Group Viii Metal Containing Catalyst Utilized Patents (Class 562/534)
  • 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: 4467113
    Abstract: A catalyst having heteropoly-acid structure and the general formula:Mo.sub.a V.sub.b P.sub.c Cu.sub.d As.sub.e X.sub.f O.sub.gwherein,X represents one or more elements selected from the group consisting of tin, lead, cerium, cobalt, iron, zirconium, thorium, tungsten, germanium, nickel, rhenium, bismuth, antimony, chromium, boron, magnesium, silver, aluminum, zinc and titanium and a, b, c, d, e, f and g represent the atomic ratio of the elements where,a is 10,b is a number of 3 or less than 3 excluding 0,c is a number of 0.5 to 6,d is a number of 3 or less than 3 excluding 0,e is a number of 3 or less than 3 excluding 0,f is a number of 0 to 3,g is a number determined depending on the valency and atomic ratio of other elements.There is also provided a process for producing methacrylic acid by oxidizing methacrolein with molecular oxygen or molecular oxygen-containing gas in the vapor phase in the presence of the catalyst defined above.
    Type: Grant
    Filed: November 19, 1979
    Date of Patent: August 21, 1984
    Assignee: Nippon Kayaku Kabushiki Kaisha
    Inventors: Mutsumi Matsumoto, Hideki Sugi
  • Patent number: 4453006
    Abstract: A method for preparing attrition resistant, high percentage active component catalysts comprises using two types of silica, one of which is fumed silica, in a two stage catalyst preparation.
    Type: Grant
    Filed: February 12, 1981
    Date of Patent: June 5, 1984
    Assignee: The Standard Oil Company
    Inventors: Wilfrid G. Shaw, Christos Paparizos, James L. Callahan
  • Patent number: 4440948
    Abstract: Methacrylic acid is prepared by reacting methacrolein with molecular oxygen in the vapor phase at a temperature of from 230.degree. C. to 450.degree. C. in the presence of a catalyst having the formula Mo.sub.12 P.sub..alpha.' X.sub..beta.' Y.sub..gamma.' O.sub..delta.' wherein X is at least one member of the group consisting of Cs and Tl:Y is at least one member of the group consisting of Cs and Tl; Y is at least one member of the group consisting of V, Zr, Nb, Ni, Ta and Fe; .alpha.'=0.1-3; .beta.'=0.2-9; .gamma.'=0.1-7; .delta.'=36-100.
    Type: Grant
    Filed: September 22, 1976
    Date of Patent: April 3, 1984
    Assignee: Asahi Glass Company, Ltd.
    Inventors: Yoshio Oda, Keiichi Uchida, Takeshi Morimoto, Seisaku Kumai
  • Patent number: 4433167
    Abstract: A catalyst comprising (1) palladium, (2) phosphorus, (3) antimony, (4) X and (5) oxygen wherein X denotes at least one element selected from the group consisting of potassium, sodium, rubidium, lithium, cerium, beryllium, magnesium, calcium, vanadium, strontium, zinc, thorium and rhenium.There is also provided a process for the manufacture of methacrylic or acrylic acid by oxidizing methacrolein or acrolein with molecular oxygen in the vapor phase in the presence of the catalyst defined above.
    Type: Grant
    Filed: March 4, 1982
    Date of Patent: February 21, 1984
    Assignee: Nippon Kayaku Kabushiki Kaisha
    Inventors: Masanobu Ogawa, Toshitake Kojima
  • Patent number: 4415752
    Abstract: A novel catalyst comprising the elements Mo, V and Nb, and an oxidation process, is provided for oxidizing alpha-beta unsaturated aliphatic aldehydes in the vapor phase with molecular oxygen to produce the corresponding alpha-beta unsaturated carboxylic acid.
    Type: Grant
    Filed: April 22, 1980
    Date of Patent: November 15, 1983
    Assignee: Union Carbide Corporation
    Inventors: Harry J. Decker, Erlind M. Thorsteinson
  • Patent number: 4414411
    Abstract: A novel catalyst comprising the elements Mo, V and Ti, and an oxidation process, is provided for oxidizing alpha beta unsaturated aliphatic aldehydes in the vapor phase with molecular oxygen to produce the corresponding alpha-beta unsaturated carboxylic acid.
