Alkali Or Alkaline Earth Metal Containing Catalyst Patents (Class 570/157)
  • Patent number: 8034984
    Abstract: Dehydrohalogenation processes for the preparation of fluoropropenes from corresponding halopropanes, in which the fluoropropenes have the formula CF3CY?CXNHP, wherein X and Y are independently hydrogen or a halogen selected from fluorine, chlorine, bromine and iodine; and N and P are independently integers equal to 0, 1 or 2, provided that (N+P)=2.
    Type: Grant
    Filed: September 22, 2010
    Date of Patent: October 11, 2011
    Assignee: Honeywell International Inc.
    Inventors: Daniel C. Merkel, Rajiv R. Singh, Hsueh S. Tung
  • Publication number: 20110245549
    Abstract: The disclosed integrated manufacturing process includes a combined liquid phase reaction and purification operation which directly produces trans-1-chloro-3,3,3-trifluoropropene and 3-chloro-1,1,1,3-tetrafluoropropane which is a precursor to the manufacture of trans-1,3,3,3-tetrafluoropropene. The mixture of co-products is easily separated by conventional distillation and 3-chloro-1,1,1,3-tetrafluoropropane is then dehydrochlorinated to produce trans-1,3,3,3-tetrafluoropropene by contacting in the liquid phase with a caustic solution or in the vapor phase using a dehydrochlorination catalyst.
    Type: Application
    Filed: April 5, 2010
    Publication date: October 6, 2011
    Applicant: HONEYWELL INTERNATIONAL INC.
    Inventors: Daniel C. Merkel, Robert Johnson, Hsueh Sung Tung, Haiyou Wang, Konstantin A. Pokrovski
  • Patent number: 7985884
    Abstract: Disclosed is a process for the manufacture of 2,3,3,3-tetrafluoropropene comprising: (a) dehydrofluorinating 1,1,1,2,3-pentafluoropropane in the presence of a dehydrofluorination catalyst comprised of chromium (III) oxide, and alkali metal, to produce a product mixture comprising 2,3,3,3-tetrafluoropropene and less than 20 parts per hundred 1,3,3,3-tetrafluoro-1-propene; and (b) recovering said 2,3,3,3-tetrafluoropropene from the product mixture produced in (a).
    Type: Grant
    Filed: June 3, 2010
    Date of Patent: July 26, 2011
    Assignee: E. I. du Pont de Nemours and Company
    Inventors: Mario Joseph Nappa, Andrew Jackson
  • Patent number: 7982073
    Abstract: A process is disclosed for making CF3CF?CHF. The process involves contacting at least one hexafluoropropane selected from the group consisting of CF3CF2CH2F and CF3CHFCHF2 with a chromium oxyfluoride catalyst in a reactor to obtain a product mixture comprising CF3CF?CHF, and recovering CF3CF?CHF from the product mixture. A process is disclosed for making CF3CH?CHF. The process involves contacting CF3CH2CHF2 with a chromium oxyfluoride catalyst in a reactor to obtain a product mixture comprising CF3CH?CHF, and recovering CF3CH?CHF from the product mixture. A process is disclosed for making CF3CF?CH2. The process involves contacting CF3CF2CH3 with a chromium oxyfluoride catalyst in a reactor to obtain a product mixture comprising CF3CF?CH2, and recovering CF3CF?CH2 from the product mixture.
    Type: Grant
    Filed: July 11, 2007
    Date of Patent: July 19, 2011
    Assignee: E. I. du Pont de Nemours and Company
    Inventors: Mario Joseph Nappa, Velliyur Nott Mallikarjuna Rao
  • Publication number: 20100312025
    Abstract: Disclosed is a process for the manufacture of 2,3,3,3-tetrafluoropropene comprising: (a) dehydrofluorinating 1,1,1,2,3-pentafluoropropane in the presence of a dehydrofluorination catalyst comprised of chromium (III) oxide, and alkali metal, to produce a product mixture comprising 2,3,3,3-tetrafluoropropene and less than 20 parts per hundred 1,3,3,3-tetrafluoro-1-propene; and (b) recovering said 2,3,3,3-tetrafluoropropene from the product mixture produced in (a).
    Type: Application
    Filed: June 3, 2010
    Publication date: December 9, 2010
    Applicant: E.I. DU PONT DE NEMOURS AND COMPANY
    Inventors: MARIO JOSEPH NAPPA, Andrew Jackson
  • Patent number: 7803973
    Abstract: Dehydrohalogenation processes for the preparation of fluoropropenes from corresponding halopropanes, in which the fluoropropenes have the formula CF3CY?CXNHP, wherein X and Y are independently hydrogen or a halogen selected from fluorine, chlorine, bromine and iodine; and N and P are independently integers equal to 0, 1 or 2, provided that (N+P)=2.
    Type: Grant
    Filed: April 16, 2008
    Date of Patent: September 28, 2010
    Assignee: Honeywell International Inc.
    Inventors: Daniel C. Merkel, Rajiv R. Singh, Hsueh Sung Tung
  • Patent number: 7786333
    Abstract: A process for the production of fluorinated olefins, preferably fluorinated propenes, by contacting a feed stream containing a fluorinated olefin and hydrogen with a first amount of catalyst to produce the hydrofluorocarbon, wherein a first exit stream contains unreacted fluorinated olefin and hydrogen; contacting the first exit stream with a second amount of catalyst to produce a hydrofluorocarbon, wherein the second amount of catalyst is preferably greater than the first amount of catalyst; and contacting the hydrofluorocarbon with a catalyst for dehydrohalogenation to produce a product stream of fluorinated olefin.
