Molybdenum Containing Catalyst Utilized Patents (Class 568/479)
  • Publication number: 20040199008
    Abstract: A catalyst suited for catalytic vapor-phase oxidation of isobutylene, t-butanol or propylene to produce respectively corresponding unsaturated aldehyde and unsaturated carboxylic acid is provided. Said catalyst consists of ring-formed shaped bodies composed of (i) a catalyst composition containing at least molybdenum and bismuth as the active ingredients and (ii) inorganic fibers. The catalyst excels in mechanical strength, can give the object products at high yield and shows little activity degradation with time.
    Type: Application
    Filed: April 20, 2004
    Publication date: October 7, 2004
    Inventors: Hiroto Kasuga, Eiichi Shiraishi
  • Patent number: 6781018
    Abstract: Dimethyl ether is converted to formaldehyde using a supported catalyst comprising molybdenum and/or vanadium oxides. The surface density of the oxide(s) ranges from greater than that for the isolated monomeric oxides upwards, so long as there is a substantial absence of bulk crystalline molybdenum and/or vanadium oxide(s). Conversion and selectivity to formaldehyde are improved as compared to data reported for known catalysts. Also disclosed is a supported catalyst comprising molybdenum and/or vanadium oxides wherein the support comprises one or more reducible metal oxides, preferably a layer or layers of one or more reducible metal oxides disposed on the surface of a particulate alumina or zirconia support.
    Type: Grant
    Filed: February 20, 2003
    Date of Patent: August 24, 2004
    Assignee: The Regents of the University of California
    Inventors: Haichao Liu, Enrique Iglesia
  • Publication number: 20040127746
    Abstract: The present invention provides novel extrusion-molded catalysts which is suitably usable in the synthesis of an unsaturated aldehyde and an unsaturated carboxylic acid by vapor-phase catalytic oxidation, which are prepared by molding-molding catalyst particles (or powders) comprising at least molybdenum, bismuth and iron as metallic elements participating in its catalytic action on this reaction, and which exhibit high catalytic activity and high selectivity for the unsaturated aldehyde and unsaturated carboxylic acid being desired products. When previously formed catalyst particles are subjected to extrusion molding, the catalyst particles are kneaded, for example, with a &bgr;-1,3-glucan and a liquid. Then, the kneaded material is subjected to an extrusion molding step in which a ceramic material is used for at least a part of the catalyst flow path. Thereafter, the extrusion-molded material is dried, calcined and otherwise treated to obtain a final extrusion-molded catalyst.
    Type: Application
    Filed: February 19, 2004
    Publication date: July 1, 2004
    Inventors: Masahide Kondo, Seiichi Kawato, Toru Kuroda
  • Patent number: 6703528
    Abstract: There are disclosed are a method for producing at least one compound selected from a carbonyl compound and a hydroxy adduct compound by an oxidative cleavage or addition reaction of an olefinic double bond of an olefin compound, which contains reacting an olefin compound with hydrogen peroxide, utilizing as a catalyst, at least one member selected from (a) tungsten, (b) molybdenum, or (c) a tungsten or molybdenum metal compound containing (ia) tungsten or (ib) molybdenum and (ii) an element of Group IIIb, IVb, Vb or VIb excluding oxygen, and a catalyst composition.
    Type: Grant
    Filed: August 10, 2001
    Date of Patent: March 9, 2004
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Koji Hagiya, Naoyuki Takano, Akio Kurihara
  • Patent number: 6632965
    Abstract: The present invention provides a process for producing acrolein and acrylic acid by the vapor-phase oxidation of propylene in the presence of Mo—Bi—Fe-based compound oxide catalysts packed in a fixed-bed multitubular reactor wherein acrolein and acrylic acid can be stably produced in high yield for a long period of time. This process is characterized in that each reaction tube having two or more reaction zones disposed along the axis of the tube is packed with catalysts having different ratios of the Bi and/or Fe content to the Mo content in such a way that the ratio decreases from the gas inlet side toward the gas outlet side.
    Type: Grant
    Filed: August 4, 2000
    Date of Patent: October 14, 2003
    Assignee: Nippon Shokubai Co. Ltd.
    Inventors: Michio Tanimoto, Hiromi Yunoki, Hideyuki Hironaka, Naomasa Kimura
  • Publication number: 20030191344
    Abstract: The present invention provides a process in which, when an unsaturated aldehyde and/or an unsaturated carboxylic acid are produced by carrying out a catalytic gas phase oxidation reaction by using a fixed-bed multitubular reactor which is packed with a molybdenum-containing catalyst, the deterioration of the catalyst as located at a hot spot portion can be suppressed; so that the reaction can be continued for a long time while a high yield is maintained, regardless of where the hot spot portion occurs and also even if the concentration of a raw gas is high.
    Type: Application
    Filed: March 9, 2003
    Publication date: October 9, 2003
    Applicant: Nippon Shokubai Co., Ltd.
    Inventor: Hiromi Yunoki
  • Publication number: 20030187305
    Abstract: Coated catalysts which are suitable for the gas-phase catalytic oxidation of propene to acrolein are prepared by a process in which rings are used as supports and water is used as a binder.
    Type: Application
    Filed: April 10, 2003
    Publication date: October 2, 2003
    Inventors: Jochen Petzoldt, Signe Unverricht, Heiko Arnold
  • Patent number: 6624332
    Abstract: The method of the present invention involves the in situ formation of metal-molybdate catalyst particles active for methanol oxidation to formaldehyde, with iron as an example, the catalyst is made by mixing particulate forms of Fe2O3 and MoO3 which form an active Fe2(MoO4)3/MoO3 component inside the reactor during methanol oxidation.
