.degree. C. at a pressure of 1 to 7 bar with a space velocity of 100 to 5000 h.sup.-1 related to standard conditions in the presence of at least one metal compound selected from the group consisting of chlorides and oxides of manganese, nickel and cobalt supported on a catalyst carrier with reduced formation of oxychlorinated by-products.
    Type: Grant
    Filed: February 11, 1987
    Date of Patent: June 28, 1988
    Assignee: Wacker-Chemie GmbH
    Inventors: Ludwig Schmidhammer, Peter Hirschmann, Herbert Patsch, Rudolf Strasser
  • Patent number: 4740644
    Abstract: 1,2-Dichloroethane is prepared by oxychlorination of ethylene in the presence of a catalyst which contains, on a conventional carrier, copper(II) chloride in a concentration such that the amount of copper ions is from 1 to 20% by weight, based on the total weight of the catalyst, by a process in which the catalyst is obtained by impregnating the carrier with an aqueous solution which contains copper(II) chloride and hydrogen chloride in amounts such that the weight ratio of copper ions to hydrogen chloride is from 13:1 to 130:1.
    Type: Grant
    Filed: June 20, 1986
    Date of Patent: April 26, 1988
    Assignee: BASF Aktiengesellschaft
    Inventors: Hans-Dieter Eichhorn, Hans H. Schneehage, Luc Cordemans, Werner Hebgen, Christof Jaeckh, Wolf D. Mross
  • Patent number: 4740643
    Abstract: The operation of a fluid-bed reactor in which the catalyst has a proclivity to stickiness deleterious to efficiently carrying out a reaction of the gaseous components fed to the reactor, is controlled by monitoring the fluctuations in temperature at various locations in the bed, and computing the standard deviation of temperature at predetermined intervals of time. When the fluid-bed consists essentially of a supported catalyst performing at peak efficiency, near which it has a proclivity to "stickiness", slight fluctuations, less than 1.degree. F., of operating temperature are correlatable to the quality of fluidization and the risk of an uncontrollable upset in the reactor.
    Type: Grant
    Filed: April 4, 1986
    Date of Patent: April 26, 1988
    Assignee: The B. F. Goodrich Company
    Inventor: John P. Lenczyk
  • Patent number: 4740642
    Abstract: A fluidizable catalyst composition is provided containing about 2% to about 8% by weight of copper (about 4% to about 17% by weight of copper salt), from about 0.2% to about 10% by weight of a rare earth metal salt(s), preferably the chloride salt(s), and from about 0.25% to about 2.3% by weight of an alkali metal salt(s), preferably the chloride salt(s), all weight percents based upon the total weight of the catalyst composition. The metals are codeposited on a fluidizable, high surface area alumina support. The weight of the alkali metal employed is not over 2.5% by weight (as the chloride) and the weight ratio of the rare earth metal salt(s) to the alkali metal salt(s) must be at least 0.8:1. Such catalyst compositions are extremely useful as fluid bed catalysts in the vapor phase oxychlorination reaction of ethylene, oxygen and hydrogen chloride to produce 1,2-dichloroethane (EDC).
    Type: Grant
    Filed: August 21, 1986
    Date of Patent: April 26, 1988
    Assignee: The BF Goodrich Company
    Inventors: Jamal S. Eden, Joseph A. Cowfer
  • Patent number: 4668833
    Abstract: A process for hydrogenating acetylene in hydrogen chloride gas using the catalytic palladium supported on silicon carbide carrier whose iron content is specified to be not more than 1,000 ppm. The catalyst has the advantages of enhancing the conversion of acetylene into ethylene, improving the selectivity of ethylene, and retaining catalytic activity over a long time at a large space velocity. This process can be effectively applied to the hydrogenation of acetylene in hydrogen chloride gas separated from the thermally decomposed products of 1,2-dichloroethane which occurs in the production of vinyl chloride; namely, the hydrogen chloride gas that contains thus hydrogenated acetylene (ethylene) can be recycled in such an effective way that 1,2-dichloroethane can be produced economically.
    Type: Grant
    Filed: April 24, 1986
    Date of Patent: May 26, 1987
    Assignee: Kanegafuchi Chemical Industry Co., Ltd.