    Type: Grant
    Filed: May 5, 1980
    Date of Patent: November 8, 1983
    Assignee: Union Carbide Corporation
    Inventors: Harry J. Decker, Erlind M. Thorsteinson
  • Patent number: 4410725
    Abstract: A novel catalyst comprising the elements Mo, V and Ta, and an oxidation process, is provided for oxidizing alpha-beta unsaturated aliphatic aldehydes in the vapor phase with molecular oxygen to produce the corresponding alpha-beta unsaturated carboxylic acid.
    Type: Grant
    Filed: September 13, 1974
    Date of Patent: October 18, 1983
    Assignee: Union Carbide Corporation
    Inventors: Harry J. Decker, Erlind M. Thorsteinson
  • Patent number: 4404397
    Abstract: A stabilized heteropoly molybdate catalyst precursor in calcined form and containing anionic molybdenum in defect state is surface impregnated with certain metal cations. The stabilized precursor is one obtained by incorporating into the reaction product of a molybdate and a soluble phosphate, silicate or arsenate, an aqueous chloride ion and a compound of phosphotungstate, silicotungstate, vanadium arsenate, silico-arsenate, phosphovanadate, or silicovanadate, followed by drying and calcining. During the chloride ion stabilization step other metals may be optionally incorporated in forming the stabilized precursor.The obtained precursor is catalytically active in the conversion of the unsaturated aldehydes to the corresponding unsaturated carboxylic acids with or without incorporation of the metal cation during the chloride ion stabilization step.
    Type: Grant
    Filed: December 29, 1980
    Date of Patent: September 13, 1983
    Assignee: Air Products and Chemicals, Inc.
    Inventor: Chelliah Daniel
  • Patent number: 4391880
    Abstract: Process and system for cooling a reaction effluent containing volatized catalyst wherein the effluent is contacted with circulating cooled solid catalyst in dilute phase transport contact, with the volatized catalyst being condensed onto the solid catalyst.
    Type: Grant
    Filed: January 2, 1981
    Date of Patent: July 5, 1983
    Assignee: The Lummus Company
    Inventor: Utah Tsao
  • Patent number: 4380664
    Abstract: At least one olefinic hydrocarbon of 3 to 4 carbon atoms is oxidized catalytically in the gas phase in the presence of molecular oxygen at 200.degree.-450.degree. C. to produce the corresponding aldehyde and acid over a calcined catalyst of the formula Mo.sub.a Sb.sub.b Bi.sub.c Fe.sub.d Ni.sub.e Sn.sub.f X.sub.g Y.sub.h O.sub.i wherein X is at least one alkali metal selected from the group consisting of potassium, rubidium and cesium; Y is at least one metal selected from the group consisting of cobalt, uranium, germanium, tungsten and titanium; a to h are atomic ratios wherein a=12, b=0.2 to 20, c=0.2 to 12, d=0.2 to 12, e=0.2 to 12, f=0 to 20, g=0.01 to 4 and h=0 to 6; and i is determined according to the oxidation states of the metal atoms in the catalyst.
    Type: Grant
    Filed: March 29, 1978
    Date of Patent: April 19, 1983
    Assignee: Mitsubishi Rayon Company, Ltd.
    Inventors: Hiromichi Ishii, Hideo Matsuzawa, Masao Kobayashi, Kantaro Yamada
  • Patent number: 4365087
    Abstract: In the production of acrylic acid by a two-stage, vapor-phase catalytic oxidation of propylene, a composite oxide catalyst expressed by the formula Mo.sub.a Bi.sub.b Ni.sub.c Co.sub.d Fe.sub.e Na.sub.f Mn.sub.g B.sub.h K.sub.i Si.sub.j O.sub.x is used in the first-stage reaction, which is carried out under specific reaction and operational conditions, and the second-stage reaction is carried under specific reaction and operational conditions while oxygen is supplied by a specific mode.
    Type: Grant
    Filed: January 29, 1980
    Date of Patent: December 21, 1982
    Assignee: Mitsubishi Petrochemical Company Limited
    Inventors: Koju Kadowaki, Kohei Sarumaru, Takeshi Shibano
  • Patent number: 4358608
    Abstract: The present invention relates to a process for the production of unsaturated aliphatic acids and the catalyst therefor, by the vapor phase oxidation of the corresponding unsaturated aliphatic aldehydes with molecular oxygen, optionally in the presence of steam, in the presence of an oxidation catalyst consisting of the oxides of the elements molybdenum, vanadium, and tungsten, plus at least one of the oxides selected from the group consisting of rhenium, and titanium and optionally one or more of the oxides of the elements manganese, iron, copper, tin, aluminum, cobalt, nickel, phosphorus, zinc, bismuth, silver, cadmium, niobium,arsenic, chromium, the alkali and the alkaline earth elements.
