Catalyst Contains Phosphorus Patents (Class 568/480)
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Publication number: 20110295041Abstract: A method of preparing a catalyst for producing acrolein by oxidation of propylene at high space velocity, said catalyst is a Mo—Bi—Fe—Co based composite metal oxide. Producing unsaturated aldehyde via partial oxidation of lower unsaturated olefin at high space velocity using said catalyst is suitable for process with or without off-gas recirculating. Said catalyst is prepared by co-precipitation, the reaction conditions for using said catalyst to produce unsaturated aldehyde are, the space velocity of unsaturated lower olefin relative to catalyst being 120˜200 h-1(STP), reaction temperature being 300˜420° C. and absolute pressure being 0.1˜0.5 MPa; a single-stage unsaturated lower olefin conversion ratio of greater than 98.0% and carbon oxide yield of less than 3.3% with an overall yield of unsaturated lower aldehyde and acid of greater than 94.0% are obtained. The process to prepare the said catalyst is simple, easy to be repeated, and capable of industrial scale-up.Type: ApplicationFiled: May 26, 2011Publication date: December 1, 2011Applicant: Shanghai HuaYi Acrylic Acid Co. Ltd.Inventors: Jian Wang, Xuemei Li, Yan Zhuang, Kaimin Shi, Kun Jiao, Jianxue Ma, Xiaodong Chu, Jingming Shao
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Publication number: 20090287018Abstract: A catalyst for use in the production of an unsaturated aldehyde and/or an unsaturated carboxylic acid, the catalyst comparing (or, preferably, being composed of) a mixed oxide containing molybdenum, bismuth and iron, which has improved mechanical strength, is produced by a method including the steps of (1) drying an aqueous solution or an aqueous slurry containing raw materials of the catalyst and then firstly calcining a dried product in a molecular oxygen-containing gas atmosphere to obtain a calcined product; (2) heating the calcined product obtained in Step (1) in the presence of a reducing material to obtain a reduced product having a mass loss of 0.05 to 6%; and (3) secondly calcining the reduced product obtained in Step (2) in a molecular oxygen-containing gas atmosphere.Type: ApplicationFiled: May 15, 2009Publication date: November 19, 2009Applicant: SUMITOMO CHEMICAL COMPANY, LIMITEDInventors: Naoki MIURA, Eiichi Shiraishi, Koichi Nagai
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Publication number: 20090171118Abstract: The invention concerns a compound comprising a combination of two crystal phases. The first crystal phase corresponds to the formula: AaEbVcModPeOfHg wherein A is an alkali-metal; E is Te, Sb or Bi; and 0?a?3, 0<b?3, 0?c?3, 0<d?13, 0<e?2, 0?g?3. The second crystal phase corresponds to the formula ZgMohXiOj wherein: Z is selected among trivalent rare earths; X is selected among the elements V, Ga, Fe, Bi, Ce, Ti, Sb, Mn, Zn, Te; and 0<g?3, 0?h?3, 0?i?1. The indices f and j represent the number of oxygen atoms required for satisfying the relative valency and atomic proportions of the elements present. The invention also concerns the method for preparing said compound, and its use in particular as catalyst for oxidizing alkanes.Type: ApplicationFiled: February 14, 2007Publication date: July 2, 2009Inventors: Jean-Marc Millet, Philippe Lacorre, Quyen Huynh
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Publication number: 20080242815Abstract: The invention provides a process which enables, in preparation of acrolein by catalytic gas-phase oxidation of propylene in the presence of molecular oxygen or a molecular oxygen-containing gas or in preparation of acrylic acid by catalytic gas-phase oxidation of acrolein in the presence of molecular oxygen or a molecular oxygen-containing gas, using single kind of atalyst, to suppress occurrence of localized extraordinarily high temperature spots (hot spots) in the catalyst layer and can stably maintain high acrolein or acrylic acid yield for a long time. The process is characterized by use of an oxide catalyst containing molybdenum as an essential component and having relative standard deviation of its particle size in a range of 0.02 to 0.20.Type: ApplicationFiled: March 28, 2008Publication date: October 2, 2008Inventor: Naohiro Fukumoto
