Metal Oxide Containing Catalyst Patents (Class 570/169)
  • Patent number: 5334787
    Abstract: An improved process for the manufacture of CF.sub.3 CHF.sub.2 by contacting 1,2-dichloro-1,1,2-trifluoroethane (CClF.sub.2 CHClF) or 1-chloro-1,1,2,2-tetrafluoroethane (CHF.sub.2 CClF.sub.2) or mixtures of CF.sub.3 CHCl.sub.2 and CClF.sub.2 CHClF or mixtures of CF.sub.3 CHClF and CHF.sub.2 CClF.sub.2 with HF in the presence of a Cr.sub.2 O.sub.3 catalyst prepared by pyrolysis of ammonium dichromate, the reaction being conducted under controlled conditions whereby the production of CF.sub.3 CHF.sub.2 is maximized, and the formation of chloropentafluoroethane (CF.sub.3 CClF.sub.2) and other perhalo derivatives is minimized. The subject hydrogen-containing compound is useful as a blowing agent, propellant, refrigerant, fire extinguishing agent, or sterilant carrier gas.
    Type: Grant
    Filed: November 12, 1992
    Date of Patent: August 2, 1994
    Assignee: E. I. Du Pont de Nemours and Company
    Inventors: Vinci M. Felix, William H. Gumprecht, Barry A. Mahler
  • Patent number: 5334785
    Abstract: An improved process for the vapor phase fluorination, especially fluorination of 1,1,1-trifluoro-2-chloroethane (CFC-133a) with HF to produce 1,1,1,2-tetrafluoroethane (HFC-134a) employs a catalyst which preferably consists essentially of boehmite and Cr(OH)Cl.sub.2.2H.sub.2 O, combined and extruded to form particulates and then heated in nitrogen.
    Type: Grant
    Filed: June 23, 1993
    Date of Patent: August 2, 1994
    Assignee: Allied-Signal Inc.
    Inventors: Li Wang, Timothy J. Barder, Mark Kaiser, Russell W. Johnson, Blaise J. Arena
  • Patent number: 5283382
    Abstract: Process for the preparation of fluorinated alkanes by contacting a starting material of halogenated alkene or alkane with 1 to 150 molar equivalents based on catalyst of HF, 1 to 30 molar equivalents based on catalyst of a dehydrating agent and less than 100 molar equivalents based on catalyst of a starting material, the catalyst being selected from niobium oxide or tantalum oxide, at a temperature of 0.degree. C. to 185.degree. C. The preferred dehydrating agent is a combination of chlorosulfonic acid and thionyl chloride.
    Type: Grant
    Filed: October 23, 1992
    Date of Patent: February 1, 1994
    Assignee: E. I. du Pont de Nemours and Company
    Inventor: Mario J. Nappa
  • Patent number: 5281568
    Abstract: A chromium-containing fluorination catalyst which comprises an activity-promoting amount of zinc or a compound of zinc, a process for increasing the activity of a chromium-containing fluorination catalyst by introducing an activity promoting amount of zinc or a compound of zinc to the catalyst and a process for the production of fluorinated hydrocarbons, in particular 1,1,1,2-tetrafluorethane which comprises reacting a hydrocarbon or a halogenated hydrocarbon, in particular 1-chloro-2,2,2-trifluoroethane with hydrogen fluoride in the vapour phase in the presence of the zinc-promoted chromium-containing catalyst.
    Type: Grant
    Filed: January 21, 1992
    Date of Patent: January 25, 1994
    Assignee: Imperial Chemical Industries PLC
    Inventors: John D. Scott, Michael J. Watson
  • Patent number: 5276224
    Abstract: A process for preparing 1,1,1-trifluoro-2,2-dichloroethane by hydrofluorination, in the gas phase, of perchloroethylene in the presence of a catalyst comprising chrome oxides supported on AlF.sub.3 in the gamma and/or beta form.
    Type: Grant
    Filed: November 25, 1992
    Date of Patent: January 4, 1994
    Assignee: Ausimont S.p.A.
    Inventors: Diego Carmello, Giorgio Guglielmo
  • Patent number: 5264639
    Abstract: A process for producing a 2,2-difluoropropane of the following formula (2), which comprises fluorinating a chlorine-containing 2,2-halogenopropane of the following formula (1) by hydrogen fluoride or a fluorinating agent:C.sub.3 H.sub.a Cl.sub.b F.sub.c (1)C.sub.3 H.sub.a Cl.sub.b-x F.sub.c+x (2)wherein a, b, c and x are integers satisfying the following conditions:a.gtoreq.0, b.gtoreq.1, c.gtoreq.0, x.gtoreq.1, a+b+c=8.