    Type: Grant
    Filed: October 31, 2001
    Date of Patent: September 23, 2003
    Assignee: Lehigh University
    Inventors: Israel E. Wachs, Laura E. Briand
  • Patent number: 6620973
    Abstract: A catalyst composition for the production of unsaturated aldehydes by the oxidation of the corresponding olefins, and methods of making and using such catalyst compositions. The catalysts of the present invention include compositions of the formula: MoaPdbBicFedX1eX2fX3gOz, wherein X1 is an element selected from Co, Ni, V, Pt, Rh, or mixtures thereof; X2 is an element selected from Al, Ga, Ge, Mn, Nb, Zn, Ag, P, Si, W, or mixtures thereof; X3 is an element selected from K, Mg, Rb, Ca, Sr, Ba, Na, In, or mixtures thereof; a is 1; b is 0<b<0.3; c is 0<c<0.9; d is 0<d<0.9; e is 0<e<0.9; f is 0<f<0.9; g is 0<g<0.3; and z is an integer representing the number of oxygen atoms required to satisfy the valency of Mo, Pd, Bi, Fe, X1, X2, and X3 in the catalyst composition. Using the methods of the present invention, one may effectively oxidize the desired starting materials at relatively high levels of conversion, selectivity, and productivity, and with minimal side products.
    Type: Grant
    Filed: October 19, 2001
    Date of Patent: September 16, 2003
    Assignee: Saudi Basic Industries Corporation
    Inventors: Khalid Karim, Yajnavalkya Subrai Bhat, Syed Irshad Zaheer, Asad Ahmad Khan
  • Publication number: 20030162998
    Abstract: The present invention provides: a production process for a catalyst for synthesis of an unsaturated aldehyde and/or an unsaturated carboxylic acid, which production process is suitable for producing the catalyst with good reproducibility, wherein the catalyst is excellent in activity, selectivity, and physical strength; this catalyst; and a production process for the unsaturated aldehyde and/or the unsaturated carboxylic acid by using this catalyst.
    Type: Application
    Filed: February 5, 2003
    Publication date: August 28, 2003
    Applicant: Nippon Shokubai Co., Ltd.
    Inventor: Hiromi Yunoki
  • Patent number: 6545178
    Abstract: In the production of acrolein and acrylic acid by the catalytic gas phase oxidation of propylene with a molecular oxygen-containing gas, a method is provided which enables acrolein and acrylic acid to be stably produced with a high yield for a long time from propylene by effectively repressing such secondary reactions as are responsible for the formation of organic acids, high boiling compounds, and tarry compounds, the deposition of carbonized materials, and the deterioration of the quality of products. The content of unsaturated hydrocarbons (excluding propylene) of 2-5 carbon atoms in the raw material for propylene is kept below 500 ppm (by weight). Particularly, it is proper to use a raw material for propylene which has a content of unsaturated hydrocarbons (excluding propylene) of 2-5 carbon atoms of not more than 200 ppm (by weight) and a total content of diene and acetylenic compounds of 2-5 carbon atoms of not more than 200 ppm (by weight).
    Type: Grant
    Filed: May 18, 1999
    Date of Patent: April 8, 2003
    Assignee: Nippon Shokubai Co., Ltd.
    Inventors: Michio Tanimoto, Daisuke Nakamura, Tatsuya Kawajiri
  • Patent number: 6509508
    Abstract: A reaction for producing (metho)acrolein and (meth)acrylic acid by vaporn-phase oxidation of at least a compound selected from propyl-ene, isobytylene, t-bytanol and methyl-t-butyl ether. For the process Complex oxide catalysts represented by the formula, MoaWbBicFedAeBfCgDhEiOx (in which A is Ni or Co; B is Na, K, Rb, Cs or Tl; C is an alkaline earth metal; D is P, Te, Sb, Sn, Ce, Pb, Nb, Mn, As, B or Zn; E is Si, Al, Ti or Zr; and where a is 12, 0≦b≦10, 0<c≦10, 0<d≦10, 2≦e≦15, 0<f≦10, 0≦g≦10, 0≦h≦4 and 0≦i≦30) are provided. The catalysts are characterized in that the molar ratio of the total nitrate anions to the molybdenum at the time of catalyst preparation is more than 1 but not more than 1.8.
    Type: Grant
    Filed: February 14, 2002
    Date of Patent: January 21, 2003
    Assignee: Nippon Shoku Bai Co Ltd
    Inventors: Naomasa Kimura, Michio Tanimoto, Hideo Onodera
  • Patent number: 6437193
    Abstract: An improved method for the selective vapor phase oxidation of propylene to acrolein in a recirculating solids reactor system using a bismuth molybdate multimetal oxide involving specific reactant concentrations (preferably 5 mol % to 30 mol % propylene, 0 to 20 mol % oxygen, and the remainder inert gas), particle size (1 to 300 micrometers), temperature (250 to 450° C.) and gas (1 to 15 seconds) and solids (2 to 60 seconds) residence times. Such a process leads to improved selectivity and propylene conversion.
    Type: Grant
    Filed: April 6, 2000
    Date of Patent: August 20, 2002
    Assignees: E. I. du Pont de Nemours and Company, Atofina
    Inventors: Rashmikant Maganlal Contractor, Mark William Andersen, Daniel Campos, Gerard Hecquet, Roland Kotwica, Charlotte Pham, Michel Simon, Mireille Stojanovic
  • Patent number: 6423875
    Abstract: In a process for the preparation of acrolein and/or acrylic acid from propane, the propane is subjected, in a first reaction stage, to an oxydehydrogenation with molecular oxygen under homogeneous and/or heterogeneous catalysis to give propene and the product gas mixture formed in the first reaction stage is then used for the preparation of acrolein and/or acrylic acid by gas-phase catalytic propene oxidation.