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Patent number: 6639114Abstract: Ethylenically unsaturated compounds are hydroformylated in the presence of a hydroformylation catalyst comprising at least one complex of a metal of transition group VIII with at least one phosphorus-containing compound as ligand, where this compound contains two groups which contain P atoms and are bound to a molecular skeleton derived from bisphenol A.Type: GrantFiled: February 13, 2002Date of Patent: October 28, 2003Assignee: BASF AktiengesellschaftInventors: Wolfgang Ahlers, Rocco Paciello, Dieter Vogt, Jarl Ivar van der Vlugt
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Patent number: 6632965Abstract: 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: GrantFiled: August 4, 2000Date of Patent: October 14, 2003Assignee: Nippon Shokubai Co. Ltd.Inventors: Michio Tanimoto, Hiromi Yunoki, Hideyuki Hironaka, Naomasa Kimura
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Patent number: 6620973Abstract: 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: GrantFiled: October 19, 2001Date of Patent: September 16, 2003Assignee: Saudi Basic Industries CorporationInventors: Khalid Karim, Yajnavalkya Subrai Bhat, Syed Irshad Zaheer, Asad Ahmad Khan
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Patent number: 6509508Abstract: 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: GrantFiled: February 14, 2002Date of Patent: January 21, 2003Assignee: Nippon Shoku Bai Co LtdInventors: Naomasa Kimura, Michio Tanimoto, Hideo Onodera
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Patent number: 6506944Abstract: C6 compounds of the formula (I) E—CH2—CH═CH—CH2—E1 (I) are prepared by self metathesis or cross metathesis of compounds of the formulae (II) and/or (III) R—CH═CH—CH2—E (II) R1—CH═CH—CH2—E1 (III) where E, E1 are independently —CHO, —COOH, —COOR2, —C(O)NR3R4, —CN, R, R1 are independently H, C1-12-alkyl, C6-12-aryl or C7-13-alkylaryl and R2, R3, R4 are independently H, C1-12-alkyl, C7-13-aralkyl, in the presence of a homogeneous catalyst comprising ruthenium compounds or ruthenium complexes.Type: GrantFiled: February 17, 2000Date of Patent: January 14, 2003Assignee: BASF AktiengesellschaftInventors: Peter Schwab, Michael Schulz
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Patent number: 6486357Abstract: A method of oxidizing an organic alcohol, wherein the organic alcohol is contacted with a stoichiometric excess of oxygen in the presence of an effective catalytic amount of a maganese-containing octahedral molecular sieve or octahedral layer. Primary alcohols are selectively oxidized to aldehydes, and secondary alcohols are selectively oxidized to ketones.Type: GrantFiled: August 14, 2001Date of Patent: November 26, 2002Assignee: The University of ConnecticutInventors: Steven L. Suib, Young Chan Son, Amy R. Howell
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Patent number: 6437193Abstract: 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: GrantFiled: April 6, 2000Date of Patent: August 20, 2002Assignees: E. I. du Pont de Nemours and Company, AtofinaInventors: Rashmikant Maganlal Contractor, Mark William Andersen, Daniel Campos, Gerard Hecquet, Roland Kotwica, Charlotte Pham, Michel Simon, Mireille Stojanovic
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Patent number: 6410785Abstract: 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: GrantFiled: July 18, 2001Date of Patent: June 25, 2002Assignee: BASF AktiengesellschaftInventors: Peter Zehner, Otto Machhammer, Heiko Arnold, Klaus Joachim Müller-Engel
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Patent number: 6410800Abstract: 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: GrantFiled: September 29, 2000Date of Patent: June 25, 2002Assignee: Korea Research Institute of Chemical TechnologyInventors: Tae Sun Chang, Deug Hee Cho, Dong Koo Lee
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Patent number: 6395936Abstract: In a process for the catalytic gas-phase oxidation of propene to acrolein, the reaction gas starting mixture is passed with a propene loading of ≧160 l(S.T.P.)/l·h over a fixed-bed catalyst which is housed in two spatially successive reaction zones A,B, the reaction zone B being kept at a higher temperature than the reaction zone A.Type: GrantFiled: September 10, 2001Date of Patent: May 28, 2002Assignee: BASF AktiengesellschaftInventors: Heiko Arnold, Signe Unverricht, Ulrich Hammon, Hans-Peter Neumann, Klaus Harth, Andreas Tenten
