By Dehydrogenation Patents (Class 560/214)
  • Patent number: 10703704
    Abstract: A process for continuously removing water in situ from an oxidative esterification reaction is provided. The process includes (a) conducting a first oxidative esterification reaction in a first reactor or reaction zone, wherein the total number of reactors or reaction zones is n and n is at least 2; (b) removing a crude product stream from the first reactor or reaction zone; (c) introducing the crude product stream to a distillation column to generate a column overheads stream and a column bottoms stream; (d) passing a portion of the columns bottoms stream to the product recovery zone; and (e) passing a portion of the column overheads stream to a subsequent reactor or reaction zone. Steps (a)-(e) can be repeated.
    Type: Grant
    Filed: October 2, 2015
    Date of Patent: July 7, 2020
    Assignees: Dow Global Technologies LLC, Rohm and Haas Company
    Inventors: Zubin B. Kuvadia, Kirk W. Limbach, Dmitri A. Kraptchetov, Mark A. Silvano
  • Patent number: 9394222
    Abstract: The invention relates to a process for producing methacrylic acid, comprising: converting a C3-oxygenate into propanoic acid, wherein said C3-oxygenate is a compound selected from the group consisting of 1-propanol, monopropylene glycol, monohydroxyacetone, 2-hydroxypropanal, glycerol and dihydroxyacetone; and reacting the propanoic acid with formaldehyde or a precursor of formaldehyde into methacrylic acid. Said C3-oxygenate preferably contains 2 oxygen atoms, and most preferably it is monopropylene glycol.
    Type: Grant
    Filed: January 8, 2014
    Date of Patent: July 19, 2016
    Assignee: Shell Oil Company
    Inventor: Jean-Paul Lange
  • Patent number: 8592624
    Abstract: A production process for the manufacture of ethylenically unsaturated acids or esters thereof is described. The process includes the steps of reaction of an alkanoic acid, or ester of an alkanoic acid, of the formula R3—CH2—COOR4 where R3 and R4 are each independently hydrogen or an alkyl group, in the presence of a catalyst system to produce an ethylenically unsaturated acid or ester product. The process is characterised in that the acid or ester product is subsequently contacted with a dienophile to thereby remove discolouration therefrom. An ethylenically unsaturated acid or ester crude product purification process is also described.
    Type: Grant
    Filed: May 15, 2009
    Date of Patent: November 26, 2013
    Assignee: Lucite International UK Limited
    Inventors: David William Johnson, Trevor Huw Morris
  • Patent number: 8575300
    Abstract: Disclosed herein is a telechelic diacrylate fluoropolymer and a process for manufacture of the fluoropolymer. The diacrylate copolymer is of formula CH2?CR?COO—(CH2)n—R—(CH2)n—OOCCR??CH2, wherein R is selected from the group consisting of i) an oligomer comprising copolymerized units of vinylidene fluoride and perfluoro(methyl vinyl ether), ii) an oligomer comprising copolymerized units of vinylidene fluoride and hexafluoropropylene, iii) an oligomer comprising copolymerized units of tetrafluoroethylene and perfluoro(methyl vinyl ether), and iv) an oligomer comprising copolymerized units of tetrafluoroethylene and a hydrocarbon olefin, R? is H or—CH3, n is 1-4 and wherein said oligomer has a number average molecular weight of 1000 to 25,000 daltons.
    Type: Grant
    Filed: November 14, 2012
    Date of Patent: November 5, 2013
    Assignees: E I du Pont de Nemours and Company, Le Centre National de la Recherche Scien
    Inventors: Ming-Hong Hung, Bruno Ameduri, Georgi Kostov
  • Publication number: 20130245312
    Abstract: The invention is to a process for producing an acrylate product. The process includes the steps of contacting an alkanoic acid and an alkylenating agent over a catalyst composition under conditions effective to produce the acrylate product. The catalyst composition comprises vanadium, bismuth and titanium. Preferably, the catalyst comprises 0.3 wt % to 30 wt % vanadium, 0.1 wt % to 69 wt % bismuth and 0.1 wt % to 61 wt % tungsten, in an active phase.
    Type: Application
    Filed: October 31, 2012
    Publication date: September 19, 2013
    Applicant: CELANESE INTERNATIONAL CORPORATION
    Inventors: Dick Nagaki, Tianshu Pan, Craig J. Peterson, Elizabeth Bowden, Josefina T. Chapman, Sean Mueller
  • Publication number: 20110190464
    Abstract: The present invention relates to a method for the synthesis of an acrylic acid ester of formula CH2?CH—COOR, where R is an alkyl radical having between 1 and 18 carbon atoms and optionally where one of the carbon atoms in the alkyl radical may be replaced with a nitrogen atom. In an embodiment of the invention, glycerol is subjected to a dehydration reaction in the presence of an acid catalyst to obtain acrolein. The acrolein formed is transformed by catalytic oxidation into acrylic acid, which is subjected to an esterification reaction by means of an alcohol of the formula ROH in which R has the meaning as above. The invention also relates to bioresourced esters produced according to the method, and to synthesized polymers using the esters of the invention as polymerization monomers or comonomers.