    Type: Grant
    Filed: February 20, 2001
    Date of Patent: July 23, 2002
    Assignee: BASF Aktiengesellschaft
    Inventors: Otto Machhammer, Andreas Tenten, Harald Jachow, Susanne Haupt, Heiko Arnold, Signe Unverricht
  • Patent number: 6417376
    Abstract: A process for selectively oxidizing an organic molecule by reacting said organic molecule and oxygen in the presence of a selective oxidation catalyst supported on a mesh-like structure.
    Type: Grant
    Filed: September 29, 1999
    Date of Patent: July 9, 2002
    Assignee: ABB Lummus Global Inc.
    Inventors: Chuen Y. Yeh, Lawrence L. Murrell, Pal Rylandshom, Robert E. Trubac, Rudolf A. Overbeek, Chiung Y. Huang, Cemal Ercan, Nelleke Vander Puil, Herbert E. Barner
  • Patent number: 6410800
    Abstract: The present invention relates to a process for preparing acrolein by the oxidation of propylene and more particularly, to the process for preparing acrolein in the presence of a solid catalyst having core-shell structure represented in the formula 1, [BinAaOx][(100-z)%EeFe1NigMomOy+z%SiO2]  (1) wherein A is at least one element selected from the group consisting of boron, phosphorus, and molybdenum; E is at least one element having the atomic valence of 2; when m is 1, n is 0.001-3, a is 0-3, e is 0-3, f is 0.01-5, g is 0.1-5, and z is 0-90; and x and y are numbers such that the valence requirements of the other elements for Oxygen in the core and shell catalytic phase, respectively, are satisfied.
    Type: Grant
    Filed: September 29, 2000
    Date of Patent: June 25, 2002
    Assignee: Korea Research Institute of Chemical Technology
    Inventors: Tae Sun Chang, Deug Hee Cho, Dong Koo Lee
  • Patent number: 6410785
    Abstract: In a process for the preparation of acrolein by gas-phase partial oxidation under heterogeneous catalysis, a reaction gas starting mixture which contains propene and molecular oxygen in a molar C3H6:O2 ratio of >1 is reacted in reaction zones connected in series, at elevated temperatures, over solid-state catalysts, further molecular oxygen being added to the reaction gas mixture in the course of the partial oxidation.
    Type: Grant
    Filed: July 18, 2001
    Date of Patent: June 25, 2002
    Assignee: BASF Aktiengesellschaft
    Inventors: Peter Zehner, Otto Machhammer, Heiko Arnold, Klaus Joachim Müller-Engel
  • Patent number: 6399818
    Abstract: As an improvement in the process for preparing unsaturated aldehydes and unsaturated carboxylic acids through vapor-phase catalytic oxidation of at least one starting compound selected from propylene, isobutylene, t-butanol and methyl-t-butyl ether with molecular oxygen or a molecular oxygen-containing gas, using a fixed bed shell-and-tube type reactor which is filled with shaped catalysts, a process capable of effectively inhibiting occurrence of hot spots or excessive heat generation at the hot spots and producing unsaturated aldehydes and unsaturated carboxylic acids at high yields is provided.
    Type: Grant
    Filed: May 11, 2001
    Date of Patent: June 4, 2002
    Assignee: Nippon Shokubai Co. Ltd.
    Inventors: Michio Tanimoto, Tadashi Sento
  • Patent number: 6346646
    Abstract: A process for producing methacrolein and methacrylic acid by catalytically oxidizing isobutylene or tertiary butanol in the presence of a catalyst comprising a compound oxide containing molybdenum, bismuth and iron as the essential components, wherein a catalytic oxidation reaction is started at a temperature of (T−3)° C. or lower wherein T° C. is defined as the boundary temperature of activation energy of a reaction for obtaining methacrolein and methacrylic acid from isobutylene using said catalyst, the reaction is continued while the reaction temperature is increased as the activity of the catalyst decreases, and an activation treatment is conducted for the catalyst at least once before the reaction temperature exceeds the boundary temperature of activation energy.
    Type: Grant
    Filed: January 27, 2000
    Date of Patent: February 12, 2002
    Assignee: Mitsubishi Rayon Co., Ltd.
    Inventors: Seigo Watanabe, Motomu Oh-Kita
  • Patent number: 6337424
    Abstract: The present invention provides a catalyst composition for the production of unsaturated aldehydes by the oxidation of the corresponding olefins, and methods of making and using such catalyst compositions. The catalysts of the present invention include compositions of the formula: MoaPdbBicFedX1eX2fX3gOz, wherein X1 is an element selected from Co, Ni, V, Pt, Rh, or mixtures thereof; X2 is an element selected from Al, Ga, Ge, Mn, Nb, Zn, Ag, P, Si, W, or mixtures thereof; X3 is an element selected from K, Mg, Rb, Ca, Sr, Ba, Na, In, or mixtures thereof; a is 1; b is 0<b<0.3;c is 0<c<0.9; d is 0<d<0.9; e is 0<e<0.9; f is 0<f<0.9; g is 0<g<0.3; and z is an integer representing the number of oxygen atoms required to satisfy the valency of Mo, Pd, Bi, Fe, X1, X2, and X3 in the catalyst composition.