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Patent number: 6346646Abstract: 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: GrantFiled: January 27, 2000Date of Patent: February 12, 2002Assignee: Mitsubishi Rayon Co., Ltd.Inventors: Seigo Watanabe, Motomu Oh-Kita
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Patent number: 6337424Abstract: 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: GrantFiled: April 28, 2000Date of Patent: January 8, 2002Assignee: Saudi Basic Industries CorporationInventors: Khalid Karim, Yajnavalkya Subrai Bhat, Syed Irshad Zaheer, Asad Ahmad Khan
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Patent number: 5583086Abstract: 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: GrantFiled: February 25, 1994Date of Patent: December 10, 1996Assignee: BASF AktiengesellschaftInventors: Andreas Tenten, Hans-Peter Neumann, Herbert Exner
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Patent number: 5491258Abstract: 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: GrantFiled: September 12, 1994Date of Patent: February 13, 1996Assignee: Mitsubishi Rayon Co., Ltd.Inventors: Seigo Watanabe, Motomu Ohkita
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Patent number: 5449821Abstract: A process for the gas phase catalytic oxidation of a C.sub.3-6 alkane, alkanol, alkene or alkenal using as a catalyst multimetal oxide compositions of the formula I, [X.sup.1.sub.a X.sup.2.sub.b O.sub.x ].sub.p [X.sup.3.sub.c X.sup.4.sub.d X.sup.5.sub.e X.sup.6.sub.f X.sup.7.sub.g X.sup.2.sub.h O.sub.y ].sub.q, where X.sup.1 is bismuth, tellurium, antimony, tin and/or copper, X.sup.2 is molybdenum and/or tungsten, X.sup.3 is an alkali metal, thallium and/or samarium, X.sup.4 is an alkaline earth metal, nickel, cobalt, copper, manganose, zinc, tin, cadmium and/or mercury, X.sup.6 is iron, chromium, cerium and/or vanadium, X.sup.6 is phosphorus, arsenic, boron and/or antimony, X.sup.7 is a rare-earth metal, titanium, zirconium, niobium, tantalum, rhenium, ruthenium, rhodium, silver, gold, aluminum, gallium, indium, silicon, geranium, lead, thorium and/or uranium, a is from 0.01 to 8, b is from 0.Type: GrantFiled: June 30, 1994Date of Patent: September 12, 1995Assignee: BASF AktiengesellschaftInventors: Hans-Peter Neumann, Hans Martan, Hermann Petersen, Walter Doerflinger
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Patent number: 5436356Abstract: A process for the carbonylation of ethylenically unsaturated compounds by reaction with carbon monoxide and a co-reactant in the presence of a substantially non-acidic catalyst system based on a palladium compound and a bidentate ligand of the formulaR.sub.1 R.sub.2 M.sub.1 RM.sub.2 R.sub.3 R.sub.4in which M.sub.1 and M.sub.2 may be phosphorus, arsenic or antimony atom, R is a bivalent organic bridging group, R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are independently substituted or non-substituted aliphatic groups, with the proviso that R.sub.1 together with R.sub.2, and/or R.sub.3 together with R.sub.4 form a bivalent cyclic group with at least 5 ring atoms whereby the two free valencies are linked to M.sub.1 or M.sub.2, respectively.Catalytic compositions employing the bidentate ligands used in this method in which M.sub.1 and M.sub.2 are phosphorous are also presented.Type: GrantFiled: January 14, 1994Date of Patent: July 25, 1995Assignee: Shell Oil CompanyInventors: Eit Drent, Dennis H. L. Pello, Melis Hasselaar
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Patent number: 5349092Abstract: Disclosed is a process for producing a multicomponent catalyst containing molybdenum and bismuth and used for synthesis of unsaturated aldehydes and unsaturated carboxylic acids, characterized in that dried starting materials for the catalyst are calcinated in an atmosphere containing 1 vol % or more of a nitrogen oxide and 0.5 vol % or more of oxygen.Type: GrantFiled: February 25, 1993Date of Patent: September 20, 1994Assignee: Mitsubishi Rayon Co., Ltd.Inventors: Seigo Watanabe, Motomu Oh-Kita