    Inventors: Hiroshi Ohshima, Osamu Kakimoto
  • Patent number: 4584123
    Abstract: A process of upgrading hydrogen chloride which contains chlorine, iron-III-chloride, acetylene and/or ethylene, for use in an oxichlorination process, wherein water in a gaseous state is added to the hydrogen chloride at temperatures between 120.degree. and 180.degree. C. within a time period of maximally 0.9 seconds after the acetylene and/or ethylene is present in the hydrogen chloride, together with chlorine and iron-III-chloride.
    Type: Grant
    Filed: July 24, 1984
    Date of Patent: April 22, 1986
    Assignee: Wacker-Chemie GmbH
    Inventors: Ludwig Schmidhammer, Gerhard Dummer, Klaus Haselwarter, Rudolf Strasser
  • Patent number: 4467127
    Abstract: An alkane is reacted with oxygen and available chlorine in the presence of a solid solution catalyst containing iron cations to yield unsaturated hydrocarbons and chlorinated saturated and unsaturated hydrocarbons. In a preferred embodiment of the process, ethane is reacted with oxygen and available chlorine in the presence of a solid solution catalyst containing iron cations to yield vinyl chloride, ethylene, and other valuable by-products. The conversion of ethane to products approaches 100 percent, vinyl chloride is prepared in up to 40 mole percent yield, and the combined yield of vinyl chloride, ethylene dichloride, ethyl chloride, and ethylene is up to 90 mole percent.
    Type: Grant
    Filed: January 14, 1983
    Date of Patent: August 21, 1984
    Assignee: The B. F. Goodrich Company
    Inventors: William J. Kroenke, Paul P. Nicholas
  • Patent number: 4461919
    Abstract: An alkane is reacted with oxygen and available chlorine in the presence of a solid solution catalyst containing iron cations to yield unsaturated hydrocarbons and chlorinated saturated and unsaturated hydrocarbons. In a preferred embodiment of the process, ethane is reacted with oxygen and available chlorine in the presence of a solid solution catalyst containing iron cations to yield vinyl chloride, ethylene, and other valuable by-products. The conversion of ethane to products approaches 100 percent, vinyl chloride is prepared in up to 40 mole percent yield, and the combined yield of vinyl chloride, ethylene dichloride, ethyl chloride, and ethylene is up to 90 mole percent.
    Type: Grant
    Filed: January 14, 1983
    Date of Patent: July 24, 1984
    Assignee: The B. F. Goodrich Company
    Inventors: William J. Kroenke, Paul P. Nicholas
  • Patent number: 4460699
    Abstract: The present invention provides a fixed bed catalyst for the oxychlorination of ethene, alpha olefins and aromatics. More specifically, this invention relates to a catalyst having an impeded center which excludes reactants, or prevents products from forming in the interior of the catalyst. The impeded center may be made inaccessible or it may be inert to reaction. Thin layers of high specific surface area carrier material cover the outer surface of the impeded center. An agent capable of catalyzing oxychlorination reactions is added to the layered catalytic carrier material.
    Type: Grant
    Filed: August 4, 1982
    Date of Patent: July 17, 1984
    Assignee: Conoco Inc.
    Inventors: Ronald J. Convers, Robert M. Owens
  • Patent number: 4451683
    Abstract: An oxychlorination catalyst contains a copper compound, magnesium oxide and aluminium oxide, and the copper compound is present as a distinct phase on a support in which at least part of the magnesium oxide is in combined form with alumina.
    Type: Grant
    Filed: January 8, 1982
    Date of Patent: May 29, 1984
    Assignee: Imperial Chemical Industries PLC
    Inventors: Phineas Davies, James R. Jennings, Jack Wolstenholme
  • Patent number: 4446249
    Abstract: A fluidizable catalyst composition is provided having cupric chloride deposited on a fluidizable, modified gamma alumina support in which the support has incorporated, prior to the deposit of copper, from 0.5% to 3.0% by weight based on the weight of the support of at least one metal selected from the group consisting of potassium, lithium, rubidium, cesium, alkaline earth metals, rare earth metals, or combinations thereof. Such catalyst compositions are extremely useful as the fluid bed catalyst in the vapor phase oxyhydrochlorination reaction of ethylene, oxygen and hydrogen chloride to produce 1,2-dichloroethane. The use of the catalysts results in improved EDC efficiency based on ethylene and avoids operating problems caused by stickiness of the catalyst in the fluid bed.