    Type: Grant
    Filed: April 28, 2000
    Date of Patent: January 8, 2002
    Assignee: Saudi Basic Industries Corporation
    Inventors: Khalid Karim, Yajnavalkya Subrai Bhat, Syed Irshad Zaheer, Asad Ahmad Khan
  • Patent number: 6090977
    Abstract: In a process for the continuous heterogeneously catalyzed gas-phase partial oxidation of an organic compound in an oxidation reactor, whose feed gas mixture comprises, apart from the organic compound to be partially oxidized and molecular oxygen as oxidant, at least one diluent gas which is essentially inert under the conditions of the heterogeneously catalyzed gas-phase partial oxidation, where the essentially inert diluent gas consists partly of combustible gases, after passage through the oxidation reactor, the combustible constituents of the inert diluent gas present in the product gas stream leaving the oxidation reactor are not recirculated to the heterogeneously catalyzed gas-phase partial oxidation, but are put to further use for the purposes of another chemical reaction.
    Type: Grant
    Filed: March 5, 1996
    Date of Patent: July 18, 2000
    Assignee: BASF Aktiengesellschaft
    Inventors: Werner Hefner, Otto Machhammer, Hans-Peter Neumann, Andreas Tenten, Wilhelm Ruppel, Herbert Vogel
  • Patent number: 6080893
    Abstract: A mixed oxide solid composition of formula (I):Mo.sub.12 W.sub.a Bi.sub.b Fe.sub.c Co.sub.d Ni.sub.e Si.sub.f K.sub.g Sn.sub.h O.sub.x (I)where O.ltoreq.a.ltoreq.5, 0.5.ltoreq.b.ltoreq.5, 0.1.ltoreq.c.ltoreq.10, 0.5.ltoreq.d.ltoreq.10, 0.ltoreq.e.ltoreq.10, 0.ltoreq.f.ltoreq.15, 0.ltoreq.g.ltoreq.1, 0.ltoreq.h.ltoreq.2 and x is the quantity of oxygen bonded to the other elements and depends on their oxidation states, is used in the manufacture of acrolein by oxidizing propylene, the solid composition reacting with propylene according to the redox reaction (1):solid.sub.oxidized +propylene.fwdarw.solid.sub.reduced +acrolein(I)To manufacture acrolein, gaseous propylene is passed over a solid composition of formula (I), to conduct the redox reaction (1) by operating at a temperature of 200 to 600.degree. C., at a pressure of 1.01.times.10.sup.4 to 1.01 to 10.sup.6 Pa (0.1 to 10 atmospheres) and with a residence time of 0.01 second to 90 seconds, in the absence of molecular oxygen.
    Type: Grant
    Filed: February 27, 1998
    Date of Patent: June 27, 2000
    Assignee: Elf Atochem, S.A.
    Inventors: Gerard Hecquet, Jean-Pierre Schirmann, Michel Simon, Gilles Descat, Eric Etienne
  • Patent number: 6028220
    Abstract: The present invention concerns a method for producing acrolein and acrylic acid by carrying out vapor phase catalytic oxidation of propylene with molecular oxygen or a gas containing molecular oxygen using a oxidation catalysts comprising Mo, Bi and Fe as an essentially element and a fixed bed multitubular reactor, which comprisesa) using a plurality of supported catalysts having different activities, which was obtained, for example, by different calcination method in the production process of the supported catalysts,b) setting a catalyst layer in a reaction tube, which is formed by dividing it into plural portions in the tube axial direction, andc) arranging the aforementioned plural supported catalysts in such order that the activity becomes high toward the outlet from the inlet of the material gas in the reaction tube axial direction.
    Type: Grant
    Filed: July 28, 1998
    Date of Patent: February 22, 2000
    Assignee: Nippon Kayaku Kabushiki Kaisha
    Inventors: Koichi Wada, Yoshimasa Seo, Akira Iwamoto, Atsushi Sudo, Fumio Sakai, Kazuo Shiraishi, Hiroyoshi Nowatari
  • Patent number: 6028230
    Abstract: The amount of high molecular weight impurity present in a polyether polyol produced by alkoxylation of an active hydrogen-containing initiator using an epoxide such as propylene oxide and a substantially amorphous highly active double metal cyanide complex catalyst may be advantageously lowered by having a non-protic Lewis acid present during the epoxide polymerization. The use of halides such as zinc chloride and aluminum chloride is especially effective for such purposes. In a preferred embodiment, minor amounts of water are also present during polymerization. The higher purity polyether polyols thereby produced are particularly useful in the preparation of slab and molded polyurethane foams, which tend to collapse or become excessively tight when elevated levels of high molecular tail are present in the polyether polyol.
    Type: Grant
    Filed: June 5, 1998
    Date of Patent: February 22, 2000
    Assignee: Arco Chemical Technology, L.P.
    Inventors: Bi Le-Khac, Ulrich B. Holeschovsky, Michael A. Rueter
  • Patent number: 5981804
    Abstract: A catalyst for the production of unsaturated aldehyde and unsaturated carboxylic acid by the vapor-phase catalytic oxidation of at least one compound selected from the group consisting of propylene, isobutylene, t-butanol and methyl-t-butyl ether and a method for the production of unsaturated aldehyde and unsaturated carboxylic acid by the use of this catalyst are provided. The catalyst of this invention comprises (A) a catalyst having Mo, Bi and Fe as essential components and used for the production of unsaturated aldehyde and unsaturated carboxylic acid by vapor-phase catalytic oxidation of propylene, isobutylene, t-butanol and/or methyl-t-butyl ether and (B) a solid acid having acid strength (Ho) of not more than -11.93. Since this catalyst excels in catalytic activity and service life, it allows unsaturated aldehyde and unsaturated carboxylic acid to be produced stably at a high yield for a long time.