    Type: Grant
    Filed: February 19, 2009
    Date of Patent: August 31, 2010
    Assignee: Honeywell International, Inc.
    Inventors: Michael Van Der Puy, George R. Cook, Peter H. Sheidle, Kevin D. Uhrich, Haiyou Wang, Hsueh Sung Tung
  • Publication number: 20100185029
    Abstract: The present invention discloses a process for the synthesis of hydrofluoroolefins (HFO). The process is based on the following two steps: the liquid phase fluorination of a hydrochloropropane(s) to hydrofluoropropane(s) (HFP) followed by the dehydrofluorination of the hydrofluoropropane(s) (HFP) to hydrofluoroolefins (HFO).
    Type: Application
    Filed: June 27, 2008
    Publication date: July 22, 2010
    Applicant: ARKEMA INC.
    Inventors: Maher Y. Elsheikh, Philippe Bonnet, Laurent Wendlinger
  • Patent number: 7714177
    Abstract: Disclosed is a process for the synthesis of 1,3,3,3-tetrafluoropropene comprising: a) reacting a compound of the formula (I) CHFX2 with a compound of formula (II) CH2?CF2 to produce a reaction product comprising a compound of formula (III) CHXFCH2CXF2, wherein each X is independently selected from the group consisting of chlorine, bromine and iodine; and (b) exposing said compound of formula (III) to reaction conditions effective to convert said compound to 1,3,3,3-tetrafluoropropene.
    Type: Grant
    Filed: January 7, 2008
    Date of Patent: May 11, 2010
    Assignee: Honeywell International Inc.
    Inventors: Sudip Mukhopadhyay, Haridasan K. Nair, Hsueh S. Tung, Michael Van Der Puy
  • Patent number: 7700815
    Abstract: Disclosed is a method for producing fluorinated organic compounds, including petnafluoropropenes, which preferably comprises converting at least one compound of formula (I): CFnXmCFaXbCH2X??(I) to at least one compound of formula (II) CF3CF?CHF??(II) where each X is independently Cl, I or Br; n is 2 or 3; m is 0 or 1, a is 1 or 2, b is 0 or 1, m+n=3 and a+b=2.
    Type: Grant
    Filed: September 28, 2007
    Date of Patent: April 20, 2010
    Assignee: Honeywell International Inc
    Inventors: Hsueh Sung Tung, Rajiv R. Singh, Michael Van Der Puy
  • Publication number: 20090306438
    Abstract: The present disclosure relates to a new and efficient manufacturing process for the production of HFC-1225ye. The process involves contacting at least one hexafluoropropane selected from the group consisting of 1,1,1,2,2,3-hexafluoropropane and 1,1,1,2,3,3-hexafluoropropane with a suitable catalyst in a reactor to obtain a product mixture containing HFC-1225ye (1,2,3,3,3-pentafluoropropene) where the pressure in the reactor ranges from about 0.5 psig to about 100 psig.
    Type: Application
    Filed: September 5, 2007
    Publication date: December 10, 2009
    Inventors: Allen Capron Sievert, Mario Joseph Nappa, Barry Asher Mahler
  • Publication number: 20090299107
    Abstract: A process for making a fluorinated olefin. The process has the step of dehydrochlorinating a hydrochlorofluorocarbon having at least one hydrogen atom and at least one chlorine atom on adjacent carbon atoms in the presence of a catalytically effective amount of a catalyst composition. The catalyst composition is represented by the following: n wt. % MX/M?OyFz, wherein 0<y<1 and 0<z<2 and wherein y+z/2=1; M is an alkali metal ion selected from the group consisting of Li+, Na+, K+, Rb+, and Cs+; X is a halogen ion selected from the group consisting of F?, Cl?, Br?, and I?, M? is a bivalent metal ion; wherein n is a weight percentage of about 0.05% to about 50% MX based on the total weight of the MX and M?OyFz, and wherein y and z are the mole fractions of oxygen and fluorine in M?OyFz, respectively. There are also methods for making catalyst compositions.
    Type: Application
    Filed: May 27, 2009
    Publication date: December 3, 2009
    Inventors: Haiyou Wang, Hsueh Sung Tung
  • Publication number: 20090216053
    Abstract: Disclosed is a process for producing hexafluoro-1,3-butadiene, which is used for an etching gas capable of being used in fine processing for semiconductors, safely in industrialization and at low cost economically. Specifically disclosed is a process for producing hexafluoro-1,3-butadiene comprises (1) a step comprising allowing a compound having four carbon atoms each which bonds to an atom selected from the group consisting of a bromine atom, an iodine atom and a chlorine atom, to react with a fluorine gas in the presence of a diluting gas in a gas phase, thereby preparing a mixture containing a product (A), and (2) a step comprising eliminating halogens excluding a fluorine atom with a metal from the product (A) prepared in the step (1) in the presence of a solvent, thereby preparing a mixture containing hexafluoro-1,3-butadiene.
    Type: Application
    Filed: April 25, 2007
    Publication date: August 27, 2009
    Applicant: Showa Denko K.K.