    Type: Application
    Filed: July 24, 2009
    Publication date: August 4, 2011
    Applicant: Arkema France
    Inventors: Jean-Luc Dubois, Alain Riondel
  • Patent number: 7847118
    Abstract: A process for continuous heterogeneously catalyzed partial dehydrogenation of at least one hydrocarbon to be dehydrogenated in a reactor which is manufactured from a composite material which consists, on its side in contact with the reaction chamber, of a steel B with specific elemental composition which, on its side facing away from the reaction chamber, either directly or via an intermediate layer of copper, or of nickel, or of copper and nickel, is plated onto a steel A with specific elemental composition, and also partial oxidations of the dehydrogenated hydrocarbon and the reactor itself.
    Type: Grant
    Filed: June 25, 2007
    Date of Patent: December 7, 2010
    Assignee: BASF SE
    Inventors: Claus Hechler, Wilhelm Ruppel, Martin Dieterle, Karl-Heinrich Klappert, Klaus Joachim Mueller-Engel, Goetz-Peter Schindler, Catharina Klanner, Hans-Juergen Bassler
  • Publication number: 20070299278
    Abstract: A process for continuous heterogeneously catalyzed partial dehydrogenation of at least one hydrocarbon to be dehydrogenated in a reactor which is manufactured from a composite material which consists, on its side in contact with the reaction chamber, of a steel B with specific elemental composition which, on its side facing away from the reaction chamber, either directly or via an intermediate layer of copper, or of nickel, or of copper and nickel, is plated onto a steel A with specific elemental composition, and also partial oxidations of the dehydrogenated hydrocarbon and the reactor itself.
    Type: Application
    Filed: June 25, 2007
    Publication date: December 27, 2007
    Applicant: BASF Aktiengesellschaft
    Inventors: Claus HECHLER, Wilhelm Ruppel, Gotz-Peter Schindler, Catharina Klanner, Hans-Jurgen Bassler, Martin Dieterle, Karl-Heinrich Klappert, Klaus Joachim Muller-Engel
  • Patent number: 6835849
    Abstract: The invention relates to the synthesis of alkenoate esters from a corresponding lactone and an alcohol in the presence of a basic catalyst. More specifically, this invention relates to the synthesis of methyl-4-pentenoate ester from 5-methyl butyrolactone and methanol.
    Type: Grant
    Filed: July 11, 2003
    Date of Patent: December 28, 2004
    Assignee: E. I. du Pont de Nemours and Company
    Inventor: Leo Ernest Manzer
  • Patent number: 6624326
    Abstract: A novel method for preparing a heteropolyacid catalyst containing a heteropolyacid composed of molybdophosphoric acid and/or molybdovanadophosphoric acid, or a salt of the heteropolyacid, is provided. The method comprises preparing an aqueous solution or aqueous dispersion which (1) contains the nitrogen-containing heterocyclic compound, nitrate anions and ammonium ions, (2) the ammonium ion content not exceeding 1.7 mols per mol of the nitrate anion content, and (3) the ammonium ion content not exceeding 10 mols per 12 mols of the molybdenum atom content by mixing raw materials containing the catalyst-constituting elements with the nitrogen-containing heterocyclic compound in the presence of water, drying and calcining the same. This heteropolyacid catalyst excels over conventional catalysts in performance, life and strength.
    Type: Grant
    Filed: May 29, 2002
    Date of Patent: September 23, 2003
    Assignee: Nippon Shokubai Co., Ltd.
    Inventors: Hiroto Kasuga, Kaori Nakatani, Eiichi Shiraishi
  • Patent number: 5543558
    Abstract: A method includes producing an unsaturated organic compound from an organic component of an organic-containing feed. A reactor is provided which contains a molten metal bath. The molten metal bath includes a metal, such as a suitable transition metal, which can interact with an organic component of the feed. The feed is directed into the molten metal bath at a rate which causes the metal to interact with the organic component. Operating conditions are established and maintained in the reactor to cause the metal to interact with the organic component. At least one carbon-carbon double bond is formed in the organic component to produce an unsaturated organic compound that is discharged from the molten metal bath.
