Group Viii Metal With Additional Nonhydrocarbon Agent Or Complexed With Hydrocarbon Patents (Class 585/277)
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Patent number: 5648577Abstract: The present invention is directed toward a catalyst composition prepared by a process comprising: (a) impregnating an oxide precursor selected from the group consisting of rare earth oxide precursors, yttria precursors and mixtures thereof, onto an inorganic refractory oxide support; (b) drying said support at a temperature of about 100.degree. to about 120.degree. C. followed by calcining said support at a temperature of about 400.degree. to about 600.degree. C.; and (c) compositing or depositing on said support of step (b), a catalyst precursor salt represented by (ML)(Mo.sub.y W.sub.1-y O.sub.4).sub.a wherein M comprises Cr and/or one or more divalent promoter metals selected from the group consisting of Mn, Fe, Co, Ni, Cu, Zn and mixtures thereof, wherein y is any value ranging from 0 to 1, and wherein L is one or more neutral, nitrogen-containing ligands at least one of which is a chelating polydentate ligand; a=1 when chromium is not one of the promoter metals and 0.5.ltoreq.a.ltoreq.Type: GrantFiled: June 2, 1995Date of Patent: July 15, 1997Assignee: Exxon Research and Engineering CompanyInventors: Teh Chung Ho, Stuart Leon Soled, Sabato Miseo, Gary Brice McVicker, Michel Daage, Viktor Buchholz
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Patent number: 5639927Abstract: A process of producing cycloolefin, comprises the step of subjecting a monocyclic aromatic hydrocarbon to partial hydrogenation reaction in the presence of water and a ternary catalyst containing (a) ruthenium, (b) zinc and (c) at least one selected from the group consisting of gold, silver and copper.Type: GrantFiled: December 18, 1995Date of Patent: June 17, 1997Assignee: Mitsubishi Chemical CorporationInventors: Toshiyuki Suzuki, Tatsuya Ezaki
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Patent number: 5627293Abstract: The invention relates to ferrocenyldiphosphine ligands containing a silylene group, ferrocenyldiphosphines bound to inorganic or polymeric organic supports by this silylene group, their preparation and also their metal complexes with transition metals such as rhodium or iridium. The invention also relates to the use of these complexes for hydrogenating organic double or triple bonds, in particular olefinic double bonds and carbon-heteroatom double bonds. The complexes are particularly suitable for enantioselective hydrogenation using chiral diphosphines and prochiral unsaturated compounds.The preparation of these immobilized ferrocenyldiphosphines has only been made possible by the provision of correspondingly functionalized ferrocenyldiphosphines. These compounds and their preparation are likewise novel.Accordingly, the invention also provides compounds of the formula I ##STR1## in which R.sub.1 is C.sub.1 -C.sub.8 alkyl, phenyl or phenyl substituted by from 1 to 3 C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.Type: GrantFiled: February 23, 1996Date of Patent: May 6, 1997Assignee: Ciba-Geigy CorporationInventor: Benoit Pugin
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Patent number: 5587348Abstract: A catalyst composition comprises palladium, at least one chemically bound alkali metal (preferably potassium), chemically bound fluorine and an inorganic support material (preferably alumina), wherein the atomic ratio of fluorine to alkali metals about 1.3:1 to about 4:1. Preferably, silver is also present in the catalyst composition. The above-described catalyst is employed as a catalyst in the selective hydrogenation of C.sub.2 -C.sub.10 alkynes (preferably acetylene) to the corresponding alkenes in the presence of sulfur impurities.Type: GrantFiled: April 19, 1995Date of Patent: December 24, 1996Assignee: Phillips Petroleum CompanyInventors: Scott H. Brown, Stan A. Zisman, James B. Kimble
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Patent number: 5583274Abstract: C.sub.2 -C.sub.6 alkynes (preferably acetylene) contained in feeds which also contain sulfur impurities are hydrogenated to the corresponding alkenes in the presence of a supported palladium catalyst which has been promoted with alkali metal fluoride (preferably potassium fluoride).Type: GrantFiled: January 20, 1995Date of Patent: December 10, 1996Assignee: Phillips Petroleum CompanyInventors: Tin-Tack P. Cheung, Marvin M. Johnson