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Patent number: 5300707Abstract: Catalyst compositions well adopted for the oxidation of olefins into .alpha.,.beta.-unsaturated aldehydes, e.g., for the oxidation of propylene into acrolein, comprise a particulate support substrate uniformly coated with 15% to 33% by weight of an adherent layer of a catalytically active phase, such support substrate comprising inert and solid spheres having a diameter ranging from 0.5 to 6 mm, such catalytically active phase comprising a catalytically effective amount of bismuth and iron molybdate, dopant amounts of phosphorus and potassium and, optionally, at least one other catalytically active metal or non-metal, and the phosphorus and the potassium each being present in such catalytically active phase in an atomic quantity ranging from 0.005 to 0.06 per 12 atoms of molybdenum, or of molybdenum plus any tungsten therein.Type: GrantFiled: March 9, 1993Date of Patent: April 5, 1994Assignee: Rhone-Poulenc ChimieInventors: Jack Caillod, Philippe Jaeger, Olivier Legendre
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Patent number: 5225389Abstract: Catalyst compositions well adopted for the oxidation of olefins into .alpha.,.beta.-unsaturated aldehydes, e.g., for the oxidation of propylene into acrolein, comprise a particulate support substrate uniformly coated with 15% to 33% by weight of an adherent layer of a catalytically active phase, such support substrate comprising inert and solid spheres having a diameter ranging from 0.5 to 6 mm, such catalytically active phase comprising a catalytically effective amount of bismuth and iron molybdate, dopant amounts of phosphorus and potassium and, optionally, at least one other catalytically active metal or non-metal, and the phosphorus and the potassium each being present in such catalytically active phase in an atomic quantity ranging from 0.005 to 0.06 per 12 atoms of molybdenum, or of molybdenum plus any tungsten therein.Type: GrantFiled: December 20, 1991Date of Patent: July 6, 1993Assignee: Rhone-Poulenc ChimieInventors: Jack Caillod, Philippe Jaeger, Olivier Legendre
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Patent number: 5183936Abstract: 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: GrantFiled: October 25, 1991Date of Patent: February 2, 1993Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: William G. Etzkorn, Gordon G. Harkreader
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Patent number: 5144090Abstract: 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: GrantFiled: June 6, 1991Date of Patent: September 1, 1992Assignee: Mitsui Toatsu Chemicals, IncorporatedInventors: Tadatoshi Honda, Tokio Nagayama, Nobuhiko Horiuchi, Jun Kitagawa, Kazunori Kawahara, Masami Murakami
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Patent number: 4837360Abstract: 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: GrantFiled: September 23, 1982Date of Patent: June 6, 1989Assignee: Mitsubishi Petrochemical Company Ltd.Inventors: Koju Kadowaki, Kohei Sarumaru, Takeshi Shibano
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Patent number: 4709070Abstract: 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: GrantFiled: November 9, 1984Date of Patent: November 24, 1987Assignee: Nitto Chemical Industry Co., Ltd.Inventors: Yutaka Sasaki, Yutaka Kiyomiya, Toshio Nakamura
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Patent number: 4622424Abstract: 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: GrantFiled: September 6, 1985Date of Patent: November 11, 1986Assignee: The Standard Oil CompanyInventors: James L. Callahan, Arthur F. Miller, Wilfrid G. Shaw
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Patent number: 4604370Abstract: A process for regenerating a Mo.Bi-based multi-oxide catalyst the catalytic performance of which has deteriorated as a result of its use in vapor-phase catalytic oxidation of propylene or isobutene to prepare acrolein or methacrolein, respectively, which process comprises: heating the deteriorated Mo.Bi-based multi-oxide catalyst in an atmosphere consisting essentially of air at a temperature of 380.degree. C. to 540.degree. C., so as to attain at least partial restoration of the catalytic performance thereof.Type: GrantFiled: July 9, 1985Date of Patent: August 5, 1986Assignee: Mitsubishi Petrochemical Company, LimitedInventors: Kohei Sarumaru, Takeshi Shibano, Yoichi Ishii, Etsuji Yamamoto