    Type: Grant
    Filed: June 22, 1981
    Date of Patent: November 9, 1982
    Assignee: The Standard Oil Company
    Inventors: Wilfrid G. Shaw, David B. Terrill, David R. Woodbury
  • Patent number: 4350830
    Abstract: A method for preparing acrylic acid by oxidation of acrolein over a new and improved catalyst providing conversions of acrolein of greater than 99% with yields of acrylic acid in excess of 95%. The catalyst consists essentially of the oxides of molybdenum, vanadium, chromium, copper and titanium and optionally silicon on an inert carrier. Catalysts useful in the process contain the elements previously mentioned in the atomic ratios ofMo.sub.15 V.sub.5-10 Cu.sub.2-5 Cr.sub.0.2-2 Ti.sub.
    Type: Grant
    Filed: October 17, 1979
    Date of Patent: September 21, 1982
    Assignee: The Dow Chemical Co.
    Inventors: David L. Childress, William V. Hayes, Richard L. Poppe
  • Patent number: 4341900
    Abstract: The gas phase catalytic oxidation of an unsaturated aldehyde with molecular oxygen at 240.degree. to 450.degree. C. to give the corresponding unsaturated carboxylic acid is conducted in the presence of a catalyst of the following formula:Mo.sub.12 P.sub.a Q.sub.b R.sub.c X.sub.d Y.sub.e Z.sub.f O.sub.gwherein Mo is molybdenum, P is phosphorus, O is oxygen, Q is calcium and/or magnesium, R is at least one metal element selected from the group consisting of potassium, rubidium, cesium and thallium, X is at least one element selected from the group consisting of boron, silicon, manganese, iron, cobalt, zinc, germanium, uranium, tin, lead, chromium, titanium, tantalum, antimony, niobium and bismuth, Y is at least one metal element selected from the group consisting of vanadium, copper and nickel, Z is strontium and/or barium, and wherein the subscripts represent the atomic ratio of each component and a is 0.5 to 6, b is 0.2 to 6, c is 0.2 to 6, d is 0.
    Type: Grant
    Filed: March 3, 1976
    Date of Patent: July 27, 1982
    Assignee: Mitsubishi Rayon Company, Limited
    Inventors: Hiromichi Ishii, Hideo Matsuzawa, Masao Kobayashi, Masato Otani
  • Patent number: 4339355
    Abstract: A novel catalyst comprising the elements Mo, V and Nb is provided for oxidizing alpha-beta unsaturated aliphatic aldehydes in the vapor phase with molecular oxygen to produce the corresponding alpha-beta unsaturated carboxylic acid.
    Type: Grant
    Filed: October 11, 1977
    Date of Patent: July 13, 1982
    Assignee: Union Carbide Corporation
    Inventors: Harry J. Decker, Erlind M. Thorsteinson
  • Patent number: 4339394
    Abstract: Certain multiply promoted Sn-Sb oxides are superior catalysts for the ammoxidation of olefins to the corresponding unsaturated nitriles, the selective oxidation of olefins to unsaturated aldehydes and acids, and the oxydehydrogenation of olefins to diolefins.
    Type: Grant
    Filed: October 1, 1980
    Date of Patent: July 13, 1982
    Assignee: The Standard Oil Co.
    Inventors: Robert K. Grasselli, Dev D. Suresh, James F. Brazdil, Frances I. Ratka
  • Patent number: 4320227
    Abstract: A process for producing methacrolein and methacrylic acid by oxidizing isobutyl aldehyde with molecular oxygen or molecular oxygen-containing gas in the vapor phase characterized by the use of a catalyst of heteropoly-acid or a mixture of heterpoly-acid and its salt which has the general formula:Mo.sub.a V.sub.b P.sub.c X.sub.d Y.sub.e O.sub.fwherein Mo, V, P and O represent respectively molybdenum, vanadium, phosphorus and oxygen, X represents one or more elements selected from the group consisting of copper, tin, thorium, aluminum, germanium, nickel, iron, cobalt, zinc, titanium, lead, rhenium, zirconium, cerium, chromium, bismuth and arsenic, Y represents one or more elements selected from the group consisting of potassium, rubidium, cesium and thallium and a, b, c, d, e and f represent the atomic ratio of the elements where,a is 10,b is a number of 6 or less than 6 excluding 0,c is a number of 0.5 to 6,d is a number of 3 or less than 3 excluding 0,e is a number of 0 to 0.