    Type: Grant
    Filed: May 20, 1992
    Date of Patent: November 23, 1993
    Assignee: Asahi Glass Company Ltd.
    Inventors: Shinsuke Morikawa, Shunichi Samejima, Hidekazu Okamoto, Keiichi Ohnishi, Shin Tatematsu, Toshihiro Tanuma, Takashi Ohmori
  • Patent number: 5262574
    Abstract: A process for preparing 1,1,1-trifluoro-2,2-dichloroethane by hydrofluorination, in the gas phase, of perchloroethylene in the presence of a catalyst comprising chrome oxides supported on AlF.sub.3 in the gamma and/or beta form.
    Type: Grant
    Filed: November 18, 1991
    Date of Patent: November 16, 1993
    Assignee: Ausimont S.p.A.
    Inventors: Diego Carmello, Giorgio Guglielmo
  • Patent number: 5258561
    Abstract: A chlorofluorination process is disclosed which employs a catalyst comprising chromium oxide for producing halohydrocarbons of the formula CHXFCF.sub.3 (where X is selected from Cl and F). The process is characterized by feeding a combination of components comprising, (i) at least one halohydrocarbon starting compound of the formula CY.sub.3 CH.sub.2 R.sup.1 (where R.sup.1 is selected from the group of H and F and each Y is independently selected from the group of Cl and F), (ii) hydrogen fluoride and (iii) chlorine to a reaction zone; contacting said combination of compounds in said reaction zone with a catalyst comprising chromium oxide at an elevated temperature to produce reaction zone products containing halohydrocarbon reaction products of the formula CHXFCF.sub.3 together with halohydrocarbons of the formula CZ.sub.3 CHR.sup.2 R.sup.3 (wherein R.sup.2 is selected from the group of H and Cl, R.sup.
    Type: Grant
    Filed: November 6, 1992
    Date of Patent: November 2, 1993
    Assignee: E. I. Du Pont de Nemours and Company
    Inventors: Mario J. Nappa, V. N. Mallikarjuna Rao
  • Patent number: 5243105
    Abstract: 1,1,1,2-tetrafluoroethane (HFA 134a) is manufactured from trichloroethylene by a two-stage process comprising reacting trichloroethylene with hydrogen fluoride under superatmospheric pressure in a first reaction zone to form 1,1,1-trifluoro-2-chloroethane (133a) and reacting the 1,1,1-trifluoro-2-chloroethane with hydrogen fluoride in a second reaction zone to form 1,1,1,2-tetrafluoroethane; the entire product stream from the 133a reaction zone together with additional HF of required is fed through the 134a reaction zone. The two reaction zones may be provided within a single reaction vessel.
    Type: Grant
    Filed: December 11, 1991
    Date of Patent: September 7, 1993
    Assignee: Imperial Chemical Industries PLC
    Inventors: John D. Scott, Rachel A. Steven
  • Patent number: 5243107
    Abstract: 1,1,1,2-tetrafluoroethane (HFA 134a) is manufactured from trichloroethylene by a two-stage process comprising reacting trichloroethylene with hydrogen fluoride in one reactor to form 1,1,1-trifluoro-2-chloroethane (133a) and reacting the 1,1,1-trifluoro-2-chloroethane with hydrogen fluoride in another reactor to form 1,1,1,2-tetrafluoroethane. The invention is characterised by reversing the reactor sequence and passing the entire product stream from the HFA 134a reactor together with trichloroethylene through the 133a reactor and separating 134a and hydrogen chloride from the recycle stream between the 133a reactor and the 134a reactor.
    Type: Grant
    Filed: September 5, 1991
    Date of Patent: September 7, 1993
    Assignee: Imperial Chemical Industries PLC
    Inventors: John D. Scott, Rachel A. Steven
  • Patent number: 5233105
    Abstract: Bismuth/alkaline earth metal catalysts which contain 0.005-0.8 g-atom of bismuth per mol of the alkaline earth metal compound employed and can furthermore contain promoters and/or inert additives, and lanthanide catalysts with or without catalyst supports can be employed as catalysts for halogen-fluorine exchange in organic compounds by means of hydrogen fluoride.