    Type: Grant
    Filed: May 17, 1982
    Date of Patent: May 1, 1984
    Assignee: The B. F. Goodrich Company
    Inventor: Jamal S. Eden
  • Patent number: 4424143
    Abstract: A catalyst suitable for use in the preparation of 1,2-dichloroethane by oxychlorination of ethylene containing cupric chloride and, as a promotor, a combination of potassium chloride and cesium chloride, which can inhibit production of ethyl chloride by-product and has excellent selectivity to 1,2-dichloroethane and catalyst life.
    Type: Grant
    Filed: March 31, 1982
    Date of Patent: January 3, 1984
    Assignee: Kanegafuchi Kagaku Kogyo Kabushiki Kaisha
    Inventors: Ken Shiozaki, Akira Ohnishi
  • Patent number: 4414136
    Abstract: Highly active, improved ethylene oxychlorination catalysts are prepared by forming alumina having specific pore volume characteristics and impregnating such alumina with an oxychlorination catalyst such as CuCl.sub.2. The improved catalysts of the present invention utilize an alumina carrier having a pore volume distribution such that substantially no pores are present which have diameters of less than 150 .ANG.ngstroms and the total alumina carrier has a surface area of at least 30 square meters per gram.
    Type: Grant
    Filed: April 2, 1982
    Date of Patent: November 8, 1983
    Assignee: Conoco Inc.
    Inventor: Ronald J. Convers
  • Patent number: 4391880
    Abstract: Process and system for cooling a reaction effluent containing volatized catalyst wherein the effluent is contacted with circulating cooled solid catalyst in dilute phase transport contact, with the volatized catalyst being condensed onto the solid catalyst.
    Type: Grant
    Filed: January 2, 1981
    Date of Patent: July 5, 1983
    Assignee: The Lummus Company
    Inventor: Utah Tsao
  • Patent number: 4386228
    Abstract: A process for initiating a fluidized bed process for oxychlorination of methane and/or chlorinated derivatives thereof with hydrogen chloride and air.
    Type: Grant
    Filed: February 2, 1979
    Date of Patent: May 31, 1983
    Assignee: Stauffer Chemical Company
    Inventor: Richard J. Ayen
  • Patent number: 4382021
    Abstract: A supported catalyst containing copper and alkali metals, wherein the content of copper is from 1.0 to 12% by weight, based on total catalyst and expressed as metal, and the total content of the alkali metals potassium, lithium and sodium is from 0.3 to 9% by weight, based on total catalyst.The novel catalyst is useful for the preparation of 1,2-dichloroethane by oxychlorination of ethylene.
    Type: Grant
    Filed: November 25, 1981
    Date of Patent: May 3, 1983
    Assignee: BASF Aktiengesellschaft
    Inventors: Peter R. Laurer, Gerd Krome, Luc Cordemans, Reinhard Seifert, Eckehard Danz
  • Patent number: 4380682
    Abstract: The present invention relates to a novel process of halogenating aliphatic hydrocarbons which comprises, first non-selectively oxyhalogenating a C.sub.2 -C.sub.6 aliphatic hydrocarbon to a partially halogenated intermediate product having an overall avarage empirical formula in which the atomic ratio of halogen to carbon is greater than 1:1, then vapor phase halogenating said intermediate product to form an end product having an atomic ratio of carbon to hydrogen is at least 2:1; thereby selectively coproducing or consuming hydrogen chloride.
    Type: Grant
    Filed: February 22, 1982
    Date of Patent: April 19, 1983
    Assignee: Diamond Shamrock Corporation
    Inventors: Frederick C. Leitert, Carl G. Vinson, Jr.
  • Patent number: 4377491
    Abstract: An oxychlorination catalyst precursor is described which is constituted by porous microspheroidal alumina particles impregnated with 3 to 7% by weight of cupric chloride (expressed in terms of the copper metal) and containing from 0.5 to 2% by weight of water, in which the copper is uniformly distributed over the entire surface area of the particles with a degree of non-uniformity not greater than .+-.7%.A process for the preparation of such a catalyst precursor is also described.The precursor is activated to give a catalyst which is readily fluidizable and which enables the oxychlorination of ethylene to dichloroethane to be carried out with high activity and selectivity values.
    Type: Grant
    Filed: January 3, 1982
    Date of Patent: March 22, 1983
    Assignee: Euteco Impianti S.p.A.