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Patent number: 5569803Abstract: A method for producing a cycloolefin, which comprises partially hydrogenating a monocyclic aromatic hydrocarbon in the presence of water and a ruthenium catalyst supported on silica modified by zirconium oxide.Type: GrantFiled: December 23, 1994Date of Patent: October 29, 1996Assignee: Mitsubishi Chemical CorporationInventors: Takahiko Takewaki, Naoko Fujita, Toshiharu Yokoyama, Takao Maki
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Patent number: 5563308Abstract: Compounds of formula I ##STR1## wherein R.sub.1 is C.sub.1 -C.sub.8 alkyl, phenyl or phenyl which is substituted by 1 to 3 C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy groups; R.sub.2 and R.sub.3 are each independently of the other typically C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, phenyl, or C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl, or phenyl which is substituted by one to three identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or halogen;R.sub.10 and R.sub.11 are identical and are typically C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl or phenyl which is substituted by 1 to 3 identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or halogen; or R.sub.10 and R.sub.11 are different and are C.sub.1 -C.sub.Type: GrantFiled: June 5, 1995Date of Patent: October 8, 1996Assignee: Ciba-Geigy CorporationInventors: Felix Spindler, Amina Wirth-Tijani, Heidi Landert
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Patent number: 5563309Abstract: Compounds of formula I ##STR1## wherein R.sub.1 is C.sub.1 -C.sub.8 alkyl, phenyl or phenyl which is substituted by 1 to 3 C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy groups; R.sub.2 and R.sub.3 are identical and are C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl or C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl, or phenyl which is substituted by one to three identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy,--SiR.sub.4 R.sub.5 R.sub.6, halogen, --SO.sub.3 M,--CO.sub.2 M,--PO.sub.3 M,--NR.sub.7 R.sub.8 and --[.sup..sym. NR.sub.7 R.sub.8 R.sub.9 ]X.sup..crclbar. ; or R.sub.1 and R.sub.3 are different and are C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl, phenyl or phenyl which is substituted by one to three identical or different members selected from the group consisting of C.sub.1 -C.Type: GrantFiled: June 2, 1995Date of Patent: October 8, 1996Assignee: Ciba-Geigy CorporationInventors: Antonio Togni, Felix Spindler, Nadia Zanetti, Amina Tijani
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Patent number: 5545784Abstract: Molecular sieves are modified by an ion exchange process where metal cations are introduced into the molecular sieves by means of solid state ion exchange. The solid state ion exchange can be carried out as follows: a weighed amount of calcined and activated zeolite is intimately mixed with a precalculated amount of PtCl.sub.2, PdCl.sub.2, RhCl.sub.3, CuCl.sub.2, V.sub.2 O.sub.5 or another compound of the noble metals (e.g., corresponding halides or oxides), the solids mixture is then heated in a current of inert gas (e.g., a current of helium gas or of nitrogen) to temperatures of 400.degree. to 600.degree. C., then cooled down to room temperature and subsequently reduced in a current of hydrogen for 10 to 14 hours at 280.degree. to 350.degree. C. in order to produce small metal clusters from the cationically introduced metal.Type: GrantFiled: April 11, 1995Date of Patent: August 13, 1996Assignee: Degussa AktiengesellschaftInventors: Jens Weitkamp, Stefan Ernst, Thomas Bock, Thomas Kromminga, Akos Kiss, Peter Kleinschmit
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Patent number: 5510503Abstract: The invention relates to novel enantiomerically pure bisphosphines of the general formula (I) ##STR1## in which R, R.sup.1 and R.sup.2 have the meanings given in the description, a process for the preparation thereof and the use thereof in metal complexes as catalysts for asymmetric hydrogenations.Type: GrantFiled: September 2, 1994Date of Patent: April 23, 1996Assignee: Bayer AktiengesellschaftInventors: Christian Laue, Georg Schroder, Dieter Arlt, Rolf Grosser
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Patent number: 5498584Abstract: Disclosed in a process for the homogeneous, catalytic hydrogenation of epoxyalkenes and epoxycyclo-alkenes, especially conjugated .gamma.,.delta.-epoxyalkenes and epoxycycloalkenes, to the corresponding epoxyalkanes and epoxycycloalkanes using a solution of a complex rhodium catalyst whereby the olefinic unsaturation is hydrogenated without significant hydrogenolysis of the conjugated epoxy group.Type: GrantFiled: September 23, 1994Date of Patent: March 12, 1996Assignee: Eastman Chemical CompanyInventor: Thomas A. Puckette