    Type: Grant
    Filed: December 23, 1993
    Date of Patent: August 6, 1996
    Assignee: Molten Metal Technology, Inc.
    Inventors: Christopher J. Nagel, Robert D. Bach
  • Patent number: 5132449
    Abstract: The invention relates to the stabilization of the activity and/or the reactivation of molybdoheteropoly acid catalysts in vapor-phase oxidations, such as the oxidehydrogenation of isobutyric acid or its lower esters to methacrylic acid or its lower esters, by means of an oxidizing treatment of the catalyst in which compounds of catalyst constituents are added, at temperatures ranging from 200.degree. to 400.degree. C., with an oxygen-containing gas.The inventive activation measures can be carried out either during the catalytic vapor-phase reaction, such as oxihydrogenation in particular, or intermittently to alternate therewith, and optionally also physically separated in part from each other.
    Type: Grant
    Filed: August 20, 1990
    Date of Patent: July 21, 1992
    Assignee: Rohm GmbH
    Inventors: Klaus Langerbeins, Ruediger Jelitte, Wolfgang Ruppert, Gerhard Emig, Otto Watzenberger, 1
  • Patent number: 5068399
    Abstract: Disclosed is a process for preparing, .alpha., .beta.-unsaturated carboxylic acid ester from .alpha.-hydroxycarboxylic acid ester, a .alpha.-alkoxycarboxylic acid ester or .beta.-alkoxycarboxylic acid ester as a starting material by a vapor-phase catalytic reaction in the presence of a crystalline aluminosilicate modified with an alkali metal and a platinum group element as a catalyst.According to the process, .alpha., .beta.-unsaturated carboxylic acid can be produced efficiently.
    Type: Grant
    Filed: September 17, 1990
    Date of Patent: November 26, 1991
    Assignee: Mitsubishi Gas Chemical Company, Inc.
    Inventors: Susumu Naito, Takao Kouzai, Ritoko Ikeda
  • Patent number: 4978776
    Abstract: A process for the manufacture of methyl methacrylate from isobutyric acid employing a catalytic oxidative dehydrogenation reaction in the vapor phase followed by condensation, liquid-liquid extraction, esterification, separation and purification steps.
    Type: Grant
    Filed: May 15, 1990
    Date of Patent: December 18, 1990
    Assignee: Norsolor
    Inventors: Samuel Yves, Daniel Cauvy
  • Patent number: 4966990
    Abstract: A process for producing methacrylic acid and/or methacrylic acid ester by oxidative dehydrogenation of isobutyric acid and/or isobutyric acid ester, wherein the improvement comprises using a catalyst having the composition represented by(Mo).sub.a (V).sub.b (P).sub.c (Cu).sub.d (As).sub.e (X).sub.f (O).sub.g(where X denotes at least one element selected from the group consisting of lithium, beryllium, magnesium, barium, tin, lead, chromium, tungsten, and tellurium; subscripts a, b, c, d, e, f, and g each denote the ratio of the respective elements; b, c, d, e, and f are in the range of 0.ltoreq.b.ltoreq.3, 0.2.ltoreq.c.ltoreq.2, 0.005.ltoreq.d.ltoreq.2, 0.005.ltoreq.e.ltoreq.0.2, and 0.005.ltoreq.f.ltoreq.2, respectively, when a is 12, and the value of g is determined according to the ratio and valence of the other elements), and at least a part of the composition having the heteropoly acid structure.
    Type: Grant
    Filed: February 24, 1989
    Date of Patent: October 30, 1990
    Assignee: Mitsubishi Kasei Corporation
    Inventors: Masayuki Otake, Takashi Ushekubo
  • Patent number: 4886891
    Abstract: The present invention provides a process for preparing a 1,1-disubstituted ethylene derivative of the formula ##STR1## which comprises reacting lead with a carbinol derivative of the formula ##STR2## wherein R.sup.1, R.sup.2, R.sup.3, X, Y, m and n are defined in the specification. The reaction is conducted more advantageously in the presence of a metal having higher ionization tendency than lead.
    Type: Grant
    Filed: December 18, 1987
    Date of Patent: December 12, 1989
    Assignee: Otsuka Kagaku Kabushiki Kaisha
    Inventors: Shigeru Torii, Masatoshi Taniguchi, Michio Sasaoka, Yoshihisa Tomotaki, Mitsuo Akada, Hideo Tanaka, Akira Suzuki, Shiro Yamashita
  • Patent number: 4864057
    Abstract: A process is provided for the oxydehydrogenation of saturated carboxylic acids or a lower alkyl ester thereof with oxygen in the presence of iron phosphorus oxide catalysts containing promoters selected from the group Ag, Al, B, Be, Cd, Co, Cu, Ga, Ge, In, Mn, Ni, Te, Th, Ti, Tl, U, V, Zn, Zr, rare earths and mixtures thereof.