    Inventors: Roberto Canavesi, Roberto Ghezzi, Vittorio Tagliabue
  • Patent number: 4375569
    Abstract: An alkane is reacted with oxygen and available chlorine in the presence of a solid solution catalyst containing iron cations to yield unsaturated hydrocarbons and chlorinated saturated and unsaturated hydrocarbons. In a preferred embodiment of the process, ethane is reacted with oxygen and available chlorine in the presence of a solid solution catalyst containing iron cations to yield vinyl chloride, ethylene, and other valuable by-products. The conversion of ethane to products approaches 100 percent, vinyl chloride is prepared in up to 40 mole percent yield, and the combined yield of vinyl chloride, ethylene dichloride, ethyl chloride, and ethylene is up to 90 mole percent.
    Type: Grant
    Filed: October 10, 1978
    Date of Patent: March 1, 1983
    Assignee: The B. F. Goodrich Company
    Inventors: William J. Kroenke, Paul P. Nicholas
  • Patent number: 4356336
    Abstract: In the production of a chlorinated hydrocarbon, such as chlorinated methanes, a purge stream is recovered from the chlorinated hydrocarbon effluent, which contains inerts and unreacted hydrocarbon. The unreacted methane present in the purge stream is combusted to recover the fuel values thereof; e.g., as a fuel in the waste chlorinated hydrocarbon combustion to recover chlorine values, with the inerts then being purged from the system.
    Type: Grant
    Filed: June 15, 1978
    Date of Patent: October 26, 1982
    Assignee: The Lummus Company
    Inventor: Angel Sy
  • Patent number: 4351819
    Abstract: In an integrated process for oxychlorination and combustion of chlorinated hydrocarbons, chlorinated hydrocarbon is burned to recover chlorine values essentially as hydrogen chloride. Hydrogen chloride is recovered from the effluent from the combustion by absorption with aqueous hydrogen chloride. Hydrogen chloride recovered by the absorption is subsequently recovered and employed in an oxychlorination reaction. A gas containing hydrogen chloride, water vapor and some oxygen recovered from the oxychlorination is cooled to condense aqueous hydrogen chloride which is employed in the absorption for recovering hydrogen chloride. The remaining gas is employed in the combustion of chlorinated hydrocarbons.
    Type: Grant
    Filed: January 26, 1981
    Date of Patent: September 28, 1982
    Assignee: The Lummus Company
    Inventors: Herbert Riegel, Chiung-Yuan Huang
  • Patent number: 4346069
    Abstract: In an integrated process for oxychlorination and combustion of chlorinated hydrocarbons, chlorinated hydrocarbons is burned to recover chlorine values essentially as hydrogen chloride. Combustion effluent and off-gas from an oxychlorination reaction are simultaneously treated to recover anhydrous hydrogen chloride for use in the oxychlorination reaction. In accordance with one embodiment, off-gas from the oxychlorination is employed in the combustion, prior to hydrogen chloride recovery in order to utilize any oxygen values therein. The process has particular applicability to an oxychlorination reaction of the type wherein a molten salt containing the higher and lower valent chlorides of a multivalent metal is contacted with hydrogen chloride and oxygen to recover hydrogen chloride by enriching the higher valent metal chloride content of the molten salt.
    Type: Grant
    Filed: January 26, 1981
    Date of Patent: August 24, 1982
    Assignee: The Lummus Company
    Inventors: Herbert Riegel, Chiung-Yuan Huang
  • Patent number: 4339620
    Abstract: There is disclosed a method and composition for improving the fluidization characteristics and alleviating or inhibiting stickiness in a supported cupric chloride catalyst used as fluid bed catalyst in oxyhydrochlorinations reactions. The method involves the in situ preparation of the supported cupric chloride catalyst by addition of bare support on which no cupric chloride is deposited to the supported cupric chloride catalyst in the fluidized bed, or the use in the bed as the initial charge or as addition to the bed as makeup, of a composition which is a mixture of supported cupric chloride catalyst and bare support. In either event, as the oxyhydrochlorination proceeds, a portion of the cupric chloride on the supported catalyst becomes released therefrom and deposited in situ on the bare support, and stickiness of the cupric chloride containing catalyst particles to one another in the fluid bed is alleviated or inhibited.