    Type: Grant
    Filed: January 4, 1980
    Date of Patent: March 16, 1982
    Assignee: Nippon Kayaku Kabushiki Kaisha
    Inventors: Mutsumi Matsumoto, Kouichi Wada
  • Patent number: 4317927
    Abstract: Catalysts having improved attrition resistance are produced by incorporating a substantially uniform appearing coating of completely calcined, catalytically active oxide material onto an inert porous support containing sorbed aqueous silica sol. Such catalysts are useful in the gas phase oxidation of unsaturated aldehydes to unsaturated acids, especially acrolein to acrylic acid.
    Type: Grant
    Filed: September 15, 1980
    Date of Patent: March 2, 1982
    Assignee: Celanese Corporation
    Inventors: Charles A. Dalton, William E. Slinkard
  • Patent number: 4303550
    Abstract: The present invention relates to a method for the regeneration of deactivated PMA based catalysts by imbibing an aqueous volatile base within the pore structure of the deactivated catalyst so as to form a fluid phase within the pore structure, adding a volatile acid to the fluid phase to form a precipitate. The precipitate is thereafter dried and calcined to yield the regenerated catalyst. A second method for regeneration is also provided and includes the steps of imbibing a volatile solvent within the pore structure of the deactivated catalyst, adding a volatile acid to the system, and then adding a volatile base to the system to form a precipitate within the pore structure. The precipitate is again dried and calcined to yield the regenerated catalyst.
    Type: Grant
    Filed: December 28, 1979
    Date of Patent: December 1, 1981
    Assignee: Standard Oil Company
    Inventors: James L. Callahan, Wilfrid G. Shaw, Arthur F. Miller
  • Patent number: 4297247
    Abstract: A coated catalyst comprising (a) an inert carrier having a particle diameter of not less than 100 .mu.m and a surface area of up to 20 m.sup.2 /g and (b) a coating which firmly adheres to the outer surface and in the edge zone, near the surface, of the carrier particles, and which contains the catalytic material, can be prepared by applying the catalytic material in the form of a powder of particle size not more than 300 .mu.
    Type: Grant
    Filed: March 3, 1980
    Date of Patent: October 27, 1981
    Assignee: BASF Aktiengesellschaft
    Inventors: Richard Krabetz, Walter Herrmann, Heinz Engelbach, Peter Palm, Karl Sommer, Heinrich Spahn
  • Patent number: 4277375
    Abstract: A novel catalyst comprising the elements Mo, V and Ta is provided for oxidizing alpha-beta unsaturated aliphatic aldehydes in the vapor phase with molecular oxygen to produce the corresponding alpha-beta unsaturated carboxylic acid.
    Type: Grant
    Filed: October 11, 1977
    Date of Patent: July 7, 1981
    Assignee: Union Carbide Corporation
    Inventors: Harry J. Decker, Erlind M. Thorsteinson
  • Patent number: 4259211
    Abstract: Catalysts which consist of a molded carrier, the surface of which is coated with an active catalyst composition of the general formula Mo.sub.12 A.sub.a B.sub.b C.sub.c D.sub.d O.sub.x, where A is V and/or W, B is Cu and/or Fe and/or Mn and/or Ni and/or Cr, C is Nb and/or Ta and/or Bi and/or Sb and/or Sn and/or Th and/or Ce and/or U, D is Li and/or Na and/or K and/or Rb and/or Cs and/or Tl and a is from 0.1 to 18, b is from 0 to 8, c is from 0 to 10, d is from 0 to 2 and x is from 36 to 135, which are particularly active and selective for the oxidation of acrolein and methacrolein with oxygen-containing gases to give acrylic acid and methacrylic acid, respectively, are obtained by first manufacturing the catalyst composition, before applying it to the carrier, from thermally easily decomposed salts of the components by mixing aqueous solutions, slurries or moist solid masses of the salts of the components, drying the mixture and calcining the dried composition at from 140.degree. to 600.degree. C.