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Patent number: 5457251Abstract: Disclosed is a method for partially hydrogenating a monocyclic aromatic hydrocarbon to produce a cycloolefin, comprising reacting a monocyclic aromatic hydrocarbon with hydrogen in the presence of a particulate hydrogenation catalyst comprised mainly of metallic ruthenium, in a reaction system comprising a continuous aqueous phase having the particulate hydrogenation catalyst suspended therein, an oil phase containing the monocyclic aromatic hydrocarbon, and a gaseous phase comprising hydrogen gas, while applying a shearing force to the reaction system at a specific maximum shear rate. By the method of the present invention, not only can a cycloolefin be produced at high selectivity and in high yield, but also the catalytic activity can be stably maintained at a high level for a prolonged period of time.Type: GrantFiled: January 21, 1993Date of Patent: October 10, 1995Assignee: Asahi Kasei Kogyo Kabushiki KaishaInventors: Kunihiko Yamashita, Hideaki Obana, Issei Katsuta
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Patent number: 5417844Abstract: The invention relates to a process for the selective hydrogenation of diolefins in steam cracking petrol in the presence of a nickel catalyst and is characterized in that prior to the use of the catalyst, a suphur-containing organic compound is incorporated into the catalyst outside of the reactor.Type: GrantFiled: November 18, 1992Date of Patent: May 23, 1995Assignee: Institut Francais du PetroleInventors: Jean-Paul Boitiaux, Patrick Sarrazin
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Patent number: 5414170Abstract: The present invention provides an improved process for selectively hydrogenating acetylenes in an olefin plant process stream by selectively hydrogenating the acetylenes downstream of a front end depropanizer and upstream of further separation zones such as a demethanizer and/or de-ethanizer.Type: GrantFiled: May 12, 1993Date of Patent: May 9, 1995Assignee: Stone & Webster Engineering CorporationInventors: Richard H. McCue, Edna B. Hicks
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Patent number: 5406012Abstract: A composition comprising a crystalline aluminumphosphate material having a three-dimensional microporous crystal framework structure whose chemical composition expressed in terms of mole ratios of oxides isAl.sub.2 O.sub.3 : 1.0.+-.0.2 P.sub.2 O.sub.5 ;and which is further defined as having an x-ray powder diffraction pattern characterized by d spacings at less than about 40 degrees two-theta as measured using copper K-alpha radiation that are substantially as shown in the Table and a metal in an amount of up to about 25 percent by weight is disclosed. The composition can be prepared by impregnating the crystalline aluminumphosphate material with the metal in an amount of up to about 25 percent by weight. The resultant heterocatalyst system can be used to shape-selectively hydrogenate an unsaturated organic compound, such as, for example an olefin, aldehyde or ketone.Type: GrantFiled: May 23, 1989Date of Patent: April 11, 1995Assignee: The Dow Chemical CompanyInventor: Mark E. Davis
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Patent number: 5382729Abstract: Compounds of formula I ##STR1## wherein R.sub.1 denotes identical or different radicals and is linear or branched C.sub.1 -C.sub.12 alkyl, unsubstituted C.sub.5 -C.sub.6 cycloalkyl or C.sub.5 -C.sub.6 cycloalkyl which is substituted by C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy, or is phenyl or benzyl, or both substituents R.sub.1 of a group (R.sub.1).sub.2 P are o,o-diphenylene, R.sub.2 is hydrogen, linear or branched C.sub.1 -C.sub.12 alkyl, phenyl or benzyl, R.sub.3 is C.sub.1 -C.sub.12 alkylene, R.sub.4 is C.sub.2 -C.sub.18 alkylene, phenylene or benzylene, and R.sub.5 is C.sub.1 -C.sub.6 alkyl or phenyl, can be applied to solid carriers, such as silica gel or aerosils, and complexed with rhodium or iridium compounds. These materials are heterogeneous and separable catalysts for the assymetrical hydrogenation of prochiral compounds containing carbon double bonds or carbon/hetero atom double bonds, for example ketones and imines.Type: GrantFiled: February 16, 1994Date of Patent: January 17, 1995Assignee: Ciba-Geigy CorporationInventors: Benoit Pugin, Felix Spindler, Manfred Muller