    Inventors: Hiromoto Ohno, Toshio Ohi
  • Publication number: 20090149680
    Abstract: There is provided methods for making a catalyst composition represented by the formula MX/M?F2 wherein MX is an alkali metal halide; M is an alkali metal ion selected from the group consisting of Li+, Na+, K+, Rb+, and Cs+; X is a halogen ion selected from the group consisting of F?, Cl?, Br?, and I?; M?F2 is a bivalent metal fluoride; and M? is a bivalent metal ion. One method has the following steps: (a) dissolving an amount of the alkali metal halide in an amount of solvent sufficient to substantially dissolve or solubilize the alkali metal halide to form an alkali metal halide solution; (b) adding an amount of the bi-valent metal fluoride to the alkali metal halide solution to form a slurry of the alkali metal halide and bi-valent metal fluoride; and (c) removing substantially all of the solvent from the slurry to form a solid mass of the alkali metal halide and bi-valent metal fluoride.
    Type: Application
    Filed: November 21, 2008
    Publication date: June 11, 2009
    Inventors: Haiyou Wang, Hsueh Sung Tung
  • Patent number: 7491857
    Abstract: An aminated oligonucleotide probe is provided, in which the amino group possesses improved reactivity. The present invention relates to an oligonucleotide probe, which is represented by general formula 1: (wherein R1 is a hydrogen atom or a protecting group for an amino group, R2 and R3 are each independently a divalent organic group, and A is an oligonucleotide).
    Type: Grant
    Filed: November 17, 2005
    Date of Patent: February 17, 2009
    Assignees: National Institute of Advanced Industrial Science and Technology, DNA Chip Research Inc.
    Inventors: Yasuo Komatsu, Naoshi Kojima, Kosuke Sato, Ken Nonaka, Yumi Fujinawa
  • Patent number: 7345209
    Abstract: Disclosed is a process for the synthesis of 1,3,3,3-tetrafluoropropene that comprises, in one preferred embodiment, providing a compound of the formula CF3CH2CHFX, wherein X is a selected from the group consisting of chlorine, bromine and iodine, and exposing said compound to reaction conditions effective to convert said compound to 1,3,3,3-tetrafluoropropene. Other processes for forming 1,3,3,3-tetrafluoropropene are also disclosed.
    Type: Grant
    Filed: April 29, 2005
    Date of Patent: March 18, 2008
    Assignee: Honeywell International Inc.
    Inventors: Sudip Mukhopadhyay, Haridasan K. Nair, Hsueh S. Tung, Michael Van Der Puy
  • Patent number: 7312367
    Abstract: The invention provides an economic process for the manufacture of the hydrofluorocarbon 1,1,3,3,3-pentafluoropropene (HFC-1225zc). HFC-1225zc can be made from the dehydrochlorination of 1-chloro-1,1,3,3,3-pentafluoropropane (HCFC-235fa). Alternatively, HFC-1225zc can also be made from the dehydrofluorination of 1,1,1,3,3,3-hexafluoropropane (HFC-236fa). HFC-1225zc) is a compound that has the potential to be used as a low Global Warming Potential refrigerant, blowing agent, aerosol propellant, or solvent.
    Type: Grant
    Filed: June 14, 2006
    Date of Patent: December 25, 2007
    Assignee: Honeywell International Inc.
    Inventors: Hsueh Sung Tung, Daniel C. Merkel, Rajiv R. Singh
  • Patent number: 7271301
    Abstract: A gold-lined pyrolysis reactor is used to pyrolyze compounds to form fluoroolefins like tetrafluoroethylene and hexafluoropropylene in high yield, with minimum to no formation of perfluoroisobutylene, chlorotrifluoroethylene, coke, salts, or polymer.
    Type: Grant
    Filed: February 22, 2006
    Date of Patent: September 18, 2007
    Assignee: E.I. du Pont de Nemours and Company
    Inventors: Peter Gideon Gelblum, Norman Herron, Charles Joseph Noelke, Velliyur Nott Mallikarjuna Rao
  • Patent number: 7230146
    Abstract: Dehydrohalogenation processes for the preparation of fluoropropenes from corresponding halopropanes, in which the fluoropropenes have the formula CF3CY?CXNHP, wherein X and Y are independently hydrogen or a halogen selected from fluorine, chlorine, bromine and iodine; and N and P are independently integers equal to 0, 1 or 2, provided that (N+P)=2.
    Type: Grant
    Filed: October 27, 2003
    Date of Patent: June 12, 2007
    Assignee: Honeywell International Inc.
    Inventors: Daniel C. Merkel, Rajiv R. Singh, Hsueh Sung Tung
  • Patent number: 7164050
    Abstract: A process for preparing a halo-olefin to minimize one or more side reactions which form at least one impurity, said process comprising contacting a halogenated hydrocarbon with a metal dehalogenating agent dissolved in a solvent under conditions sufficient to dehalogenate said halogenated hydrocarbon to produce a product stream comprising said halo-olefin and at least one impurity, said metal dehalogenating agent having an average particle size within a range of average particle sizes, said impurity concentration of said product stream being essentially constant within said range and increasing significantly below said range.
    Type: Grant
    Filed: May 2, 2005
    Date of Patent: January 16, 2007
    Assignee: Honeywell International Inc.