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Patent number: 4564703Abstract: In a process for preparing methacrylic acid by the vapor-phase catalytic oxidation of methacrolein or a methacrolein-containing mixture with molecular oxygen in the presence of an oxidation catalyst; the improvement wherein said process comprisesa first-stage oxidation step of oxidizing methacrolein or a methacrolein-containing mixture as a starting material,a first-stage separating step of separating the resulting methacrylic acid from the reaction product obtained in the first-stage oxidation step,a second-stage oxidation step of oxidizing the mixture containing the unreacted methacrolein and obtained in the first-stage separating step, anda second-stage separating step of separating the resulting methacrylic acid from the reaction product obtained in the second-stage oxidation step, andwith or without at least one additional oxidation step and separating step subsequent to the second-stage separating step,and wherein the conversion of methacrolein in the first-stage oxidation step is adjusted to 30-85 moleType: GrantFiled: April 16, 1979Date of Patent: January 14, 1986Assignee: Nippon Zeon Co., Ltd.Inventors: Haruhisa Yamamoto, Shinichi Akiyama
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Patent number: 4556731Abstract: Iron-bismuth-molybdate catalysts further containing specific promoter elements have been found to exhibit excellent redox stability even under high stress conditions in the catalytic oxidation of olefins to unsaturated aldehydes and acids.Type: GrantFiled: April 19, 1982Date of Patent: December 3, 1985Assignee: The Standard Oil CompanyInventors: Andrew T. Guttmann, Robert K. Grasselli
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Patent number: 4473506Abstract: Oxide complex catalysts of iron, selenium and tellurium provide good yields of acrylonitrile in the ammoxidation of propylene with high selectivities at low temperature.Type: GrantFiled: October 18, 1982Date of Patent: September 25, 1984Assignee: The Standard Oil CompanyInventors: James D. Burrington, James F. Brazdil, Robert K. Grasselli
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Patent number: 4453006Abstract: 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: GrantFiled: February 12, 1981Date of Patent: June 5, 1984Assignee: The Standard Oil CompanyInventors: Wilfrid G. Shaw, Christos Paparizos, James L. Callahan
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Patent number: 4442308Abstract: A process is disclosed for preparing acrolein from propylene and methacrolein from isobutylene or tertiary butanol, by oxidation in oxygen-containing gas mixtures on specially prepared coated catalysts comprised of an inert support and a coating, enclosing this support, of an oxidic catalyst material containing the elements nickel, cobalt, iron, bismuth, phosphorus, molybdenum and tantalum or samarium and, if appropriate, also alkali metal or alkaline earth metal in certain atomic ratios. This coated catalyst is obtained by spraying a suspension of the starting material for the coating, which suspension contains a binder and, if appropriate, a pore-former, from above in an increasing amount onto a bed of the support, which bed is mechanically agitated and loosened up by a gas stream blow in from below, the ratio between suspending medium sprayed on and removed again by the gas stream remaining approximately constant.Type: GrantFiled: June 21, 1982Date of Patent: April 10, 1984Assignee: Degussa AktiengesellschaftInventors: Dietrich Arntz, Gunter Prescher, Johannes Heilos
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Patent number: 4424141Abstract: Bismuth molybdate catalysts formed from a precatalyst slurry which uses an organic liquid or mixture of an organic liquid and water as the liquid medium of the slurry exhibit superior catalytic properties.Type: GrantFiled: January 5, 1981Date of Patent: January 3, 1984Assignee: The Standard Oil Co.Inventors: Robert K. Grasselli, Dev D. Suresh, Maria S. Friedrich