    Type: Grant
    Filed: November 24, 1978
    Date of Patent: March 31, 1981
    Assignee: BASF Aktiengesellschaft
    Inventors: Richard Krabetz, Walter Herrmann, Norbert Scholz, Heinz Engelbach, Gerd-Juergen Engert, Carl-Heinz Willersinn, Gerd Duembgen, Fritz Thiessen
  • Patent number: 4250339
    Abstract: Methacrolein is produced by a vapor phase oxidation of isobutylene or tertiary butanol in the presence of a complex oxide catalyst having the formulaMo.sub.a Co.sub.b Fe.sub.c Bi.sub.d Tl.sub.e X.sub.f Y.sub.g Z.sub.h O.sub.iwherein X represents V and/or Nb; Y represents La and/or Ce; and Z represents Cs and/or Te and a, b, c, d, e, f, g, h and i represent atomic ratios wherein a=12; b=3 to 15; c=0.4 to 5; d=0.4 to 5; e=0.01 to 2; f=0.01 to 2; g=0 to 2; h=0 to 2; and i is determined by the valences of the non-oxygen components of the catalyst and is usually in a range of 40 to 79.
    Type: Grant
    Filed: November 30, 1979
    Date of Patent: February 10, 1981
    Assignee: Toyo Soda Manufacturing Co., Ltd.
    Inventors: Teruhisa Sakamoto, Kazuhiko Sekizawa, Keiichi Kihara
  • Patent number: 4250054
    Abstract: The present invention relates to a process for the production of unsaturated aliphatic acids and the catalyst therefor, by the vapor phase oxidation of the corresponding unsaturated aliphatic aldehydes with molecular oxygen, optionally in the presence of steam, in the presence of an oxidation catalyst consisting of the oxides of the elements molybdenum, vanadium, tungsten and lanthanum, and optionally one or more of the oxides of the elements manganese, iron, copper, aluminum, cobalt, nickel, phosphorus, zinc, bismuth, silver, cadmium, niobium, arsenic, chromium, the alkali and the alkaline earth elements.
    Type: Grant
    Filed: June 1, 1976
    Date of Patent: February 10, 1981
    Assignee: The Standard Oil Company (Ohio)
    Inventors: Wilfrid G. Shaw, Ernest C. Milberger, Serge R. Dolhyj
  • Patent number: 4238359
    Abstract: A catalyst composition for use in preparing unsaturated carboxylic acids by the vapor-phase oxidation of unsaturated aldehydes, said catalyst composition comprising an oxide composition containing as essential ingredients (1) phosphorus, (2) molybdenum and (3) X in which X is at least one element selected from the group consisting of thallium and metals of Groups IA and II of the periodic table, characterized in that said oxide composition has a surface area of 4 to 20 m.sup.2 /g and a pore volume of 0.08 to 0.5 ml/g, whereby said catalyst composition has an excellent reproducibility of catalytic activity and a process for preparing aforesaid catalyst composition.
    Type: Grant
    Filed: May 11, 1979
    Date of Patent: December 9, 1980
    Assignee: Nippon Zeon Co. Ltd.
    Inventors: Shinichi Akiyama, Haruhisa Yamamoto, Nobuaki Yoneyama, Shinji Matsumoto
  • Patent number: 4230887
    Abstract: C.sub.2 -C.sub.6 monocarboxylic and dicarboxylic acids are scrubbed from gas phase mixtures of such acids and water by gas absorption techniques utilizing a liquid solvent comprising a polyoxyalkylene glycol or a monoalkyl or dialkyl ether thereof. The solvent enriched with the acid is subjected to distillation to recover a substantially anhydrous acid product.
    Type: Grant
    Filed: February 16, 1978
    Date of Patent: October 28, 1980
    Assignee: Celanese Corporation
    Inventors: William T. Mitchell, Phillip S. Snyder
  • Patent number: 4223161
    Abstract: The present invention relates to a process for the production of unsaturated aliphatic acids and the catalyst therefor, by the vapor phase oxidation of the corresponding unsaturated aliphatic aldehydes with molecular oxygen, optionally in the presence of steam, in the presence of an oxidation catalyst consisting of the oxides of the elements molybdenum, vanadium, tungsten and lanthanum, and optionally one or more of the oxides of the elements manganese, iron, copper, aluminum, cobalt, nickel, phosphorus, zinc, bismuth, silver, cadmium, niobium, arsenic, chromium, the alkali and the alkaline earth elements.