    Type: Grant
    Filed: December 22, 1997
    Date of Patent: November 9, 1999
    Assignee: Nippon Shokubai Co., Ltd.
    Inventors: Ikuo Kurimoto, Tatsuya Kawajiri, Hideo Onodera, Michio Tanimoto, Yukio Aoki
  • Patent number: 5929275
    Abstract: A catalyst for the production of unsaturated aldehyde and unsaturated acid, obtained by loading a catalytically active component on a carrier and calcining the loaded catalyst, characterized by an average particle diameter of the catalyst of 4 to 16 mm, an average particle diameter of the carrier of 3 to 12 mm, a calcining temperature of 520 to 600.degree. C. and an amount of the catalytically active component loaded on the carrier of 5 to 80% by weight ?weight of the catalytically active component)/(weight of the catalytically active component+weight of the carrier+weight of a strength improver)!, and a process for producing unsaturated aldehyde and unsaturated acid with the catalyst.
    Type: Grant
    Filed: May 9, 1997
    Date of Patent: July 27, 1999
    Assignee: Nippon Kayaku Co., Ltd.
    Inventors: Koichi Wada, Akira Iwamoto, Yoshimasa Seo, Atsusi Sudo, Fumio Sakai, Kazuo Shiraishi, Hideaki Miki
  • Patent number: 5892108
    Abstract: A method for packing of catalyst, which comprises mixing, into a shaped catalyst containing at least molybdenum and iron, used in the gas-phase catalytic oxidation of propylene, isobutylene, tert-butyl alcohol or methyl tert-butyl ether with molecular oxygen to synthesize an unsaturated aldehyde and an unsaturated carboxylic acid both corresponding to the raw material used, metal-made Raschig rings as auxiliary packing material having a bulk volume of 0.3-3.5 times that of the shaped catalyst and a packing density of 0.5-1.5 kg/l, and packing the resulting mixture into a fixed bed type reactor; and a process for producing an unsaturated aldehyde and an unsaturated carboxylic acid, which comprises subjecting propylene, isobutylene, tert-butyl alcohol or methyl tert-butyl ether to gas-phase catalytic oxidation using molecular oxygen, in a fixed bed type reactor wherein a catalyst is packed by the above method.
    Type: Grant
    Filed: May 6, 1997
    Date of Patent: April 6, 1999
    Assignee: Mitsubishi Rayon Co., Ltd.
    Inventors: Tohru Shiotani, Miezi Sugiyama, Toru Kuroda, Motomu Oh-Kita
  • Patent number: 5864051
    Abstract: A catalyst for the selective oxidation of alkanes and alkenes has been developed. The catalyst consists of a noble metal component such as platinum and a SbOx component. A unique feature of the catalyst is that the noble metal component is present as particles of which from about 1 to about 30 mole % of each particle is in the form of a noble metal/Sb alloy. Optionally a modifier and/or a refractory inorganic oxide may also be added to the catalyst. A process for preparing the catalyst is also presented.
    Type: Grant
    Filed: November 10, 1997
    Date of Patent: January 26, 1999
    Assignee: UOP
    Inventors: Yasuhiro Iwasawa, Kiyotaka Asakura, Tomoya Inoue
  • Patent number: 5728894
    Abstract: Disclosed is a method for producing methacrolein, which comprises subjecting isobutylene and/or tert-butanol to gas phase catalytic oxidation with a molecular oxygen-containing gas in the presence of an oxide catalyst composition represented by the formula Mo.sub.12 Bi.sub.a Ce.sub.b K.sub.c A.sub.e B.sub.f O.sub.g, wherein A is Co solely, or a mixture of Co and Mg wherein the atomic ratio of Mg to Co is not more than 0.7, B is Rb, Cs or a mixture thereof, and a, b, c, d, e, f and g are, respectively, the specific atomic ratios of Bi, Ce, K, Fe, A, B and O, relative to 12 atoms of Mo.
    Type: Grant
    Filed: August 26, 1996
    Date of Patent: March 17, 1998
    Assignee: Ashahi Kasei Kogyo Kabushiki Kaisha
    Inventors: Osamu Nagano, Toru Watanabe
  • Patent number: 5583086
    Abstract: Cesium based multimetal oxide compositions which are suitable as catalysts for the gas-phase-catalytic oxidative preparation of methacrolein from isobutene or tert-butanol or its methyl ether. The catalysts are characterized by increased selectivity for the formation of methacrolein. The catalysts have locally delimited regions of an oxide composition, preferably (Bi.sub.2 W.sub.2 O.sub.9), surrounded by the remaining constituents of the multimetal oxide.
    Type: Grant
    Filed: February 25, 1994
    Date of Patent: December 10, 1996
    Assignee: BASF Aktiengesellschaft
    Inventors: Andreas Tenten, Hans-Peter Neumann, Herbert Exner
  • Patent number: 5491258
    Abstract: For providing a molded catalyst or a supported catalyst which has an excellent mechanical strength and is intended for producing methacrolein and methacrylic acid from isobutylene or tertiary butanol, the surface of a molded catalyst or a supported catalyst which contains molybdenum, bismuth and iron is coated with one or more highly depolymerizable organic high-molecular weight compounds.When used, the catalyst is packed into a reactor and then heated to remove the organic high-molecular weight compound(s) by depolymerization.
    Type: Grant
    Filed: September 12, 1994
    Date of Patent: February 13, 1996
    Assignee: Mitsubishi Rayon Co., Ltd.