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Patent number: 5378767Abstract: A method for hydrogenating unsaturated low molecular weight polymers, preferably polydiene monool, diol and polyol polymers, which comprises contacting the polymers under hydrogenation conditions with hydrogen in the presence of a fixed bed heterogeneous catalyst which is comprised of platinum, palladium or a mixture of the two supported on an alpha alumina support.Type: GrantFiled: June 18, 1993Date of Patent: January 3, 1995Assignee: Shell Oil CompanyInventor: Stephen N. Massie
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Patent number: 5347027Abstract: The present invention provides an electroless process for making a catalyst in a liquid or gaseous medium comprising contacting a base metal with a chemical cleaning agent and simultaneously or sequentially treating said base metal under reducing conditions with a noble metal-containing material, the catalyst prepared using the process, and a method of using the catalyst.Type: GrantFiled: April 22, 1993Date of Patent: September 13, 1994Assignee: OSi Specialties, Inc.Inventors: James S. Ritscher, Wei T. Yang, George M. Omietanski, Robert L. Ocheltree, Earl E. Malson
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Patent number: 5334791Abstract: A process is provided for hydrogenating a non-aromatic unsaturated hydrocarbon, comprising reacting the hydrocarbon with a catalyst precursor which includes a source of a group VIIIB transition metal from the second or third rows of the periodic table and a heterobifunctional ligand constructed with a phosphine center and an imine nitrogen center, in the presence of hydrogen and a promoter selected from secondary or tertiary acyclic alkyl amines in a suitable solvent which solubilizes the hydrocarbon, the catalyst precursor, the hydrogen, and the promoter.Type: GrantFiled: May 22, 1992Date of Patent: August 2, 1994Assignee: Ligands Inc.Inventors: Ronald G. Cavell, David J. Law, Robert W. Reed
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Patent number: 5321176Abstract: Hydrogenation of a polyene to a monoene using a ruthenium catalyst that is promoted with water.Type: GrantFiled: December 22, 1992Date of Patent: June 14, 1994Assignee: E. I. Du Pont de Nemours and CompanyInventor: Kathryn M. Sanchez
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Patent number: 5306853Abstract: Compounds of formula II ##STR1## wherein the groups (R.sub.1).sub.2 P(CH.sub.2).sub.m bzw.n are in o- or m-position to each other and the substituents R.sub.1 are identical or different radicals, m and n are each independently of the other 0 or 1, R.sub.1 is linear or branched C.sub.1 -C.sub.12 alkyl, unsubstituted C.sub.5 -C.sub.6 cycloalkyl or C.sub.5 -C.sub.6 cycloalkyl which is substituted by C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy, or is phenyl or benzyl, or both substituents R.sub.1 in a group (R.sub.1).sub.2 P together are o,o'-diphenylene, --R.sub.2 --X-- is a bond or --(C.sub.x H.sub.2x --O).sub.y --, or X-- is O-- and R.sub.2 is C.sub.1 -C.sub.6 alkylene, x is an integer from 2 to 6 and y is an integer from 2 to 6, R.sub.3 is C.sub.2 -C.sub.18 alkylene, phenylene or benzylene, and R.sub.4 is C.sub.1 -C.sub.6 alkyl or phenyl, can be applied to solid carriers, such as silica gel or aerosils, and complexed with rhodium or iridium compounds.Type: GrantFiled: June 17, 1993Date of Patent: April 26, 1994Assignee: Ciba-Geigy CorporationInventors: Benoit Pugin, Manfred Muller, Felix Spindler
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Patent number: 5300716Abstract: A process for the preparation of a polyunsaturated olefinic compound, i.e. undeca-1,3,5-triene, in its (3E,5Z) isomeric form, consisting of four consecutive steps starting from deca-1,4-diyne, is disclosed.Said process has the advantage of making it possible to obtain the desired isomer in its essentially pure form.Type: GrantFiled: September 6, 1991Date of Patent: April 5, 1994Assignee: Firmenich SAInventor: Christian Chapuis
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Patent number: 5268521Abstract: Disclosed herein is a catalyst for especially for selective hydrogenation among a carbon-carbon double bond, a carbonyl group and an aromatic unsaturated ring such as benzene. The catalyst comprising platinum and zeolite can be employed for selectively hydrogenating the carbon-carbon double bond and the carbonyl group of an organic compound without the hydrogenation of the aromatic unsaturated. The catalyst comprising the platinum supported on a support which comprises powders of an inorganic component to which is supported polyethylene glycol or an ethylvinylbenzene-divinylbenzene copolymer can be employed for selectively hydrogenating the carbon-carbon double bond of an organic compound without the hydrogenation of the carbonyl group and the aromatic unsaturated ring.Type: GrantFiled: November 22, 1991Date of Patent: December 7, 1993Assignee: Tanaka Kikinzoku Kogyo K.K.Inventors: Kenji Tamaru, Kikuo Shoji, Kazuki Noda