    Type: Grant
    Filed: August 17, 1982
    Date of Patent: September 5, 1989
    Inventors: S. Erik Pedersen, James L. Callahan, Harley F. Hardman
  • Patent number: 4791080
    Abstract: Method for regenerating catalysts containing molybdenum, phosphorus, and vanadium in oxidic association and useful for the oxydehydrogenation of isobutyric acid or its lower esters to form methacrylic acid or its lower esters, by oxidizing the spent catalyst with an oxygen containing gas at temperatures from 200.degree. C. to 400.degree. C., suitably intermittently and in alternation with oxydehydrogenation.
    Type: Grant
    Filed: July 27, 1987
    Date of Patent: December 13, 1988
    Assignee: Rohm GmbH
    Inventors: Wilheim Gruber, Klaus Langerbeins, Wolfgang Ruppert
  • Patent number: 4777285
    Abstract: Alkenecarboxylates of the formula I ##STR1## where R.sub.1 is alkyl of 1 to 6 carbon atoms and n is 2, 3 or 4, are prepared by a process which comprises reacting a lactone of the formula II ##STR2## where R.sub.2 is hydrogen or methyl and m is 1 or 2, with an alkanol of 1 to 6 carbon atoms in the presence of an acidic catalyst at from 150.degree. to 400.degree. C.
    Type: Grant
    Filed: March 19, 1987
    Date of Patent: October 11, 1988
    Assignee: BASF Aktiengesellschaft
    Inventors: Rudolf Kummer, Uwe Vagt, Rolf Fischer, Walter Seufert, Rainer Becker
  • Patent number: 4743706
    Abstract: This invention relates to a novel vapor phase process for the production of unsaturated acids and esters, such as acrylic acid and methyl acrylate, by reacting a primary alcohol with a saturated monocarboxylic acid, ester, or anhydride in the presence of oxygen over a solid catalyst.
    Type: Grant
    Filed: October 22, 1984
    Date of Patent: May 10, 1988
    Assignee: The Standard Oil Company
    Inventors: Andrew T. Guttmann, Robert K. Grasselli
  • Patent number: 4720575
    Abstract: The molybdovanadophosphoric acid H.sub.8 PMo.sub.10 VO.sub.39, its PMo.sub.10 VO.sub.35 anhydride, methods for their preparation, and methods for making methacrylic acid and its esters by oxidation/dehydrogenation wherein the above acid and/or its anhydride is employed as a catalyst.
    Type: Grant
    Filed: March 7, 1986
    Date of Patent: January 19, 1988
    Assignee: Rohm GmbH
    Inventor: Wilhelm Gruber
  • Patent number: 4677225
    Abstract: A process for producing acrylic acid or methacrylic acid by reacting acetic acid or propionic acid with formaldehyde in a gas phase is described, characterized by carrying out the reaction in the presence of a solid catalyst containing at least one of boron oxide or phosphorus oxide and having an acid site of an acid strength, pKa.ltoreq.-3.0. The solid catalyst is of high activity and is satisfactory in both selectivity and conversion and, furthermore, its high selectivity can be maintained for long periods of time. Thus the desired product, acrylic acid or methacrylic acid, can be produced in high yield.
    Type: Grant
    Filed: May 21, 1985
    Date of Patent: June 30, 1987
    Assignee: Toagosei Chemical Industry Co., Ltd.
    Inventors: Hiroshi Niizuma, Toshiro Miki, Shiro Kojima, Kishiro Azuma, Hiroyuki Kato, Yuichi Murakami, Tsutomu Ito
  • Patent number: 4607122
    Abstract: A novel method of converting alkanoic acids, such as isobutyric acid, to alpha-beta unsaturated acids, such as methacrylic acid, is disclosed which exhibits a higher degree of selectivity than those vapor phase oxydehydration methods heretofore known to the art. The preferred method comprises contacting a Dawson structure phosphomolybdic acid catalyst with isobutyric acid under specified reaction conditions to achieve a high selectivity for methacrylic acid.
    Type: Grant
    Filed: April 27, 1981
    Date of Patent: August 19, 1986
    Assignee: Atlantic Richfield Company
    Inventors: Wilfred P. Shum, John F. White, Eva M. Beals
  • Patent number: 4600795
    Abstract: In the recovery and purification of methacrylic acid or its esters produced by the vapor phase catalytic oxydehydrogenation of isobutyric acid or its esters the problem of downstream plugging is avoided by the inclusion of a small amount of surfactant in the gaseous effluent at or near the point of its condensation.