    Inventors: Stephen A. Cottrell, William R. Jones
  • Patent number: 7091388
    Abstract: The invention provides an economic process for the manufacture of the hydrofluorocarbon 1,1,3,3,3-pentafluoropropene (HFC-1225zc). HFC-1225zc can be made from the dehydrochlorination of 1-chloro-1,1,3,3,3-pentafluoropropane (HCFC-235fa). Alternatively, HFC-1225zc can also be made from the dehydrofluorination of 1,1,1,3,3,3-hexafluoropropane (HFC-236fa). HFC-1225zc) is a compound that has the potential to be used as a low Global Warming Potential refrigerant, blowing agent, aerosol propellant, or solvent.
    Type: Grant
    Filed: September 26, 2003
    Date of Patent: August 15, 2006
    Assignee: Honeywell International Inc.
    Inventors: Hsueh Sung Tung, Daniel C. Merkel, Rajiv R. Singh
  • Patent number: 7030283
    Abstract: This invention relates to a process for the preparation of 1,1-difluoroolefins, e.g., difluorovinyl cycloaliphatic compounds such as difluorovinylcyclohexane and derivatives by the dehydrofluorination of a trifluoromethyl-substituted cycloaliphatic compound and the resulting compositions. This method utilizes a “sterically hindered super-base” system represented by the formula M+?NRR?; where M is Na or K and R is a secondary, or tertiary alkyl or cycloalkyl group of amines for effecting dehydrofluorination of the trifluoromethyl group leading to the difluorovinyl based cycloaliphatic compounds. The sterically hindered super base can be formed by the, in situ, reaction of a sodium or potassium alkoxide, e.g., KtBuO with a lithium dialkylamide where the lithium is bonded to nitrogen atom of an amine bearing secondary or tertiary aliphatic groups.
    Type: Grant
    Filed: January 23, 2004
    Date of Patent: April 18, 2006
    Assignee: Air Products and Chemicals, Inc.
    Inventors: Gauri Sankar Lal, Kathryn Sue Hayes, Guido Peter Pez
  • Patent number: 7026521
    Abstract: A gas phase reaction process for producing a hydrofluorocarbon from a hydrochlorofluorocarbon or chlorofluorocarbon reactant by contacting, in the presence of a catalyst, the hydrochlorofluorocarbon or chlorofluorocarbon reactant with a reducing agent selected from methane, methyl chloride and mixtures thereof, to produce the hydrofluorocarbon.
    Type: Grant
    Filed: March 28, 2005
    Date of Patent: April 11, 2006
    Assignee: Honeywell International Inc.
    Inventors: Sudip Mukhopadhyay, HsuehSung Tung, Daniel C. Merkel, Robert C. Johnson
  • Patent number: 6548720
    Abstract: A process is disclosed for producing the pentfluropropenes of the formula CF3CX═CF2, where X is H or Cl. The process involves hydrodehalogenating CF3CCl2CF3 with hydrogen at an elevated temperature in the vapor phase over a catalyst comprising an elemental metal, metal oxide, metal halide and/or metal oxyhalide (the metal being copper, nickel, chromium and the halogen of said halides and said oxyhalides being fluorine and/or chlorine. Processes for producing the hydrofluorocarbons CF3CH2CHF2, CF3CHFCF3 and CF3CH2CF3 are also disclosed which involve (a) hydrodehalogenating CF3CCl2CF3 with the hydrogen as indicated above to produce a product comprising CF3CCl═CF2, CF3CH═CF2, HCl and HF; and (b) either reacting the CF3CCl═CF2 and/or CF3CH═CF2 produced in (a) in the vapor phase with hydrogen to produce CF3CH2CHF2, reacting CF3CCl═CF2 produced in (a) with HF to produce CF3CHFCF3, or reacting the CF3CH═CF2produced in (a) with HF to produce CF3CH2CF3.
    Type: Grant
    Filed: January 30, 2002
    Date of Patent: April 15, 2003
    Assignee: E. I. du Pont de Nemours and Company
    Inventors: William H. Manogue, V. N. Mallikarjuna Rao, Allen Capron Sievert, Steven H. Swearingen
  • Patent number: 6548719
    Abstract: A process for producing a fluoroolefin of the formula: CF3CY═CXnHp wherein Y is a hydrogen atom or a halogen atom (i.e., fluorine, chlorine, bromine or iodine); X is a hydrogen atom or a halogen atom (i.e., fluorine, chlorine, bromine or iodine); n and p are integers independently equal to 0, 1 or 2, provided that (n+p)=2; comprising contacting, in the presence of a phase transfer catalyst, a compound of the formula: CF3C(R1aR2b)C(R3cR4d), wherein R1, R2, R3, and R4 are independently a hydrogen atom or a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine, provided that at least one of R1, R2, R3, and R4 is halogen and there is at least one hydrogen and one halogen on adjacent carbon atoms; a and b are independently=0, 1 or 2 and (a+b)=2; and c and d are independently=0, 1, 2 or 3 and (c+d)=3; and at least one alkali metal hydroxide.