    Inventors: Seigo Watanabe, Motomu Ohkita
  • Patent number: 5466837
    Abstract: An ethylene stream which contains ethane as an impurity or a propylene stream which contains propane as an impurity is subjected to adsorption at a temperature of 50.degree. to 200.degree. C. in a bed of adsorbent which selectively adsorbs ethylene or propylene, thereby adsorbing substantially all of the ethylene or propylene. The purified ethylene or propylene stream is then subjected to partial oxidation in the presence of oxygen and, optionally ammonia to produce various partial oxidation products. The process is operated on a low per pass conversion with recycle of unreacted ethylene or propylene. In the system of the invention the adsorption unit may be upstream or downstream of the partial oxidation reactor.
    Type: Grant
    Filed: April 22, 1994
    Date of Patent: November 14, 1995
    Assignee: The BOC Group, Inc.
    Inventors: Ramakrishnan Ramachandran, Loc H. Dao
  • Patent number: 5326916
    Abstract: A process for producing acrolein which comprises bringing a reaction gas resulting from a catalytic oxidation of propylene into contact in a cooling tower with a condensate which is being circulated through the cooling tower and a circulating part, thereby to cool and separate the reaction gas and discharge an effluent gas from the cooling tower, the condensate in a bottom part of the cooling tower having a temperature of from 35.degree. to 50.degree. C., the effluent gas discharged from the cooling tower having a temperature of from 35.degree. to 55.degree. C.
    Type: Grant
    Filed: March 8, 1993
    Date of Patent: July 5, 1994
    Assignee: Sumitomo Chemical Co., Ltd.
    Inventors: Yoshinori Kobayashi, Yasuo Matsumoto, Tadashi Mizuno, Masamitu Fukuda
  • Patent number: 5245083
    Abstract: A catalyst is herein disclosed, which comprises a mixture of a composition (1) represented by the following general formula (1):(Mo).sub.a (Bi).sub.b (Fe).sub.c (X).sub.d (Z).sub.f (O).sub.g (1)(wherein X represents one or both of Ni and Co, Z represents at least one element selected from the group consisting of W, Be, Mg, S, Ca, Sr, Ba, Te, Se, Ce, Ge, Mn, Zn, Cr, Ag, Sb, Pb, As, B, P, Nb, Cu, Cd, Sn, Al, Zr and Ti, a, b, c, d, f and g each represents an atomic ratio of each corresponding element and if a is assumed to be 12, b ranges from 0.1 to 10, c ranges from 0 to 20, d ranges from 0 to 20 and f ranges from 0 to 4 and g is a number of oxygen atom required for satisfying the valency requirement of the foregoing elements) and a composition (2) represented by the following general formula (2):(A).sub.m (Mo).sub.n (O).sub.p (2)(wherein A represents at least one element selected from K, Rb and Cs and m, n and p each represents an atomic ratio and if m is assumed to be 2, n ranges from 1 to 9 and p is 3n+1).
    Type: Grant
    Filed: February 26, 1992
    Date of Patent: September 14, 1993
    Assignee: Mitsui Toatsu Chemicals, Inc.
    Inventor: Ikuya Matsuura
  • Patent number: 5183936
    Abstract: The process for oxidation of propylene to acrolein and the oxidation of propylene to acrylic acid in two stages with acrolein as an intermediate are improved by use of essentially inert essentially anhydrous diluent gases to replace steam in the reaction streams. In particular, the use of essentially inert essentially anhydrous diluents which raise the composite heat capacity of the diluent gas mixture to at least about 6.5 calories/(gram-mole) (.degree.C.) will improve selectively to desired products and will reduce both the waste water load on the system and by-product formation. Reduction in second-stage catalyst efficiency is compensated for by introducing steam to the feed to the second-stage, and/or by increasing the operating temperature of the second-stage, and/or by increasing the active surface area of the second-stage catalyst.
    Type: Grant
    Filed: October 25, 1991
    Date of Patent: February 2, 1993
    Assignee: Union Carbide Chemicals & Plastics Technology Corporation
    Inventors: William G. Etzkorn, Gordon G. Harkreader
  • Patent number: 5144090
    Abstract: A method for preparing acrolein or methacrolein comprises subjecting propylene, secondary propanol, isobutylene or tertiary butanol to gas phase catalytic oxidation with molecular oxygen in the presence of a catalyst represented by the following general formula (I):Mo.sub.a Bi.sub.b Fe.sub.c X.sub.d Y.sub.O Z.sub.f O.sub.g (I)wherein X represents at least one element selected from the group consisting of Ni and Co; Y represents at least one element selected from the group consisting of K, Rb, Cs and Tl; and Z represents at least one element selected from the group consisting of Be, Mg, Ca, Sr, Ba, Ce, Ti, Zr, Nb, Cr, W, Mn, Cu, Ag, Zn, Cd, B, Al, Si, Ge, Sn, Pb, P, As, Sb, S, Se and Te; a, b, c, d, e, f and g each represents an atomic ratio of the corresponding element and when a is assumed to be 12, b=0.1.about.10, c=0.1.about.20, d=2.about.20, e=0.01.about.2, f=0.about.
    Type: Grant
    Filed: June 6, 1991
    Date of Patent: September 1, 1992
    Assignee: Mitsui Toatsu Chemicals, Incorporated
    Inventors: Tadatoshi Honda, Tokio Nagayama, Nobuhiko Horiuchi, Jun Kitagawa, Kazunori Kawahara, Masami Murakami
  • Patent number: 5144091
    Abstract: A process for the catalytic gas-phase oxidation of propene or isobutene to acrolein or methacrolein in a tubular fixed bed reactor or catalytically active oxides with a .gtoreq.90% conversion of the initial olefin on a single passage, wherein the temperature of the gases containing the reactants in the direction of flow along the tubes from their entrance until the conversion of the initial olefin is from 30 to 70% is from 360.degree. to 420.degree. C. and is then adjusted to from 360.degree. to 300.degree. C. until the conversion of the initial olefin is from 80 to 90% and is thereafter maintained at from 330.degree. to 390.degree. C. until the gases emerge from the tubes, is described.