    Type: Grant
    Filed: April 19, 1982
    Date of Patent: July 15, 1986
    Assignee: Ashland Oil, Inc.
    Inventors: Peter J. Frank, Jerry R. Hite
  • Patent number: 4579967
    Abstract: This invention provides a process for converting alkyl isobutyrate to alkyl methacrylate via alkyl-hydroperoxy-isobutyrate and alkyl alpha-hydroxyisobutyrate intermediate.An important aspect of the process is the use of a particulate metal oxide substrate in the first step of the process.
    Type: Grant
    Filed: February 7, 1983
    Date of Patent: April 1, 1986
    Assignee: Celanese Corporation
    Inventor: H. Clay Linstid, III
  • Patent number: 4564699
    Abstract: An isobutyric acid ester is oxidatively dehydrogenated in the vapor phase producing the corresponding methacrylic acid ester by contact with a heterogeneous catalyst, molecular oxygen and an amine. The catalyst may be any of a number of well known oxydehydrogenation catalysts.
    Type: Grant
    Filed: May 20, 1982
    Date of Patent: January 14, 1986
    Assignee: Ashland Oil, Inc.
    Inventor: Stephen E. Reiter
  • Patent number: 4506095
    Abstract: This invention provides a process for producing alkenoate products in the presence of an ethylaluminum dichloride type catalyst, such as the production of methyl 5-hexenoate by the reaction between propylene and methyl acrylate.
    Type: Grant
    Filed: March 17, 1983
    Date of Patent: March 19, 1985
    Assignee: Celanese Corporation
    Inventor: Gerald S. Koermer
  • Patent number: 4471062
    Abstract: The present invention relates to a method for the reactivation of phosphomolybdic acid based catalysts used for the conversion of saturated and unsaturated aldehydes to acids. The method comprises the step of feeding an oxide of nitrogen over the deactivated catalyst at a temperature of from about 100.degree. C. to about 400.degree. C. The method can be employed in the reactor by terminating the feed of reactant to the reactor, adjusting the reactor temperature as may be necessary to one suitable for reactivation and sweeping the reactor with a gas. Alternatively, the catalyst can be removed from the reactor for reactivation. Reactivated phosphomolybdic acid based catalysts are also disclosed. These catalysts have a ratio of molybdenum to phosphorus of 3:1 to 15:1 and are prepared by the process of feeding an oxide of nitrogen over the catalyst at a temperature of from about 100.degree. C. to about 400.degree. C.
    Type: Grant
    Filed: June 9, 1983
    Date of Patent: September 11, 1984
    Assignee: The Standard Oil Company
    Inventors: Diane G. Farrington, James F. White
  • Patent number: 4471061
    Abstract: The present invention relates to a method for maintaining the activity of PMA based catalysts during reactor shutdown by flushing the reactor with an oxide of nitrogen gas at a temperature of from about 150.degree. C. to about 370.degree. C. The method can be employed in the reactor by terminating the feed of hydrocarbon to the reactor and then flushing the reactor. The method can be employed to treat PMA based catalysts having the general formula Mo.sub.x P.sub.y A.sub.a B.sub.b C.sub.c D.sub.d E.sub.e O.sub.z wherein A is selected from the group consisting of ammonium, cesium, potassium, rubidium and thallium; B is selected from the group consisting of copper and vanadium; C is selected from the group consisting of antimony, arsenic, bismuth and tellurium; D is palladium; E is aluminum, barium, calcium, cerium, chromium, cobalt, iron, magnesium, manganese, nickel tantalum, titanium, tungsten, zinc, zirconium, chlorine and/or bromine; x can be 3 to 15, y can be 1 to 1.5; a can be 0.1 to 3; b can be 0.
    Type: Grant
    Filed: May 24, 1983
    Date of Patent: September 11, 1984
    Assignee: The Standard Oil Company
    Inventors: Wilfrid G. Shaw, Christos Paparizos, Diane G. Farrington
  • Patent number: 4442123
    Abstract: 6-Chloro-6-deoxy-D-hexitols, a novel class of compounds, and their esters, possess male antifertility activity and are thus useful in antifertility compositions. They are prepared by reduction of 6-chloro-6-deoxy-D-hexoses.
    Type: Grant
    Filed: December 28, 1981
    Date of Patent: April 10, 1984
    Assignee: Tate & Lyle Public Limited Company
    Inventors: Elner B. Rathbone, Geoffrey M. H. Waites, William C. L. Ford
  • Patent number: 4439621
    Abstract: Isobutyric acid or a lower alkyl ester thereof is oxidatively dehydrogenated in the vapor phase producing the corresponding olefinically unsaturated derivative by contact with a heterogeneous catalyst in the presence of molecular oxygen. The catalyst is composed of the calcined oxides of iron, phosphorous, silicon, vandanium and molybdenum.