    Type: Grant
    Filed: September 25, 2001
    Date of Patent: April 15, 2003
    Assignee: Honeywell International
    Inventors: Haridasan K. Nair, Michael Van Der Puy, David Nalewajek, Timothy R. Demmin, Andrew J. Poss, David E. Bradley, Ian R. Shankland
  • Patent number: 6476281
    Abstract: A method for the production of 1,1,1,3,3-pentafluoropropene, and particularly to a method characterized by high conversion, yield and selectivity by contacting 2,2-dichloro-1,1,1,3,3,3-hexafluoropropane with hydrogen in the presence of a metal-containing catalyst. The 1,1,1,3,3-pentafluoropropene then can be reacted with hydrogen in the presence of a metal-containing catalyst to produce 1,1,1,3,3-pentafluoropropane.
    Type: Grant
    Filed: July 26, 2001
    Date of Patent: November 5, 2002
    Assignee: PCBU Services, Inc.
    Inventors: John Cheng-Ping Qian, Julia Ann Sacarias
  • Patent number: 6380446
    Abstract: Halogenated compounds are dehydrohalogenated in a multi-stage bubble reactor wherein agitation of the reactor contents is provided by in situ generation and vaporization of reaction product having a boiling point lower than that of the reactants.
    Type: Grant
    Filed: March 7, 2001
    Date of Patent: April 30, 2002
    Assignee: DuPont Dow Elastomers, L.L.C.
    Inventors: David William Drew, Terry Wayne Redwine
  • Patent number: 6376727
    Abstract: Disclosed are azeotropic compositions comprising CF3CHFCF3 and HF. Also disclosed are compositions and a process for producing compositions comprising (c1) CF3CHFCF3, CF3CH2CF3, or CHF2CH2CF3, and (c2) at least one saturated halogenated hydrocarbon and or ether having the formula: CnH2n+2−a−bClaFbOc wherein n is an integer from 1-4, a is an integer from 0-2n+1, b is an integer from 1-2n+2a, and c is 0 or 1, provided that when c is 1 then n is an integer from 2-4, and provided that component (c2) does not include the selected component (c1) compound, wherein the molar ratio of component (c2) to component (c1) is between about 1:99 and a molar ratio of HF to component (c1) in an azeotrope or azeotrope-like composition of component (c1) with HF.
    Type: Grant
    Filed: August 19, 1999
    Date of Patent: April 23, 2002
    Assignee: E. I. du Pont de Nemours and Company
    Inventors: V. N. Mallikarjuna Rao, Allen Capron Sievert
  • Patent number: 6369284
    Abstract: A process is disclosed for the manufacture of a pentafluoropropene of the formula: CFX═CYCF3 where X is selected from H and F and where Y is F when X is H and Y is H when X is F. The process involves contacting a hexafluoropropane of the formula: CF2XCHYCF3 at a temperature of from about 200° C. to 500° C. with a catalyst, optionally in the presence of an inert gas. Suitable catalysts include (1) catalysts of (a) at least one compound selected from the oxides, fluorides and oxyfluorides of magnesium, zinc and mixtures of magnesium and zinc, and optionally (b) at least one compound selected from the oxides, fluorides and oxyfluorides of aluminum; provided that the atomic ratio of aluminum to the total of magnesium and zinc in said catalyst is about 1:4, or less (e.g., 1:9), (2) lanthanum fluoride, (3) fluorided lanthanum oxide, (4) activated carbon, and (5) three-dimensional matrix carbonaceous materials.
    Type: Grant
    Filed: July 26, 1999
    Date of Patent: April 9, 2002
    Assignee: E. I. du Pont de Nemours and Company
    Inventors: Mario Joseph Nappa, V.N.Mallikarjuna Rao
  • Publication number: 20020035300
    Abstract: A process is disclosed for producing the pentafluoropropenes of the formula CF 3 CX═CF 2 , where X is H or Cl. The process involves hydrodehalogenating CF 3 CCl 2 CF 3 with hydrogen at an elevated temperature in the vapor phase over a catalyst comprising an elemental metal, metal oxide, metal halide and/or metal oxyhalide (the metal being copper, nickel, chromium and the halogen of said halides and said oxyhalides being fluorine and/or chlorine).
    Type: Application
    Filed: August 19, 1999
    Publication date: March 21, 2002
    Inventors: V.N. MALLIKARJUNA RAO, ALLEN CAPRON SIEVERT
  • Patent number: 6359183
    Abstract: Advantageous processes are disclosed for the production of vinyl fluoride. Also disclosed are advantageous methods which may be employed for the preparation of catalysts useful in such processes. Included are methods which involve (i) reducing surface B2O3 present in a bulk chromium oxide composition containing surface B2O3 by treating said composition with HF at an elevated temperature and/or (ii) treating a bulk chromium oxide composition containing B2O3 to enrich the B2O3 present on its surface by heating said composition in oxygen or an oxygen-containing environment (e.g., air) at an elevated temperature for a time sufficient to enrich the B2O3 on the surface of the composition by at least a factor of two compared to the surface analysis of the untreated bulk composition.