    Type: Grant
    Filed: October 25, 1990
    Date of Patent: August 3, 1993
    Assignee: Bayer Aktiengesellschaft
    Inventors: Hans-Helmut Schwarz, Rudolf Braden
  • Patent number: 5227350
    Abstract: A method for regenerating a used fluorination catalyst such as a chromium-containing compound comprises contacting the used catalyst at a temperature of 300.degree. C. to 500.degree. C. with a mixture of an oxidizing agent, especially air, and hydrogen fluoride and optionally an inert diluent such as nitrogen, said mixture containing up to 30% of oxidizing agent on a molar basis. The method obviates chromium loss during regeneration/refluorination of spent catalyst and provides heated hydrogen fluoride for use directly in fluorination reactions.
    Type: Grant
    Filed: July 17, 1992
    Date of Patent: July 13, 1993
    Assignee: Imperial Chemical Industries PLC
    Inventors: John D. Scott, Pravin K. Dattani
  • Patent number: 5220083
    Abstract: The present invention relates to syntheses of perfluoropropane-- .e., octafluoropropane--from acyclic three-carbon hydrocarbons or partially or totally halogenated acyclic three-carbon hydrocarbons.
    Type: Grant
    Filed: January 28, 1992
    Date of Patent: June 15, 1993
    Assignee: E. I. Du Pont de Nemours and Company
    Inventors: James L. Webster, Steven H. Swearingen, Douglas W. Bruhnke, Leo E. Manzer, Elrey L. McCann
  • Patent number: 5177273
    Abstract: A vapor phase process is disclosed for producing HCFC-225s, HCFC-235s, HCFC-226s, HFC-236s, and HFC-227s by reacting certain three-carbon reactants containing at least one less fluorine than, and at least as many hydrogen substituents as the desired product (e.g. propane propylene, allene or methylacetylene) with Cl.sub.2 and HF in the presence of a catalyst consisting essentially of chromium oxide or of chromium oxide which is combined with a refractory oxide, fluorinated and/or modified with manganese, iron, cobalt, nickel, copper and/or zinc. The temperature and contact time for the reaction are chosen to provide a product having the desired fluorine and hydrogen content.
    Type: Grant
    Filed: February 1, 1991
    Date of Patent: January 5, 1993
    Assignee: E. I. Du Pont de Nemours and Company
    Inventors: Douglas W. Bruhnke, Jan J. Lerou, V. N. Mallikarjuna Rao, William C. Seidel, Frank J. Weigert
  • Patent number: 5171901
    Abstract: Hexafluoropropanes of the formula CF.sub.3 -CHX-CF.sub.3 where X is hydrogen or chlorine are prepared by reacting hexachloropropene with hydrogen fluoride in the gas phase in the presence of a catalyst.
    Type: Grant
    Filed: December 5, 1991
    Date of Patent: December 15, 1992
    Assignee: Bayer Aktiengesellschaft
    Inventors: Karl-Rudolf Gassen, Dietmar Bielefeldt, Albrecht Marhold, Hans-Helmut Schwarz
  • Patent number: 5159126
    Abstract: 1-Chloro-1,1-difluoroethane is prepared by reacting hydrogen fluoride with vinylidene chloride, in a liquid medium containing preferably at least 40 mol % 1,1-dichloro-1-fluoroethane.
    Type: Grant
    Filed: December 4, 1990
    Date of Patent: October 27, 1992
    Assignee: Solvay S.A.
    Inventors: Rene Walraevens, James Franklin, Jean-Marie Yernaux
  • Patent number: 5091601
    Abstract: A process for preparing 1,1,1-trifluoro-2,2-dichloroethane by hydrofluorination, in the gas phase, of perchloroethylene in the presence of a catalyst comprising chrome oxides supported on AlF.sub.3 in the gamma and/or beta form.
    Type: Grant
    Filed: September 19, 1990
    Date of Patent: February 25, 1992
    Assignee: Austimont S.p.A.
    Inventors: Diego Carmello, Giorgio Guglielmo
  • Patent number: 5087779
    Abstract: A method for halogenating hydrocarbons wherein a reaction mixture including a hydrocarbon-containing feed, a hydrogen halide and an oxygen-containing gas is contacted at appropriate reaction conditions with a catalyst of copper aluminum borate to form halogenated hydrocarbons.
    Type: Grant
    Filed: April 25, 1990
    Date of Patent: February 11, 1992
    Assignee: Amoco Corporation
    Inventors: Philip O. Nubel, Larry C. Satek, Michael J. Spangler, Glenn O. Michaels
  • Patent number: 5068472
    Abstract: The present invention relates to multistep syntheses of hexafluoropropylene from hexachloropropylene. In all these syntheses the first step is a fluorination of the starting material; later steps convert the initial products to CF.sub.3 --CFCl--CF.sub.3, which is dehalogenated to the desired product.