    Type: Grant
    Filed: August 2, 1982
    Date of Patent: March 27, 1984
    Assignee: Ashland Oil, Inc.
    Inventor: Chelliah Daniel
  • Patent number: 4434298
    Abstract: Isobutyric acid or a lower alkyl ester thereof is oxidatively dehydrogenated in the vapor phase producing the corresponding .alpha.,.beta.-olefinically unsaturated derivative by contact with a heterogeneous catalyst in the presence of molecular oxygen. The catalyst is composed of the calcined mixture of salts of titanium and iron.
    Type: Grant
    Filed: November 9, 1981
    Date of Patent: February 28, 1984
    Assignee: Ashland Oil, Inc.
    Inventor: Ferdinand A. Ruszala
  • Patent number: 4427792
    Abstract: A process is provided for the preparation of iron phosphorous mixed oxide catalysts which are highly active at moderate temperatures by introducing iron and phosphorus containing compounds and promoter element containing compounds, if any, into a substantially organic liquid medium, heating, separating the resulting precursor, drying and calcining. The catalysts are useful for the dehydrogenation or oxydehydrogenation of organic compounds such as aldehydes or carboxylic acids.
    Type: Grant
    Filed: August 10, 1981
    Date of Patent: January 24, 1984
    Assignee: The Standard Oil Company
    Inventors: S. Erik Pedersen, Noel J. Bremer, James L. Callahan
  • Patent number: 4410723
    Abstract: Isobutyric acid or a lower alkyl ester thereof is oxidatively dehydrogenated in the vapor phase producing the corresponding alpha, beta-olefinically unsaturated derivative by contact with a heterogeneous catalyst in the presence of molecular oxygen. The catalyst is composed of the calcined phosphomolybdate of potassium and cerium.
    Type: Grant
    Filed: August 9, 1982
    Date of Patent: October 18, 1983
    Assignee: Ashland Oil, Inc.
    Inventor: Chelliah Daniel
  • Patent number: 4410729
    Abstract: Isobutyric acid or a lower alkyl ester thereof is oxidatively dehydrogenated in the vapor phase producing the corresponding .alpha.,.beta.-olefinically unsaturated derivative by contact with a heterogeneous catalyst in the presence of molecular oxygen. The catalyst is composed of the calcined phosphates of iron, silver and chromium.
    Type: Grant
    Filed: April 26, 1982
    Date of Patent: October 18, 1983
    Assignee: Ashland Oil, Inc.
    Inventor: Chelliah Daniel
  • Patent number: 4410727
    Abstract: Isobutyric acid or a lower alkyl ester thereof is oxidatively dehydrogenated in the vapor phase to produce the corresponding alpha, beta-olefinically unsaturated derivative by contact with a heterogeneous catalyst in the presence of oxygen. The catalyst has the empirical formula Fe.sup.II Fe.sub.2.sup.III (PO.sub.4).sub.2.(OH).sub.2 which can exist in the form of Barbosalite and/or Lipscombite.
    Type: Grant
    Filed: March 8, 1982
    Date of Patent: October 18, 1983
    Assignee: Ashland Oil, Inc.
    Inventor: Ferdinand A. Ruszala
  • Patent number: 4410728
    Abstract: Isobutyric acid or a lower alkyl ester thereof is oxidatively dehydrogenated in the vapor phase producing the corresponding .alpha.,.beta.-olefinically unsaturated derivative by contact with a heterogeneous catalyst in the presence of molecular oxygen. The catalyst is composed of the calcined phosphates of iron and cerium.
    Type: Grant
    Filed: April 19, 1982
    Date of Patent: October 18, 1983
    Assignee: Ashland Oil, Inc.
    Inventor: Chelliah Daniel
  • Patent number: 4391989
    Abstract: Isobutyric acid or a lower alkyl ester thereof is oxidatively dehydrogenated in the vapor phase to produce the corresponding .alpha.,B-olefinically unsaturated derivative by contact with a heterogeneous catalyst in the presence of molecular oxygen. The catalyst is composed of the calcined phosphates of chromium, molybdenum and tungsten.
    Type: Grant
    Filed: November 9, 1981
    Date of Patent: July 5, 1983
    Assignee: Ashland Oil, Inc.