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Patent number: 4404397Abstract: 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: GrantFiled: December 29, 1980Date of Patent: September 13, 1983Assignee: Air Products and Chemicals, Inc.Inventor: Chelliah Daniel
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Patent number: 4335056Abstract: In the recovery of acrylonitrile from the gross reaction product produced during the commercial ammoxidation of propylene to produce acrylonitrile, an ammoxidation waste gas containing at least 65% nitrogen, carbon dioxide, carbon monoxide and a small amount of unreacted propylene is produced. In accordance with the invention, this ammoxidation waste gas is passed through a catalytic converter containing an oxidation or ammoxidation catalyst to convert the unreacted propylene into valuable product.Type: GrantFiled: January 5, 1981Date of Patent: June 15, 1982Assignee: Standard Oil CompanyInventors: James L. Callahan, Wilfrid G. Shaw, David B. Terrill
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Patent number: 4332971Abstract: Olefin oxidation catalysts having improved attrition resistance are produced by incorporating a substantially uniform-appearing coating of a partially calcined catalytic material onto an inert porous support containing sorbed aqueous silica sol and then completing the calcination of the catalyst. Such catalysts are useful in a variety of exothermic chemical processes, including vapor phase oxidation of olefinically unsaturated hydrocarbons to the corresponding unsaturated aldehydes, especially propylene to acrolein.Type: GrantFiled: December 15, 1980Date of Patent: June 1, 1982Assignee: Celanese CorporationInventors: Charles A. Dalton, William E. Slinkard
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Patent number: 4323520Abstract: The present invention relates to a process for the conversion of tertiary-butyl-containing compounds to methacrylic derivatives, and more particularly to a process for the conversion of tertiary-butyl-containing compounds selected from the group consisting of alkyl tertiary-butyl ethers, tertiary-butyl alcohol, isobutylene dimer (2,2,4-trimethylpentene) and isobutylene trimer, to methacrolein, methacrylic acid or methacrylonitrile.Type: GrantFiled: May 9, 1977Date of Patent: April 6, 1982Assignee: The Standard Oil Co.Inventors: Harley F. Hardman, James L. Callahan, Robert K. Grasselli
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Patent number: 4323703Abstract: The process comprises the vapor phase oxidation of lower molecular weight olefins to the corresponding unsaturated aldehydes and unsaturated carboxylic acids in the presence of a catalyst comprising the oxides of iron, bismuth, molybdenum and at least one element of the Group II elements as essential components, and optionally the oxides of phosphorus, arsenic and an alkali metal.Type: GrantFiled: May 26, 1977Date of Patent: April 6, 1982Assignee: Standard Oil CompanyInventors: Robert K. Grasselli, Arthur F. Miller, Harley F. Hardman
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Patent number: 4306088Abstract: In the production of methacrolein by vapor phase catalytic oxidation of isobutylene and/or t-butyl alcohol, an improved process for suppressing the amount of acetone to be by-produced which comprises contacting a gaseous mixture comprising isobutylene or t-butyl alcohol, molecular oxygen and steam with a metal oxide catalyst composition comprising molybdenum and bismuth as the essential metal components, the amount of steam in the gaseous mixture being kept to be not more than 4 mol per mol of isobutylene or not more than 3 mol per mol of t-butyl alcohol.Type: GrantFiled: June 25, 1980Date of Patent: December 15, 1981Assignee: Sumitomo Chemical Company, LimitedInventors: Shuzo Nakamura, Hiroshi Ichihashi, Yoshihiko Nagaoka, Koichi Nagai
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Patent number: 4306090Abstract: Methacrolein is produced by the catalytic vapor phase oxidation of isobutylene (including compounds converted to isobutylene). The catalyst has the following formula: Mo.sub.a P.sub.b Fe.sub.c Co.sub.d Ni.sub.e Bi.sub.f Te.sub.g Sb.sub.h Cs.sub.i Zr.sub.j X.sub.k O.sub.x wherein a-k represent the number of atoms of the particular element depicted, X is another element and x is the number of oxygens present.Type: GrantFiled: August 29, 1980Date of Patent: December 15, 1981Assignee: Rohm and Haas CompanyInventors: Lawrence S. Kirch, William J. Kennelly