    Type: Grant
    Filed: December 1, 1999
    Date of Patent: March 19, 2002
    Assignee: E. I. du Pont de Nemours and Company
    Inventors: Frank J. Christoph, George W. Coulston, Velliyur Nott Mallikarjuna Rao
  • Patent number: 6166156
    Abstract: Halofluorinated alkylene monomers are made by a method comprising the steps of: (a) subjecting a first polymer which is the reaction product of a fluorinated vinyl monomer and a vinyl comonomer to dehydrohalogenation to form a second polymer; (b) treating the second polymer with an oxidizing agent to form an oxidation product consisting of a .alpha., .omega.-dicarboxylic acid or an ester derivative thereof; and (c) treating said oxidation product with a reducing agent to form a reduction product consisting of a a .alpha., .omega.-diol. Preferably, the first polymer has a structure of --[CH.sub.2 CYZ(CF.sub.2 CFX).sub.n ].sub.m -- wherein X and Y=F, Cl or Br; X and Y may be the same or different; Z=H, F, Cl, Br, alkyl or perfluoroalkyl containing from about 1 to about 10 carbon atoms; n=an integer larger than about 1; and m is an integer between about 2 and about 10.sup.5. The .alpha., .omega.-dicarboxylic acids and .alpha., .omega.-diols produced herein can be directly used as polycondensation monomers.
    Type: Grant
    Filed: November 12, 1998
    Date of Patent: December 26, 2000
    Inventors: Chengjiu Wu, Baopei Xu, James T. Yardley
  • Patent number: 6093859
    Abstract: A process is disclosed for producing the hydrofluorocarbon CF.sub.3 CH.dbd.CF.sub.2. The process involves dehydrofluorinating CF.sub.3 CH.sub.2 CF.sub.3 at an elevated temperature in the vapor phase over a catalyst of (1) aluminum fluoride, (2) fluorided alumina, (3) metal supported on a trivalent aluminum compound containing fluoride anion, (4) lanthanum fluoride, (5) fluorided lanthanum oxide, (6) metal supported on a trivalent lanthanum compound containing fluoride anion, (7) trivalent chromium compounds and/or (8) catalysts of (a) at least one compound selected from the oxides, fluorides and oxyfluorides of magnesium, zinc and mixtures of magnesium and zinc, and optionally (b) at least one compound selected from the oxides, fluorides and oxyfluorides of aluminum, provided that the atomic ratio of aluminum to the total of magnesium and zinc in said catalyst is about 1:4, or less, to produce a product containing CF.sub.3 CH.dbd.CF.sub.2 and HF. The CF.sub.3 CH.dbd.CF.sub.
    Type: Grant
    Filed: June 1, 1999
    Date of Patent: July 25, 2000
    Assignee: E. I. du Pont de Nemours and Company
    Inventors: Mario Joseph Nappa, V. N. Mallikarjuna Rao, Allen Capron Sievert
  • Patent number: 6018083
    Abstract: A process is disclosed for the separation of a mixture of HF and CF.sub.3 CClFCF.sub.3. The process involves placing the mixture in a separation zone at a temperature of from about -30.degree. C. to about 100.degree. C. and at a pressure sufficient to maintain the mixture in the liquid phase, whereby an organic-enriched phase comprising less than 50 mole percent HF is formed as the bottom layer and an HF-enriched phase comprising more than 90 mole percent HF is formed as the top layer. The organic-enriched phase can be withdrawn from the bottom of the separation zone and subjected to distillation in a distillation column to recover essentially pure CF.sub.3 CClFCF.sub.3. The distillate comprising HF and CF.sub.3 CClFCF.sub.3 can be removed from the top of the distillation column while essentially pure CF.sub.3 CClFCF.sub.3 can be recovered from the bottom of the distillation column.
    Type: Grant
    Filed: April 1, 1999
    Date of Patent: January 25, 2000
    Assignee: E. I. du Pont de Nemours and Company
    Inventors: William H. Manogue, Mario Joseph Nappa, Allen Capron Sievert, V. N. Mallikarjuna Rao
  • Patent number: 5945573
    Abstract: A process is disclosed for producing the hydrofluorocarbon CF.sub.3 CH.sub.2 CHF.sub.2. The process involves dehydrofluorinating CF.sub.3 CH.sub.2 CF.sub.3 at an elevated temperature in the vapor phase over a catalyst of (1) aluminum fluoride, (2) fluorided alumina, (3) metal supported on a trivalent aluminum compound containing fluoride anion, (4) lanthanum fluoride, (5) fluorided lanthanum oxide, (6) metal supported on a trivalent lanthanum compound containing fluoride anion, (7) trivalent chromium compounds and/or (8) catalysts of (a) at least one compound selected from the oxides, fluorides and oxyfluorides of magnesium, zinc and mixtures of magnesium and zinc, and optionally (b) at least one compound selected from the oxides, fluorides and oxyfluorides of aluminum, provided that the atomic ratio of aluminum to the total of magnesium and zinc in said catalyst is about 1:4, or less, to produce a product containing CF.sub.3 CH.dbd.CF.sub.2 and HF; and reacting the CF.sub.3 CH.dbd.CF.sub.
    Type: Grant
    Filed: January 9, 1998
    Date of Patent: August 31, 1999
    Assignee: E. I. du Pont de Nemours and Company
    Inventors: Mario Joseph Nappa, V. N. Mallikarjuna Rao, Allen Capron Sievert
  • Patent number: 5880315
    Abstract: A process for the manufacture of vinyl fluoride (i.e., CH.sub.2 .dbd.CHF, VF or 1141) from 1,1-difluoroethane (i.e., CH.sub.3 CHF.sub.2, F152a or HFC-152a) is disclosed which involves contacting the 1,1-difluoroethane at an elevated temperature (200.degree. C.-400.degree. C.) with a multiphase catalyst composition consisting essentially of (a) fluorides of at least one divalent metal selected from magnesium and zinc, and (b) fluorides of trivalent aluminum, in which phases of the divalent fluorides are homogeneously dispersed with phases of the trivalent fluorides.