    Inventor: Chelliah Daniel
  • Patent number: 4391990
    Abstract: Isobutyric acid or a lower alkyl ester thereof is oxidatively dehydrogenated in the vapor phase producing the corresponding .alpha.,.beta.-olefinically unsaturated derivative by contact with a heterogeneous catalyst in the presence of molecular oxygen. The catalyst is composed of the calcined oxides of uranium and tungsten.
    Type: Grant
    Filed: November 9, 1981
    Date of Patent: July 5, 1983
    Assignee: Ashland Oil, Inc.
    Inventor: Ferdinand A. Ruszala
  • Patent number: 4390725
    Abstract: Isobutyric acid or a lower alkyl ester thereof is oxidatively dehydrogenated in the vapor phase producing the corresponding .alpha.,.beta.-olefinically unsaturated derivative by contact with a heterogeneous catalyst in the presence of molecular oxygen. The catalyst is composed of the calcined phosphates of iron and copper.
    Type: Grant
    Filed: November 19, 1981
    Date of Patent: June 28, 1983
    Assignee: Ashland Oil, Inc.
    Inventor: Chelliah Daniel
  • Patent number: 4374269
    Abstract: Isobutyric acid or a lower alkyl ester thereof is oxidatively dehydrogenated in the vapor phase producing the corresponding .alpha.,.beta.-olefinically unsaturated derivative by contact with a heterogeneous catalyst in the presence of molecular oxygen. The catalyst is composed of the calcined oxides of uranium and niobium.
    Type: Grant
    Filed: November 19, 1981
    Date of Patent: February 15, 1983
    Assignee: Ashland Oil, Inc.
    Inventor: Ferdinand A. Ruszala
  • Patent number: 4374268
    Abstract: Isobutyric acid or a functional equivalent; e.g., a lower alkyl ester is oxidatively dehydrogenated to effect the vapor phase conversion thereof to the corresponding .alpha.,.beta.-ethylenically unsaturated derivative by contact with a heterogeneous catalyst in the presence of molecular oxygen. The catalyst is composed of calcined phosphates of iron containing cobalt or lanthanum as a modifier or dopant component.
    Type: Grant
    Filed: March 10, 1980
    Date of Patent: February 15, 1983
    Assignee: Ashland Oil, Inc.
    Inventors: Chelliah Daniel, Phyllis L. Brusky
  • Patent number: 4374270
    Abstract: Isobutyric acid or a lower alkyl ester thereof is oxidatively dehydrogenated in the vapor phase producing the corresponding .alpha.,.beta.-olefinically unsaturated derivative by contact with a heterogeneous catalyst in the presence of molecular oxygen. The catalyst is composed of the calcined oxides of iron and at least two members selected from the group consisting of antimony, niobium, tantalum and tungsten.
    Type: Grant
    Filed: December 7, 1981
    Date of Patent: February 15, 1983
    Assignee: Ashland Oil, Inc.
    Inventors: Ferdinand A. Ruszala, Thomas J. Weeks, Jr.
  • Patent number: 4370490
    Abstract: Isobutyric acid is oxidatively dehydrogenated to methacrylic acid by passing a gaseous mixture of isobutyric acid, oxygen, nitrogen and optionally water vapor at temperatures of 300.degree.-450.degree. C. and pressures of 0.5 to 5 bar over a catalyst comprising molybdenum oxide, which also contains vanadium, phosphorous and a metal selected from the group consisting of alkali metals, alkaline earth metals, zinc, silver, aluminum, titanium, lead, manganese, iron, cobalt, nickel and tin, preferably precipitated on a solid silica support and calcined at 200.degree. to 400.degree. C. At conversion levels of 80 to 100% of the isobutyric acid used, a methacrylic acid selectivity of 60 to 74% is attained.
    Type: Grant
    Filed: August 28, 1981
    Date of Patent: January 25, 1983
    Assignee: ROHM GmbH Chemische Fabrik
    Inventors: Wilhelm Gruber, Gunter Schroder
  • Patent number: 4355176
    Abstract: Isobutyric acid or a lower alkyl ester thereof is oxidatively dehydrogenated in the vapor phase producing the corresponding .alpha.,.beta.-olefinically unsaturated derivative by contact with a heterogeneous catalyst in the presence of molecular oxygen. The catalyst is composed of the calcined phosphates of iron, silver and niobium.
    Type: Grant
    Filed: November 9, 1981
    Date of Patent: October 19, 1982
    Assignee: Ashland Oil, Inc.