    Type: Grant
    Filed: July 19, 1991
    Date of Patent: September 1, 1992
    Assignee: BASF Aktiengesellschaft
    Inventors: Hans Martan, Ulrike Wegerle, Wilhelm Ruppel, Lothar Riekert, Dieter Becker, Michael Kotter
  • Patent number: 5138100
    Abstract: A method for preparing methacrolein comprises subjecting isobutylene or a tertiary butanol to gas phase catalytic oxidation with molecular oxygen in the presence of a catalyst which comprises a mixture of a composition (I) represented by the following general formula I:Mo.sub.a Bi.sub.b Fe.sub.c X.sub.d Y.sub.e Z.sub.f O.sub.g Iwherein X represents at least one element selected from the group consisting of Ni and Co; Y represents at least one element selected from the group consisting of K, Rb, Cs and Tl; Z represents at least one element selected from the group consisting of those belonging to Group 2, 3, 4, 5, 6, 7, 11, 12, 13, 14, 15 and 16 of Periodic Table in accordance with IUPAC nomenclature (1989); and a, b, c, d, e, f and g each represents an atomic ratio of each corresponding element, when a is assumed to be 12, b is 0.
    Type: Grant
    Filed: June 6, 1991
    Date of Patent: August 11, 1992
    Assignee: Mitsui Toatsu Chemicals, Inc.
    Inventor: Ikuya Matsuura
  • Patent number: 5081314
    Abstract: Dilute solutions of acrolein are produced on site and on demand by oxidizing propylene in an improved reactor using an improved catalyst, which is a mixture of molybdenum, bismuth and tellurium oxides. The catalyst is deposited on metal particles, which are of a metal selected from the group consisting of aluminum, tantalum, titanium, tungsten, niobium and mixtures thereof, and are packed to form a catalyst bed which provides improved heat transfer and distribution for better control of the process. The reaction is conducted in a reactor in which all the exposed surfaces are made of a metal selected from the group just mentioned. The produced acrolein is absorbed to form a dilute solution of acrolein in a liquid to be treated, such as irrigation water for weed control, or control of hydrogen sulfide in water used for oil and gas field water floods, or in fuel oil to inhibit growth of organisms.
    Type: Grant
    Filed: December 7, 1990
    Date of Patent: January 14, 1992
    Inventors: Charles L. Kissel, Charles M. Finley
  • Patent number: 5077434
    Abstract: Vapor phase catalytic oxidation of propylene into acrolein in the first step and then into acrylic acid in the second step has been improved (1) by utilizing as a diluent for the oxidation in the first step the effluent gas from the second step after the acrylic acid produced has been recovered therefrom and after it has been catalytically combusted and (2) by specifying operation conditions set in view of the recycle of the combusted "waste" gas.The improved process, embodying the present invention, has made it possible to produce a high concentration of acrylic acid as both gas and condensation and also to prolong the catalytic activity of a Mo-Bi composite oxide catalyst used for the first oxidation reaction.
    Type: Grant
    Filed: December 7, 1987
    Date of Patent: December 31, 1991
    Assignee: Mitsubishi Petrochemical Company Limited
    Inventors: Kohei Sarumaru, Takeshi Shibano
  • Patent number: 5072052
    Abstract: The present invention relates to a process for the production of acrolein by catalytic gas-phase oxidation of propene with air in the presence of steam and an inert gas or waste gas from the reaction, the starting materials being passed in defined quantitative ratios at 300.degree. to 380.degree. C. under 1.4 to 2.2 bar pressure over a catalyst containing the combination of elements MoFeCoNiBiP(As)K(Rb,Cs)SmSiO in the form of a bed of individual elements, the catalyst elements fulfilling certain geometric conditions and a number of critical physico-chemical parameters and a specific load of 2 to 8 mol propene/dm.sup.3 catalyst bed/h being adjusted.
    Type: Grant
    Filed: September 12, 1990
    Date of Patent: December 10, 1991
    Assignee: Degussa Aktiengesellschaft
    Inventors: Wolfgang Boeck, Dietrich Arntz, Guenter Prescher, Werner Burkhardt
  • Patent number: 4968846
    Abstract: This invention provides a method for the prevention of oxidation of resulting methacrolein immediately after its discharge from a reaction tube upon production of the methacrolein by vapor-phase oxidation of isobutylene, tertiary butanol or methallyl alcohol with a molecular-oxygen-containing gas in the presence of a catalyst. An inert gas and/or recirculated reaction gas or a mixed gas of an inert gas and/or recirculated reaction gas and air is fed and mixed with a reaction product gas immediately after an outlet of the reaction tube.
    Type: Grant
    Filed: July 12, 1988
    Date of Patent: November 6, 1990
    Assignees: Mitsui Toatsu Chemicals, Incorporated, Kyowa Gas Chemical Industry Company, Ltd.