    Type: Grant
    Filed: March 2, 1981
    Date of Patent: July 13, 1982
    Assignee: The B. F. Goodrich Company
    Inventors: Joseph A. Cowfer, Jamal S. Eden, Angelo J. Magistro
  • Patent number: 4329323
    Abstract: A process for removing ethylene and vinyl chloride from a gas stream containing them by passing a mixed gas containing ethylene, vinyl chloride and a necessary amount of chlorine through a fixed-bed reactor charged with as a catalyst an activated alumina supporting at least 4% by weight of ferric chloride in terms of iron, said catalyst having an outer surface area per unit packed catalyst volume of not less than 7.8 cm..sup.2 /ml. Ethylene and vinyl chloride are converted into and removed as 1,2-dichloroethane and 1,1,2-trichloroethane. The concentrations of ethylene and vinyl chloride can be decreased to not more than 10 p.p.m. and not more than 20 p.p.m., respectively.
    Type: Grant
    Filed: October 21, 1980
    Date of Patent: May 11, 1982
    Assignee: Kanegafuchi Kagaku Kogyo Kabushiki Kaisha
    Inventors: Ken Shiozaki, Hironobu Ibaraki
  • Patent number: 4329527
    Abstract: A process for the manufacture of 1,2-dichloroethane is described, in which 1 mol of ethylene, 0.35 to 0.7 mol of chlorine, 0.7 to 1.4 mol of hydrogen chloride and 0.2 to 0.6 mol of oxygen, optionally together with inert gas, are reacted in a reaction zone containing surfaces capable of being heated and cooled, at 180.degree. to 260.degree. C. and under a pressure of 0.09 to 1.1 MPa, in the presence of a fixed bed catalyst containing copper. The process allows better utilization of the heat generated in the chlorination of ethylene.
    Type: Grant
    Filed: December 3, 1980
    Date of Patent: May 11, 1982
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Wenzel Kuhn, Josef Riedl, Peter Widmann
  • Patent number: 4329526
    Abstract: An improvement in fluid-bed oxychlorination methods comprising in combination a generally cup-shaped container and an inverted generally cone-shaped gas distributor having a truncated apex the section of truncation defining a generally circular or polygonal opening, the lip portion of the container fitting against the similarly-shaped opening of the distributor.
    Type: Grant
    Filed: November 17, 1980
    Date of Patent: May 11, 1982
    Assignee: Monsanto Company
    Inventors: Melvin R. Bagley, Burton B. Crocker, John F. Pysz
  • Patent number: 4323716
    Abstract: An oxychlorination catalyst active in the production of dichloroethane from ethylene, hydrogen chloride and oxygen, consisting of copper chloride on a granular support consisting of alumina in the crystallographic form eta, having a total volume of pores of from 0.3 to 0.5 ml/g and a surface area of from 250 to 400 m.sup.2 /g with at least 90% of said volume attributable to pores with a radius of less than 40 A and at least 90% of said surface area attributable to pores with a radius of less than 30 A.
    Type: Grant
    Filed: January 21, 1980
    Date of Patent: April 6, 1982
    Assignee: Societa' Italiana Resine S.I.R. S.p.A.
    Inventors: Roberto Canavesi, Ferdinando Ligorati, Giancarlo Aglietti
  • Patent number: 4310713
    Abstract: 1,2-dichloroethane is made by subjecting ethylene to an oxychlorination reaction with hydrogen chloride and a gas containing molecular oxygen in gas phase, at elevated temperature and in contact with a fluidized bed copper-II-chloride catalyst on a carrier, wherein the reaction gases are cooled under pressure in two condensation stages, condensed 1,2-dichloroethane and water are removed and the bulk of unreacted starting gas and inert gas are recycled. More specifically the reaction gases are delivered to a third condensation stage and cooled therein under pressure down to a temperature within the range 5.degree. to 18.degree. C. and to the extent necessary for the recycle gas to contain 0.5 to 3 volume % of 1,2-dichloroethane. Next, the recycle gas is directly admixed upstream of the reactor, with a quantity of pure oxygen necessary to replace consumed oxygen and re-establish an oxygen content of 12 to 25 volume % therein.