    Inventor: Chelliah Daniel
  • Patent number: 4338463
    Abstract: Compositions of the empirical formula:Mo.sub.12 P.sub.0.1- Te.sub.0.01-2 M.sub.0.1-3 M'.sub.0.01-3 X.sub.a O.sub.bwhereM is at least one of K, Rb and Cs;M' is at least one of Cu and V;X is at least one of Ba, Zn, Ga, Nb, Cd, Ti, Ca, Bi, Mg, Ta, Zr, Ce, Ni, Co, Cr, Fe and Tl when a>0;a is a number of 0 to about 2; andb is a number that satisfies the valence requirements of the other elements present,are excellent catalysts for the oxydehydrogenation of saturated, lower aliphatic acids and esters to the corresponding unsaturated acids and esters.
    Type: Grant
    Filed: October 3, 1980
    Date of Patent: July 6, 1982
    Assignee: The Standard Oil Company
    Inventors: Wilfrid G. Shaw, Christos Paparizos
  • Patent number: 4331813
    Abstract: Methyl methacrylate or other .alpha.-.beta. unsaturated esters are prepared by contacting an oxydehydrogenation-esterification catalyst with a feed mixture of a saturated acid (e.g., isobutyric acid), an alkyl alcohol (e.g., methanol), oxygen, with or with H.sub.2 O, preferably with H.sub.2 O for a time sufficient to form an alkyl .alpha.-.beta. unsaturated ester as described herein.
    Type: Grant
    Filed: February 9, 1981
    Date of Patent: May 25, 1982
    Assignee: Ashland Oil, Inc.
    Inventors: Chelliah Daniel, Phillis L. Brusky
  • Patent number: 4314075
    Abstract: Olefinic acids and esters, such as methacrylic acid and methylmethacrylate, are prepared by contacting in the presence of molecular oxygen the corresponding saturated acid or ester, such as isobutyric acid or methylisobutyrate with the catalyst of the empirical formula:Mo.sub.12 P.sub.0.1-3 M.sub.0.1-3 Cu.sub.0.01-2 V.sub.0.01-2 X.sub.0.01-2 M'.sub.a O.sub.b (I)whereM is at least one of K, Rb and Cs;X is at least one of Ba, La, Ga, Al, Ag, Cd, Ti, Tl, Hg, Pb and Zn;M' is at least one of Fe, Co, Ni, Sr, Mn, In, Ta, Ge, S and Be when a >0;a is a number of 0 to about 2; andb is a number that satisfies the valence requirements of the other elements present.
    Type: Grant
    Filed: September 5, 1980
    Date of Patent: February 2, 1982
    Assignee: The Standard Oil Company
    Inventors: Wilfrid G. Shaw, Philip L. Kuch, Christos Paparizos
  • Patent number: 4311851
    Abstract: The invention includes a process wherein an olefin is carbonylated with carbon monoxide to form carboxylic acid esters in the presence of a catalyst complex of one mole of BF.sub.3 and one mole of alcohol, and the catalyst is recovered from the desired reaction product and the reaction by-products and is recycled. The carbonylation is carried out until approximately one-half of the alcohol is consumed to form a reaction mass containing the BF.sub.3, the alcohol, and carboxylic acid esters in a 2:1:1 molar ratio. In the first step, the one mole of free BF.sub.3 is vaporized from the reaction mass. The remaining admixture is a 1:1:1 mixture of the aforesaid compounds. To this mixture additional alcohol is added and the mixture is subjected to distillation. An azeotrope of the product carboxylic acid ester and the alcohol and residual alcohol are removed by the distillation, leaving a residue containing a 1:2 BF.sub.
    Type: Grant
    Filed: December 19, 1979
    Date of Patent: January 19, 1982
    Assignee: Chem Systems Inc.
    Inventors: John A. Jung, Jimmy Peress
  • Patent number: RE31010
    Abstract: In a process wherein ethylene or propylene is carbonylated with carbon monoxide to form carboxylic acid esters in the presence of a catalyst complex of one mole of BF.sub.3 and one mole of alcohol, the invention concerns a technique wherein the catalyst is recovered from the reaction product and recycled. The carbonylation is carried out until approximately one-half of the alcohol is consumed, to form a reaction mass containing the BF.sub.3, the alcohol, and the carboxylic acid ester in a 2:1:1 molar ratio. In the first step, the one mole of the free BF.sub.3 is vaporized from the reaction mass. The remaining admixture is a 1:1:1 mixture of the three aforesaid compounds. To this mixture additional alcohol is added and the mixture is subjected to distillation. A carboxylic acid ester/alcohol azeotrope and residual alcohol are removed by the distillation, to leave a residue containing a 1:2 BF.sub.3 /alcohol complex. This complex is combined with an additional mole of BF.sub.
    Type: Grant
    Filed: June 11, 1981
    Date of Patent: August 10, 1982
    Assignee: Chem Systems Inc.
    Inventor: Abraham P. Gelbein