    Type: Grant
    Filed: March 31, 1977
    Date of Patent: September 16, 1980
    Assignee: The Standard Oil Company (Ohio)
    Inventors: Wilfrid G. Shaw, Ernest C. Milberger, Serge R. Dolhyj
  • Patent number: 4180678
    Abstract: A process for preparing methacrylic acid which comprises carrying out the catalytic vapor phase oxidation of methacrolein with a member selected from the group consisting of air and a molecular oxygen-containing gas in the presence of a novel catalytic oxide composition of the general formulaY.sub.a X.sub.b P.sub.c Mo.sub.d V.sub.e O.sub.fWherein Y is at least one metallic element selected from the group consisting of copper, cobalt, zirconium, bismuth, antimony and arsenic, X is at least one alkali metal element selected from the group consisting of sodium, potassium, rubidium and cesium, and a, b, c, d, e and f represent the atomic ratios of the several elements; and when d is 12, a is 0-10 and b is 0-10, c is 0.1-10, e is 0.1-10, and f is a value that is determined by the valences and atomic ratios of the several elements, with the proviso that the sum of a plus b is greater than zero.
    Type: Grant
    Filed: December 27, 1974
    Date of Patent: December 25, 1979
    Assignee: Nippon Shokubai Kagaku Kogyo Co. Ltd.
    Inventors: Masahiro Wada, Michio Ueshima, Isao Yanagisawa, Michikazu Ninomiya
  • Patent number: 4174459
    Abstract: Methacrylic acid is produced by the vapor phase oxidation of methacrolein in the presence of a complex oxide catalyst having the formula:Mo.sub.a V.sub.b P.sub.c Ce.sub.d Cu.sub.e X.sub.f O.sub.gwherein X represents at least one of the elements selected from the group of Mn, Fe, Co, Sn and Te and a, b, c, d, e, f and g represent atomic ratios wherein a=12; b=0.01 to 2; c=0.1 to 3; d=0.01 to 2; e=0.01 to 2; f=0 to 2 and g is determined by the valences of the non-oxygen components of the catalyst and is usually in a range of 38 to 50. The catalyst can be optionally reduced by subjecting the metal oxide mixture to at least one reducing organic material selected from the group consisting of dibasic carboxylic acids, oxycarboxylic acids, and polyols.
    Type: Grant
    Filed: January 4, 1977
    Date of Patent: November 13, 1979
    Assignee: Toyo Soda Manufacturing Co., Ltd.
    Inventors: Teruhisa Sakamoto, Taketoshi Nagahama, Shigeo Nakamura, Keiichi Kihara
  • Patent number: 4172051
    Abstract: This invention relates to a process and catalyst for producing methacrylic acid by the oxidation of methacrolein. More specifically, it relates to a process for producing methacrylic acid from methacrolein by oxidizing the same with molecular oxygen or molecular oxygen-containing gas, which is characterized by the use of a composition, as a catalyst, having a heteropolyacid structure and the general formula:Mo.sub.a V.sub.b P.sub.c Al.sub.d Y.sub.e O.sub.fwherein Mo, V, P, Al and O represent respectively molybdenum, vanadium, phosphorus, aluminum and oxygen, Y represents one or more elements selected from the groups consisting of copper, tine, cobalt, iron, zirconium, thorium, lead and cerium, and suffixes a, b, c, d, e and f represent the atomic ratio of the elements where, a is 10, b is a number of 3 or less than 3 excluding 0 and, preferably, 0.5 to 2, c is a number of 0.5 to 10 and, preferably, 0.5 to 3, d is a number of 3 or less than 3 excluding 0, preferably, 0.01 to 1.
    Type: Grant
    Filed: August 19, 1977
    Date of Patent: October 23, 1979
    Assignee: Nippon Kayaku Kabushiki Kaisha
    Inventors: Mutsumi Matsumoto, Atsushi Sudo, Hideki Sugi
  • Patent number: 4166190
    Abstract: Catalysts containing tungsten, phosphorus, vanadium, molybdenum, and promoted with at least one of the elements selected from the group selected from Sn, As, Cu, Ce, B, Cr, Fe, Ni, Co, U, Mn, Ag, Ru, Rh, Cd, Sr, In, Zn, and La have been found to be especially effective for the oxidation of unsaturated aldehydes to form the corresponding unsaturated acid.
    Type: Grant
    Filed: April 29, 1976
    Date of Patent: August 28, 1979
    Assignee: The Standard Oil Company
    Inventors: James F. White, James R. Rege, Robert K. Grasselli, Dev D. Suresh
  • Patent number: 4163862
    Abstract: The present invention is a catalyst composition consisting of oxides or oxide complexes that contains catalytically significant amounts of cerium, tungsten, vanadium and molybdenum plus optionally one or more of Fe, Co, Ni, Zn, Cu, Mg, Mn, Bi, Ti, Zr, Sn, P, an alkali metal, an alkaline earth metal, lanthanum or an element of the lanthanoid series. These catalysts are especially useful for producing acrylic acid from acrolein and for producing methacrylic acid from methacrolein.