    Type: Grant
    Filed: December 19, 1989
    Date of Patent: November 26, 1991
    Assignee: E. I. Du Pont de Nemours and Company
    Inventors: James L. Webster, Swiatoslaw Trofimenko, Paul R. Resnick, Douglas W. Bruhnke, Jan J. Lerou, William H. Manogue, Leo E. Manzer, Elrey L. McCann, Steven H. Swearingen, James A. Trainham, Cristobal Bonifaz
  • Patent number: 5057634
    Abstract: The present invention relates to multistep syntheses of hexafluoropropylene from acyclic three-carbon hydrocarbons or partially halogenated acyclic three-carbon hydrocarbons. In all these syntheses the first step is a vapor-phase chlorofluorination of the starting material to one or more saturated chlorofluorocarbons. Novel catalysts are also provided.
    Type: Grant
    Filed: December 19, 1989
    Date of Patent: October 15, 1991
    Assignee: E. I. Du Pont de Nemours and Company
    Inventors: James L. Webster, Elrey L. McCann, Douglas W. Bruhnke, Jan J. Lerou, William H. Manogue, Leo E. Manzer, Steven H. Swearingen, Swiatoslaw Trofimenko, Cristobal Bonifaz
  • Patent number: 5043491
    Abstract: The present invention relates to multistep syntheses of hexafluoropropylene from propane, propylene or partially halogenated acyclic three-carbon hydrocarbons. In all these syntheses the first step is a vapor-phase chlorofluorination of the starting material to the unsaturated chlorofluorocarbon CF.sub.3 CClCCl.sub.2.
    Type: Grant
    Filed: December 19, 1989
    Date of Patent: August 27, 1991
    Assignee: E. I. Du Pont de Nemours and Company
    Inventors: James L. Webster, Elrey L. McCann, Douglas W. Bruhnke, Jan J. Lerou, Leo E. Manzer, William H. Manogue, Paul R. Resnick, Swiatoslaw Trofimenko
  • Patent number: 4996379
    Abstract: 1,1,1,2-Tetrafluoroethane, a refrigerant, is formed with little formation of isomers or chlorofluoroethanes having not very different boiling points by reacting 1,1-dichloro-1,2,2,2-tetrafluoroethane (R-114a), which may contain up to about 25 wt% of 1,2-dichloro-1,1,2,2-tetrafluoroethane (R-114), with hydrogen gas in the presence of a palladium-on-active alumina catalyst at a temperature lower than 200.degree. C. and not lower than 120.degree. C. R-114a almost free of R-114 is obtained by reacting 1,1,1-trichloro-2,2,2-trifluoroethane with hydrogen fluoride in vapor phase in the presence of a catalyst prepared by partially fluorinating .gamma.-alumina by treatment with hydrogen fluoride gas.
    Type: Grant
    Filed: May 26, 1989
    Date of Patent: February 26, 1991
    Assignee: Central Glass Company, Limited
    Inventors: Hideki Oshio, Sadaharu Mishumi, Kiyoshi Yagii, Satoshi Yoshikawa, Katsuyoshi Murata
  • Patent number: 4967023
    Abstract: A process for preparing 1,1,1-trifluoro-2,2-dichloroethane by hydrofluorination, in the gas phase, of perchloroethylene in the presence of a catalyst comprising chrome oxides supported on AlF.sub.3 in the gamma and/or beta form.
    Type: Grant
    Filed: September 5, 1989
    Date of Patent: October 30, 1990
    Assignee: Ausimont S.p.A.
    Inventors: Diego Carmello, Giorgio Guglielmo
  • Patent number: 4912270
    Abstract: Chromium(III) oxide and hydroxide aerogels are produced by the reaction of chromium(VI) oxide with a solvent which is reducing to chromium(VI), such as methanol, heating the solution to hypercritical conditions, and venting the solvent hypercritically. The product aerogels exhibit surface areas above 400 m.sup.2 /g, pore volumes of at least 2 cm.sup.3 /g and a substantially uniform pore size distribution. Also disclosed is a unique process which employs high pore volume, high surface area chromium(III) oxide or hydroxide as a fluorination catalyst. More particularly, reaction of C.sub.2 Cl.sub.3 F.sub.3 with HF over these catalysts produced high yields of C.sub.2 Cl.sub.2 F.sub.4 and C.sub.2 ClF.sub.5.