    Inventors: Morimasa Kuragano, Kozo Iwasaki, Yoshio Koyama, Takeshi Isobe, Hirozo Segawa, Katsuji Yoguchi
  • Patent number: 4873368
    Abstract: Propylene in admixture with molecular oxygen and steam is subjected to a two-step, vapor-phase, catalytic oxidation to convert into acrolein and then into acrylic acid. At least the first-step reaction is conducted in tubes of an apparatus of a shell-and-tube heat-exchanger type structure, and the reaction product of the first-step reaction is quenched before it is subjected to the second-step reaction. Reaction conditions in both the steps are specified.
    Type: Grant
    Filed: September 29, 1982
    Date of Patent: October 10, 1989
    Assignee: Mitsubishi Petrochemical Company Limited
    Inventors: Koju Kadowaki, Kohei Sarumaru, Takeshi Shibano
  • Patent number: 4871700
    Abstract: A method of reactivating a catalyst having reduced activity as a result of having been used in producing an unsaturated aldehyde as a main product by catalytic vapor-phase oxidation reaction of propylene, isobutylene or tertiary butanol, said catalyst being a catalytic oxide comprising molybdenum, bismuth and iron with a Mo:Fe atomic ratio of 12:at least 0.1. The method comprises heat-treating the used catalyst at a temperature of 300.degree. to 500.degree. C. in the presence of a flowing oxidizing gas containing at least 5% by volume of molecular oxygen and at least 0.1% by volume of steam.
    Type: Grant
    Filed: May 12, 1988
    Date of Patent: October 3, 1989
    Assignee: Nippon Shokubai Kagaku Kogyo Co., Ltd.
    Inventors: Shin-ichi Uchida, Kozi Deguchi, Masamitsu Sasaki
  • Patent number: 4837360
    Abstract: Acrolein and acrylic acid are produced by vapor-phase catalytic oxidation of propylene in a multi-tubular, fixed-bed reaction vessel with the use of a composite oxide catalyst represented by the formula Mo.sub.a Bi.sub.b Fe.sub.c A.sub.d B.sub.e C.sub.f D.sub.g Si.sub.h O.sub.x, wherein A, B, C, and D represent components selectable from respective groups of elements, and the subscripts a through h and x are specific numbers of atoms of respective elements and groups of elements. This catalyst is adapted and packed in each reaction tube in a manner such that its activity is controlled to increase from the inlet toward the outlet of the tube.
    Type: Grant
    Filed: September 23, 1982
    Date of Patent: June 6, 1989
    Assignee: Mitsubishi Petrochemical Company Ltd.
    Inventors: Koju Kadowaki, Kohei Sarumaru, Takeshi Shibano
  • Patent number: 4757038
    Abstract: Iron-antimony metallic oxide catalysts which have become deactivated after being used for the production of aldehydes, acids, nitriles, or dienes through oxidation, ammoxidation, or oxidative dehydrogenation of organic compounds in fluidized-bed reactors are regenerated by adding to the catalyst a molybdenum-enriched catalyst formed by supporting a molybdenum component which is volatile or capable of forming a volatile compound under reaction conditions on a metallic oxide catalyst. The metallic oxide catalysts contain as essential components (I) Fe, (II) Sb, (III) at least one element selected from the group consisting of V, Mo and W, and (IV) Te.
    Type: Grant
    Filed: May 15, 1987
    Date of Patent: July 12, 1988
    Assignee: Nitto Chemical Industry Co., Ltd.
    Inventors: Yutaka Sasaki, Yutaka Kiyomiya, Toshio Nakamura, Yoshimi Nakamura, Masanori Yamaguchi
  • Patent number: 4746753
    Abstract: Bismuth cerium molybdate catalysts promoted with alkali metal and other optional ingredients provide high yields of acrylonitrile in the ammoxidation of propylene.
    Type: Grant
    Filed: July 1, 1986
    Date of Patent: May 24, 1988
    Assignee: The Standard Oil Company
    Inventors: James F. Brazdil, Jr., Dev D. Suresh, Robert K. Grasselli
  • Patent number: 4709070
    Abstract: A process for improving the activity of tellurium containing metal oxide catalysts useful as catalysts for oxidation, ammoxidation or oxidative dehydrogenation of organic compounds by heating the catalysts together with an activity-improving agent to a temperature up to about 900.degree. C. in a gaseous atmosphere. The process can be effectively applied to deteriorated or spent catalysts, the activity of which has been deteriorated due to use for a long period of time.
    Type: Grant
    Filed: November 9, 1984
    Date of Patent: November 24, 1987
    Assignee: Nitto Chemical Industry Co., Ltd.
    Inventors: Yutaka Sasaki, Yutaka Kiyomiya, Toshio Nakamura
  • Patent number: 4622424
    Abstract: A process for conducting a combination of fixed and fluid-bed catalytic reactions is achieved by employing fixed-bed catalysts on supports within the fluid bed. The fluid-bed catalysts may move in both directions through the fixed bed, thereby giving advantages of both types of beds in one reactor.
    Type: Grant
    Filed: September 6, 1985
    Date of Patent: November 11, 1986
    Assignee: The Standard Oil Company
    Inventors: James L. Callahan, Arthur F. Miller, Wilfrid G. Shaw
  • Patent number: RE32484
    Abstract: A vapor phase catalytic oxydehydrogenation process for the conversion of a steam of mixed isomeric isoamylenes, methyl butanols or mixtures thereof to isoprene with relatively short contact times at a reactor temperature in the range of 500.degree. F. to 1100.degree. F. at from 0.5 to about 10 atmospheres pressure. The catalysts comprise an alkali metal as an essential catalytic ingredient.
    Type: Grant
    Filed: September 2, 1983
    Date of Patent: August 25, 1987
    Assignee: The Standard Oil Company
    Inventors: Robert K. Grasselli, Harley F. Hardman