    Type: Grant
    Filed: January 30, 1976
    Date of Patent: August 7, 1979
    Assignee: Standard Oil Company (Ohio)
    Inventors: Serge R. Dolhyj, Ernest C. Milberger
  • Patent number: 4157987
    Abstract: The present invention is a catalyst composition consisting of oxides or oxide complexes that contains catalytically significant amounts of cerium, tungsten, vanadium and molybdenum plus optionally one or more of Co, Ni, Zn, Cu, Mg, Mn, Bi, Ti, Zr, Sn, P, an alkali metal, an alkaline earth metal, lanthanum or an element of the lanthanoid series. These catalysts are especially useful for producing acrylic acid from acrolein and for producing methacrylic acid from methacrolein.
    Type: Grant
    Filed: April 24, 1978
    Date of Patent: June 12, 1979
    Assignee: Standard Oil Company
    Inventors: Serge R. Dolhyj, Ernest C. Milberger
  • Patent number: 4148822
    Abstract: Methacrolein or acrolein is oxidized with molecular oxygen in the presence of water vapor, a catalyst containing palladium, phosphorus, antimony(optionally) and oxygen and a phosphoric acid or a compound capable of forming phosphoric acid during the reaction.
    Type: Grant
    Filed: January 2, 1976
    Date of Patent: April 10, 1979
    Assignee: Nippon Kayaku Kabushiki Kaisha
    Inventors: Masanobu Ogawa, Toshitake Kojima
  • Patent number: 4146732
    Abstract: A process is disclosed for preparing unsaturated carboxylic acids consisting essentially in reacting in the vapor phase an unsaturated aldehyde with molecular oxygen or an oxygen-containing gas, at a temperature ranging from 200.degree. to 370.degree. C., in the presence of a solid catalyst, with a contact time between 0.5 and 5 seconds, characterized in that the catalyst consists essentially of molybdenum, vanadium, cobalt, and optionally tungsten, these elements being chemically combined with oxygen and the atomic ratios of the elements being represented by the empirical formula Mo.sub.12 V.sub.a W.sub.b Co.sub.c O.sub.dA is between 1.5 and 3.0;B is between 0 and 0.5;C is between 3.5 and 5.5; andD is a number sufficient to satisfy the valences of the other elements,Said catalyst being prepared starting from aqueous solutions of soluble salts of the elements composing it, by the coprecipitation method. Preferably, the coprecipitation is effected at a pH ranging from 2 to 5 and at a temperature between 20.
    Type: Grant
    Filed: May 17, 1977
    Date of Patent: March 27, 1979
    Assignee: Montedison S.p.A.
    Inventors: Mario Padovan, Giancarlo Battiston, Francesco Pignataro, Giordano DeAlberti, Giuseppe Leofanti
  • Patent number: 4146733
    Abstract: Methacrylic acid or acrylic acid are produced by the oxidation of methacrolein or acrolein, respectively, with molecular oxygen in the vapor phase in the presence of a catalytic oxide of molybdenum, phosphorus, arsenic, at least one element selected from the group consisting of Ag, Rh, Ru, and Au, oxygen, and optionally, at least one of Cd, Pt, Tl, Pd, Al, Ge, Cu, Ni, alkaline earth metal, NH.sub.4 and Cl.
    Type: Grant
    Filed: March 14, 1977
    Date of Patent: March 27, 1979
  • Patent number: 4139719
    Abstract: Methacrylic acid or acrylic acid are produced by the oxidation of methacrolein or acrolein, respectively, with molecular oxygen in the vapor phase in the presence of a catalytic oxide of molybdenum, phosphorus, arsenic, at least one element selected from the group consisting of U, Ti, Nb, Re, Pb, Zn, and Ga, oxygen, and optionally, at least one of Cu, a rare earth element, Ag, Ta, In, Th, Cd, Tl, alkaline earth metal, NH.sub.4, Cl, Ni, Al and Ge.
    Type: Grant
    Filed: January 31, 1977
    Date of Patent: February 13, 1979
  • Patent number: 4138365
    Abstract: A catalyst comprising (1) palladium, (2) phosphorus, (3) antimony, (4) X and (5) oxygen wherein X denotes at least one element selected from the group consisting of potassium, sodium, rubidium, lithium, cerium, beryllium, magnesium, calcium, vanadium, strontium, zinc, thorium and rhenium.There is also provided a process for the manufacture of methacrylic or acrylic acid by oxidizing methacrolein or acrolein with molecular oxygen in the vapor phase in the presence of the catalyst defined above.