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Patent number: 4298763Abstract: Acrolein and methacrolein are prepared advantageously by oxidizing propylene or isobutylene, respectively, with an oxygen-containing gas mixture under conventional conditions over a supported catalyst possessing a firmly adhering coating, from 150 to 1,500 .mu.m thick, which contains calcined catalytic material based on molybdenum oxide and has a carrier core with a surface area of less than 15 m.sup.2 /g and a diameter of more than 100 .mu.m, if a coated catalyst is used which has been prepared by applying calcined catalytic material having a particle size of from 0.1 to 300 .mu.m, in an amount of from 1 to 40 g/min/liter of carrier and water in a weight ratio of catalytic material to water of from 1:1 to 8:1, continuously and separately from one another, each at a constant speed, at below 100.degree. C.Type: GrantFiled: March 3, 1980Date of Patent: November 3, 1981Assignee: BASF AktiengesellschaftInventors: Heinz Engelbach, Richard Krabetz, Gerd Duembgen, Carl-Heinz Willersinn, Walter Beitelschmidt
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Patent number: 4267386Abstract: This invention provides an improved catalyst for vapor phase oxidation of propylene or isobutylene to the corresponding acrolein or methacrolein product. In a preferred embodiment, the oxidation catalyst corresponds to the formula:Mo.sub.12 Co.sub.4-5 Fe.sub.2-4 Ni.sub.2-3 Bi.sub.0.5-2 K.sub.0.65-1.3 P.sub.0.35-0.5 O.sub.xThis invention further provides a method of preparing the improved oxidation catalyst which in one important aspect of the preparation involves controlling the pH of an aqueous slurry admixture of catalyst components within the range of about 1-5.Type: GrantFiled: September 19, 1979Date of Patent: May 12, 1981Assignee: Celanese CorporationInventor: Thomas H. Vanderspurt
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Patent number: 4224187Abstract: This invention provides an improved catalyst for vapor phase oxidation of propylene or isobutylene to the corresponding acrolein or methacrolein product. In a preferred embodiment, the oxidation catalyst corresponds to the formula:Mo.sub.12 Co.sub.4-5 Fe.sub.2-4 Ni.sub.2-3 Bi.sub.0.5-2 K.sub.0.65-1.3 P.sub.0.35-0.5 O.sub.xThis formula further provides a method of preparing the improved oxidation catalyst which in one important aspect of the preparation involves controlling the pH of an aqueous slurry admixture of catalyst components within the range of about 1-5.Type: GrantFiled: November 13, 1978Date of Patent: September 23, 1980Assignee: Celanese CorporationInventor: Thomas H. Vanderspurt
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Patent number: 4203906Abstract: A process for catalytic vapor phase oxidation which comprises using a fixed-bed shell and tube heat exchange type reactor in which a bundle of a multiplicity of tubes filled with at least one type of oxidizing catalyst are disposed in a shell and these tubes are passed through the apertures formed in at least one perforated shield plate to partition the inside of the shell into at least two heat transfer medium feed zones and in such a manner that each of the tubes passing through the perforated shield plate is not in direct contaction with the shield plate but the outer surface of the tube and the inner surface of the aperture are spaced apart by a distance of between 0.2-5 mm, supplying feed gas to the tubes of the reactor, and conducting exothermic catalytic vapor phase oxidation while controlling the temperatures for the heat transfer medium in each of the zones so that the temperature difference between each of the zones can be maintained between 0.degree.-100.degree. C.Type: GrantFiled: July 7, 1978Date of Patent: May 20, 1980Assignee: Nippon Shokubai Kagaku Kogyo Co., Ltd.Inventors: Masahiro Takada, Hiroyuki Uhara, Takahisa Sato
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Patent number: RE32484Abstract: 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: GrantFiled: September 2, 1983Date of Patent: August 25, 1987Assignee: The Standard Oil CompanyInventors: Robert K. Grasselli, Harley F. Hardman