    Type: Grant
    Filed: December 12, 1988
    Date of Patent: March 27, 1990
    Assignee: Allied-Signal Inc.
    Inventors: Emery J. Carlson, John N. Armor, William J. Cunningham, Addison M. Smith
  • Patent number: 4843181
    Abstract: An improved gas-phase process for the manufacture of 1,1,1-trifluorodichloroethane and/or 1,1,1,2-tetrafluorochloroethane by contacting a suitable tetrahaloethylene and/or pentahaloethane with hydrogen fluoride in the presence of Cr.sub.2 O.sub.3, prepared by pyrolysis of (NH.sub.4).sub.2 Cr.sub.2 O.sub.7, the reaction being conducted under controlled conditions whereby the production of pentafluoroethane is minimized.
    Type: Grant
    Filed: October 22, 1987
    Date of Patent: June 27, 1989
    Assignee: E. I. Du Pont de Nemours and Company
    Inventors: William H. Gumprecht, Leo E. Manzer, V. N. Mallikarjuna Rao
  • Patent number: 4748285
    Abstract: This invention relates to catalysts for gaseous phase fluorination of aliphatic chlorinated derivatives by hydrofluoric acid. The catalysts comprise chromium oxide microspheres obtained by a sol-gel process. This invention also relates to gaseous phase fluorination processes for aliphatic chlorinated derivatives utilizing these catalysts.
    Type: Grant
    Filed: November 25, 1986
    Date of Patent: May 31, 1988
    Assignee: Produits Chimiques Ugine Kuhlmann
    Inventor: Louis Foulletier
  • Patent number: 4605798
    Abstract: This invention relates to a continuous gaseous-phase process for the preparation of trichlorotrifluoroethane, dichlorotetrafluoroethane and monochloropentafluoroethane, in predetermined proportions, from tetrachloroethylene, chlorine and hydrofluoric acid in the presence of a catalyst. The process is characterized by the combination of two chlorination-fluorination reactors in sequence, a parallel fluorination-dismutation reactor, and a separation unit for extracting the desired products and recycling recovered hydrofluoric acid and non-fluorinated or insufficiently fluorinated products. The process advantageously yields dichlorotetrafluoroethane containing less than 7% asymmetric isomer, and trichlorotrifluoroethane containing less than 2% asymmetric isomer.
    Type: Grant
    Filed: November 25, 1981
    Date of Patent: August 12, 1986
    Assignee: PCUK Products Chimiques Ugine Kuhlmann
    Inventors: Michel Abel, Francois Fine, Louis Foulletier, Yvan Verot
  • Patent number: 4578369
    Abstract: According to the specified process chromium oxyfluoride catalysts which have largely lost their activity are regenerated. The catalysts are mixed with magnesium oxide or magnesium hydroxide in the presence of water and converted into a paste. If necessary the mixture must be concentrated by evaporation until it exhibits the consistency of a paste. Finally the paste is dried. The paste is best converted into molded bodies such as, for example, granules before drying.
    Type: Grant
    Filed: June 25, 1985
    Date of Patent: March 25, 1986
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Thomas Muller, Gunter Siegemund
  • Patent number: 4547483
    Abstract: A process is specified for preparing a chromium- and magnesium-containing catalyst for fluorination reactions by precipitating chromium(III) hydroxide. In this process, 1 mole of a water-soluble chromium(III) salt is reacted with at least 1.5 moles of magnesium hydroxide or magnesium oxide in the presence of water, and the reaction mixture--if necessary by evaporation--is converted into a paste which contains chromium(III) hydroxide and a magnesium salt. The paste is dried and treated with hydrogen fluoride at temperatures of 20.degree. to 500.degree. C.
    Type: Grant
    Filed: June 27, 1984
    Date of Patent: October 15, 1985
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Thomas Muller, Gunter Siegemund
  • Patent number: H1188
    Abstract: A process for the preparation of 1,1-dichloro-1,2-difluoroethane (HCFC-132c) comprising contacting 1,1-dichloroethylene with lead dioxide and anhydrous hydrogen fluoride. Addition of fluorine to the double bond of vinylidene chloride can be achieved using inexpensive and readily available commercial raw materials.
    Type: Grant
    Filed: September 19, 1990
    Date of Patent: May 4, 1993
    Assignee: E. I. Du Pont de Nemours and Company
    Inventors: Mario J. Nappa, Allen C. Sievert