    Type: Grant
    Filed: January 10, 1977
    Date of Patent: February 6, 1979
    Assignee: Nippon Kayaku Kabushiki Kaisha
    Inventors: Masanobu Ogawa, Toshitake Kojima
  • Patent number: 4118419
    Abstract: The gas phase catalytic oxidation of an unsaturated aldehyde with molecular oxygen at 240.degree. to 450.degree. C to the corresponding unsaturated carboxylic acid is conducted in the presence of a catalyst of the formula:P.sub.a Mo.sub.b Bi.sub.c Sb.sub.d X.sub.e Y.sub.f O.sub.gwherein Mo is molybdenum, P is phosphorus, Bi is bismuth, Sb is antimony, O is oxygen, X is at least one element selected from the group consisting of potassium rubidium, cesium and thallium; and Y is at least one element selected from the group consisting of cobalt, zinc, niobium, chromium, nickel, iron, silicon, tantalum, cadmium, uranium, manganese, copper, thorium, selenium, aluminum, titanium, tungsten and cerium, and wherein the subscripts a-g represent the atomic ratio of each component such that a is 0.5 to 6, b is 12, c is 0.01 to 6, d is 0.01 to 12, e is 0.2 to 6, f is 0.01 to 6, and g is a value which is determined by the valencies of the elements present in the catalyst.
    Type: Grant
    Filed: November 26, 1976
    Date of Patent: October 3, 1978
    Assignee: Mitsubishi Rayon Company, Ltd.
    Inventors: Kazuhiro Ishii, Hideo Matsuzawa, Masao Kobayashi, Hiromichi Ishii
  • Patent number: 4115441
    Abstract: The present invention relates to a catalyst composition consisting of oxide complexes of vanadium, molybdenum and germanium plus an additional oxide selected from the group consisting of iron, nickel, thallium, phosphorus, indium, bismuth and the rare earths and optionally an oxide selected from the group copper, magnesium, manganese, aluminum, titanium, potassium, rubidium, cesium, niobium, tantalum, chromium, tungsten, uranium, cobalt, silver, zinc, tin, gallium, arsenic and antimony. These catalysts are especially useful for producing acrylic acid from acrolein and for producing methacrylic acid from methacrolein.
    Type: Grant
    Filed: December 30, 1976
    Date of Patent: September 19, 1978
    Assignee: The Standard Oil Company
    Inventors: Wilfrid G. Shaw, David B. Terrill
  • Patent number: 4113769
    Abstract: A process is disclosed for preparing acrylic acid or methacrylic acid comprising reacting in vapor phase acrolein or methacrolein (respectively) with molecular oxygen or an oxygen-containing gas, at a temperature between 200.degree. and 350.degree. C, in the presence of a solid catalyst, and with a contact time between 0.5 and 5 seconds, characterized in that the solid catalyst comprises molybdenum, vanadium, tungsten, cobalt, chromium and oxgyen chemically combined with these elements, the atomic ratios among the aforesaid elements being represented by the empirical formula: Mo.sub.12 V.sub.a W.sub.b Co.sub.c Cr.sub.d O.sub.e, wherein:a is between 0.5 and 10,b is between 0.5 and 8,c is between 1 and 6,d is between 0.1 and 3, ande is a number sufficient to satisfy the valence requirements of the other elements;And with the further proviso that a+b+c is equal to or greater than 8.5.
    Type: Grant
    Filed: October 20, 1976
    Date of Patent: September 12, 1978
    Assignee: Montedison S.p.A.
    Inventors: Mario Padovan, Giordano De Alberti, Giancarlo Battiston, Romano Covini
  • Patent number: 4113768
    Abstract: Methacrylic acid or acrylic acid are produced by the oxidation of methacrolein or acrolein, respectively, with molecular oxygen in the vapor phase in the presence of a catalytic oxide of molybdenum, phosphorus, bismuth, copper, oxygen, optionally a halogen selected from the group consisting of chlorine, bromine or iodine, and optionally, at least one element selected from the group consisting of Fe, Cr, Ni, Mn, Sb, Te, Rh, and Pd.
    Type: Grant
    Filed: December 6, 1976
    Date of Patent: September 12, 1978