    Type: Grant
    Filed: November 4, 1997
    Date of Patent: March 9, 1999
    Assignee: E. I. du Pont de Nemours and Company
    Inventors: V.N. Mallikarjuna Rao, Munirpallam A. Subramanian
  • Patent number: 5868943
    Abstract: A saturated solution of an alkaline earth or alkali metal halide salt is electrolyzed in a flowing mercury cathode electrolysis cell. The amalgam is added dropwise to a solution of dichlorodifluoromethane in a solution of a polar, aprotic solvent, not reducible by such amalgams. The solvent contains inhibitors of polymerization, and may contain a promoting salt of lithium or the "onium" type. Tetrafluoroethylene and unreacted dichlorodifluoromethane gases are evolved, and separated by condensing the dichlorodifluoromethane. The polar, aprotic solvent is removed from the reaction and evaporated, crystallizing the chloride salt of the alkaline earth or alkali metal. This salt is combined with the anolyte of the mercury cell to form brine. The spent mercury from the dechlorination and dimerization is also recycled to the mercury cell. The polar, aprotic solvent is condensed, and mixed with the condensed unreacted dichlorodifluoromethane for further dechlorination and dimerization.
    Type: Grant
    Filed: April 25, 1994
    Date of Patent: February 9, 1999
    Inventor: Joseph L. Donnelly, Jr.
  • Patent number: 5750808
    Abstract: A process is disclosed for the dehydrohalogenation of partially halogenated ethanes of the formula C.sub.2 H.sub.a Cl.sub.b F.sub.c where a is an integer from 1 to 4, b is an integer from 0 to 3 and c is an integer form 1 to 5 to produce olefins selected from the group consisting of C.sub.2 H.sub.a-1 Cl.sub.b-1 F.sub.c and C.sub.2 H.sub.a-1 Cl.sub.b F.sub.c-1. The process involves contacting C.sub.2 H.sub.a Cl.sub.b F.sub.c with a zeolite selected from the group consisting of NaX and CsY. Selective reaction of one isomer from a mixture of two isomers is disclosed as a means for purification of the relatively unreactive isomer. Also disclosed is a process for producing perfluorocyclobutane which involves contacting CHF.sub.2 CClF.sub.2 with such zeolites.
    Type: Grant
    Filed: July 9, 1996
    Date of Patent: May 12, 1998
    Assignee: E. I. du Pont de Nemours and Company
    Inventors: Wendell Richard Cassel, David Richard Corbin, V.N. Mallikarjuna Rao
  • Patent number: 5679875
    Abstract: The present inventions provide manufacturing methods of 1,1,1,2,3-pentafluoropropene characterized by the reaction of removing HF by means of the contact of 1,1,1,2,3,3-hexafluoropropane in the gas state with active carbon or active carbon added with metallic salt. 1,1,1,2,3-pentafluoropropene can be produced from easily available 1,1,1,2,3,3-hexafluoropropane by cost-effective industrial methods at high yields according to these inventions.The inventions also provide manufacturing methods of 1,1,1,2,3-pentafluoropropane characterized by reducing 1,1,1,2,3-pentafluoropropene with hydrogen under the presence of a hydrogenation catalyst consisting of palladium added with one or more of silver, copper, gold, tellurium, zinc, chromium, molybdenum, and thallium or under the presence of a rhodium catalyst. The desired product can be produced at high reactivities and high selectivities according to these inventions.
    Type: Grant
    Filed: November 30, 1994
    Date of Patent: October 21, 1997
    Assignee: Daikin Industries, Ltd.
    Inventors: Hirokazu Aoyama, Eiji Seki
  • Patent number: 5621147
    Abstract: A 1,1,2-trifluoro-2-(trans-4-substituted cyclohexyl)ethylene of the formula (1):R--(A).sub.m --Cy--CF=CF.sub.2 (1)wherein R is a C.sub.1-10 alkyl group, a halogen atom or a cyano group, provided that in the case of the alkyl group, an oxygen atom may be interposed in a carbon-carbon bond of the alkyl group or in a carbon-carbon bond between this alkyl group and A, some of carbon-carbon bonds in the alkyl group may be triple bonds or double bonds, one --CH.sub.2 -- group in the alkyl group may be substituted by a carbonyl group, and some or all of hydrogen atoms in the alkyl group may be substituted by fluorine atoms;Cy is an unsubstituted trans-1,4-cyclohexylene group;A is a trans-1,4-cyclohexylene group, a 1,4-phenylene group or a 1,4-cyclohexenylene group, wherein each of such cyclic groups is unsubstituted or substituted by one or more halogen atoms or cyano groups, one or more =CH-- groups constituting rings of such cyclic groups may be substituted by nitrogen atoms, and one or more --CH.sub.
    Type: Grant
    Filed: May 4, 1995
    Date of Patent: April 15, 1997
    Assignee: Asahi Glass Company Ltd.