    Type: Grant
    Filed: April 24, 1978
    Date of Patent: January 12, 1982
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Gunter Legutke, Gerhard H. Rechmeier, Harald Scholz, Kurt Schuchardt, Ernst Holler, Gunther Liesenfelder
  • Patent number: 4284833
    Abstract: The active life of an oxychlorination copper-containing catalyst is extended by the removal of sulfur-containing compounds from the gases fed to the catalyst reaction zone. A copper-containing oxychlorination catalyst which has been deactivated by the deposition of sulfur compounds thereon is reactivated in situ by operating the catalyst bed in an oxygen-free atmosphere for a sufficient period of time. The reactivation of the catalyst is completed when the conversions of hydrocarbon and chlorinating agent to chlorinated products indicate a high level of catalyst activity, as determined by an analysis of the gaseous effluent leaving the catalyst bed.
    Type: Grant
    Filed: December 19, 1977
    Date of Patent: August 18, 1981
    Assignee: Stauffer Chemical Company
    Inventors: Robert J. Blake, Guy W. Roy
  • Patent number: 4273678
    Abstract: An oxychlorination catalyst which is an intimate mixture of the oxides of magnesium, aluminum and copper obtained by calcining is prepared by precipitating the hydrated oxides of magnesium and aluminum, drying and calcining these hydrated oxides to form a mixed oxide of magnesium and aluminum, treating the mixed oxide with a copper salt solution and again calcining to provide the copper oxide.
    Type: Grant
    Filed: May 11, 1979
    Date of Patent: June 16, 1981
    Assignee: Imperial Chemical Industries Limited
    Inventors: Ruth M. Lane, Martyn H. Stacey
  • Patent number: 4265837
    Abstract: The invention provides a process for making 1,2-dichloroethane by subjecting ethylene to an oxychlorination reaction with hydrogen chloride and a gas containing molecular oxygen, in gas phase, at elevated temperature and in contact with a fluidized bed catalyst of copper-II-chloride on a carrier, wherein the reaction gases are cooled under pressure in two condensation stages, condensed 1,2-dichloroethane and water are removed, the bulk of unreacted starting gas and inert gas are recycled, the reaction gases coming from the second condensation stage are delivered to a third condensation stage, cooled therein under pressure down to a temperature within the range 5.degree. to 18.degree. C. and to the extent necessary to retain in the recycle gas 0.5 to 3 volume % of 1,2-dichloroethane, and the recycle gas is admixed, directly upstream of the reactor, with a quantity of pure oxygen necessary to replace consumed oxygen.
    Type: Grant
    Filed: April 27, 1979
    Date of Patent: May 5, 1981
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Gunter Legutke, Harald Scholz, Kurt Schuchardt
  • Patent number: 4255359
    Abstract: A non-polluting oxyhydrochlorination process is provided in which the residual gaseous effluents are purified by catalytic oxidation in the presence of a catalyst comprising platinum and/or iridium deposited on a special alumina support of eta crystallographic structure and then washing the effluent before being discharged into the atmosphere.The process of the invention is particularly applicable to a residual effluent containing essentially carbon monoxide, carbon dioxide, ethylene, 1,2-dichloroethane, and at least one chlorinated hydrocarbon from among the group consisting of chloroform, carbon tetrachloride, ethyl chloride, 1,1-dichloroethane, 1,1,1- and 1,1,]-trichloroethanes, 1,1,2,2- and 1,1,1,2- tetrachloroethanes, vinyl chloride, 1,1- and 1,2-dichloroethylenes, trichloroethylene, perchloroethylene and chloral.
    Type: Grant
    Filed: April 9, 1979
    Date of Patent: March 10, 1981
    Assignee: Rhone-Poulenc Industries
    Inventor: Jean-Pierre Brunelle
  • Patent number: 4243650
    Abstract: A reaction effluent containing vaporized salt withdrawn from a reaction zone, such as a molten salt reaction zone, is contacted with solid particles to cool the gas and condense vaporized salt onto the particles. Such contacting may be effected in either a fluidized bed of solids or in a dilute phase transport contact zone. Heat is recovered either by indirect heat transfer in the fluidized bed or by separating the solid particles and introduction thereof into a fluidized bed cooled by indirect heat transfer. Solid salt is attrited from the particles during contacting with the reaction gas and fluidizing gas, with such solid salts being returned to the reaction zone.
    Type: Grant
    Filed: June 13, 1979
    Date of Patent: January 6, 1981
    Assignee: The Lummus Company
    Inventor: Utah Tsao