    Inventors: Osamu Yokokoji, Tamaki Simizu, Seisaku Kumai
  • Patent number: 5481050
    Abstract: The invention relates to a cost effective and convenient process for the manufacture of fluorinated olefins of the formula RCF.sub.2 CH=CH.sub.2 where R is C.sub.x Cl.sub.y F.sub.z and y+z=2.times.+1. The invention is also directed to a lo practical process for converting these olefins to hydrofluorocarbons via the catalyzed fluorination with hydrogen fluoride. Hydrofluorocarbons produced via this process have application as solvents among other uses.
    Type: Grant
    Filed: March 28, 1995
    Date of Patent: January 2, 1996
    Assignee: AlliedSignal Inc.
    Inventors: Michael Van Der Puy, G. V. Bindu Madhavan, Alagappan Thenappan, Hsueh S. Tung
  • Patent number: 5463150
    Abstract: 1,1,1,4,4,4-Hexafluorobut-2-ene is prepared from chloro-fluorobutanes of the formula (I)CF.sub.3 --CH.sub.2 --CHCl--CX.sub.3 (I)in which the individual radicals X independently of each other represent chlorine and/or fluorine, by reaction with alkali metal fluoride in an aprotic polar solvent.
    Type: Grant
    Filed: February 14, 1994
    Date of Patent: October 31, 1995
    Assignee: Bayer Aktiengesellschaft
    Inventors: Norbert Lui, Albrecht Marhold, Dietmar Bielefeldt
  • Patent number: 5446217
    Abstract: The invention relates to a cost effective and convenient process for the manufacture of fluorinated olefins of the formula RCF.sub.2 CH=CH.sub.2 where R is C.sub.x Cl.sub.y F.sub.z and y+z=2x+1. The invention is also directed to a practical process for converting these olefins to hydrofluorocarbons via the catalyzed fluorination with hydrogen fluoride. Hydrofluorocarbons produced via this process have application as solvents among other uses.
    Type: Grant
    Filed: May 16, 1994
    Date of Patent: August 29, 1995
    Assignee: AlliedSignal Inc.
    Inventors: Michael Van Der Puy, G. V. Bindu Madhavan, Alagappan Thenappan, Hsueh S. Tung
  • Patent number: 5396000
    Abstract: A process is disclosed for producing CF.sub.3 CHFCH.sub.2 F using vapor phase catalytic dehydrohalogenation to produce CF.sub.3 CF.dbd.CHF and HF, followed by vapor phase catalytic hydrogenation of CF.sub.3 CF.dbd.CHF in the presence of HF.
    Type: Grant
    Filed: May 24, 1993
    Date of Patent: March 7, 1995
    Assignee: E. I. Du Pont de Nemours and Company
    Inventors: Mario J. Nappa, V. N. Mallikarjuna Rao
  • Patent number: 5387729
    Abstract: The invention relates to catalytic compositions for the hydrogenation of 1,1,2-trichloro-1,2,2-trifluoroethane to chlorotrifluoroethylene and trifluoroethylene comprising a porous oxygenated support impregnated with a metal of group VIII of the periodic table of the elements and one or more compounds chosen from the salts of an alkali or alkaline-earth metal.The invention also relates to a process for obtaining these catalytic compositions and a process of hydrogenation by means of these catalytic compositions.
    Type: Grant
    Filed: January 13, 1994
    Date of Patent: February 7, 1995
    Assignee: Solvay (Societe Anonyme)
    Inventors: Luc Lerot, Vincent Wilmet, Joseph Pirotton
  • 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: 5180860
    Abstract: A process for the dehydrohalogenation of saturated hydrogen-containing polyhalocarbons using liquid alkali metal acid fluoride and/or alkali metal fluoride compositions to form haloolefins.
    Type: Grant
    Filed: June 28, 1990
    Date of Patent: January 19, 1993
    Assignee: E. I. Du Pont de Nemours and Company
    Inventors: Richard E. Fernandez, Ralph B. Kaplan
  • Patent number: 5089454
    Abstract: The invention relates to catalytic compositions for the hydrogenation of chlorofluoroalkenes to fluoroalkenes, comprising a porous carrier impregnated with metal of group VIII of the Periodic Table of the elements and with one or more compounds chosen from the salts of an alkali metal or alkaline-earth metal.The invention also relates to a process for obtaining these catalytic compositions and a process of hydrogenation by means of these catalytic compositions.
    Type: Grant
    Filed: May 5, 1989
    Date of Patent: February 18, 1992
    Assignee: Solvay & Cie (Societe Anonyme)
    Inventors: Luc Lerot, Jean-Louis Costa, Vincent Wilmet, Joseph Pirotton
  • 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: 5068415
    Abstract: The halogenotetrafluoropropionic acid 3-iodotetrafluoropropionic acid of the formula ICF.sub.2 CF.sub.2 COOH, it is prepared by reacting iodine, tetrafluoroethylene and ethylene in a one-pot reaction under specific conditions, reacting the resulting compound ICF.sub.2 CF.sub.2 CH.sub.2 CH.sub.2 I with a base in order to eliminate hydrogen iodide and oxidizing the compound ICF.sub.2 CF.sub.2 --CH.dbd.CH.sub.2 thus obtained to give 3-iodotetrafluoropropionic acid. The halogenotetrafluoropropionic acid is an advantageous starting compound for the preparation of valuable unsaturated compounds containing functional groups.
    Type: Grant
    Filed: September 4, 1987
    Date of Patent: November 26, 1991
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Konrad von Werner, Anton Probst