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Patent number: 5254714Abstract: A process is disclosed for the enantioselective hydrogenation of olefins of the formula: ##STR1## where R is hydrogen or C.sub.1 to C.sub.6 linear or branched alkyl, Z is ##STR2## where R' is hydrogen or C.sub.1 to C.sub.6 linear or branched alkyl, --CN, C(NH)OR" where R" is C.sub.1 to C.sub.6 linear or branched alkyl, or --C(O)NH.sub.2 ; and Ar is phenyl or naphthyl unsubstituted or substituted with benzoyl or substituted benzoyl, C.sub.1 to C.sub.6 linear or branched alkyl, C.sub.1 to C.sub.6 linear or branched alkoxy, halo, or carboxylic acid or C.sub.1 to C.sub.6 linear or branched alkyl ester thereof, which comprises contacting said aromatic-substituted olefin with a catalytically effective amount of a ruthenium phosphite complex.Type: GrantFiled: October 10, 1991Date of Patent: October 19, 1993Assignee: Ethyl CorporationInventor: Merrikh Ramezanian
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Patent number: 5233110Abstract: A process for the preparation of cyclooctene which comprises irradiating 1,5-cyclooctadiene with light in the presence of a photodehydrogenation catalyst, acetone and an alcohol to partially hydrogenate the 1,5-cyclooctadiene.Type: GrantFiled: February 28, 1992Date of Patent: August 3, 1993Assignee: Agency of Industrial Science & TechnologyInventors: Taka-aki Hanaoka, Yoshihiro Sugi, Takehiko Matsuzaki, Kazuhiko Takeuchi, Hironori Arakawa
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Patent number: 5210348Abstract: A substantially benzene-free product suitable for gasoline blending is formed from a benzene-containing refinery stream. At least about 30% of the benzene initially present in the stream is catalytically alkylated with C.sub.2 -C.sub.4 olefins to form alkylated products. Most preferably, the alkylation zone is present in the distillation column and the alkylated products drop to the lower portion of the column and are recovered with the heavy fraction. Alternatively, the alkylation zone is downstream of the distillation column and a secondary distillation column removes the heavier alkylated products. The remaining light fraction is hydrogenated to convert substantially all of the remaining non-alkylated benzene to cyclohexane and is isomerized to boost the octane of C.sub.5 -C.sub.7 paraffins, preferably in a single reactor.Type: GrantFiled: May 23, 1991Date of Patent: May 11, 1993Assignee: Chevron Research and Technology CompanyInventors: C. Richard Hsieh, Richard C. Robinson
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Patent number: 5210349Abstract: Cyclic polyenes are selectively hydrogenated to cyclic monoenes under suitable hydrogenation conditions in the presence of an activated ruthenium catalyst complexes. The ruthenium catalyst complex is activated by hydrogenating a minimal amount of cyclic polyene under suitable hydrogenation conditions.Type: GrantFiled: March 4, 1992Date of Patent: May 11, 1993Assignee: Phillips Petroleum CompanyInventors: Michael S. Matson, Harold J. Swindell
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Patent number: 5189233Abstract: Disclosed is an improvement in a process for production of cyclohexane by liquid phase hydrogenation of benzene wherein no diluent is necessary, which comprises contacting benzene and hydrogen in the presence of a mixed catalyst bed comprising a first catalyst which is a less active hydrogenation catalyst selected from elements of Group VIII of the Periodic Table and a second, more active catalyst, comprising a Group VIII metal supported on an oxide, such as, for example, alumina, silica or titania at a temperature of about 40.degree. C. to about 300.degree. C. and pressure sufficient to keep the benzene liquid at the chosen reaction temperature.Type: GrantFiled: August 23, 1991Date of Patent: February 23, 1993Assignee: Texaco Chemical CompanyInventors: John M. Larkin, James H. Templeton, Donald H. Champion
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Patent number: 5180870Abstract: Hydrogenation of a polyene to a monoene using a ruthenium catalyst that is promoted with a sterically-hindered tertiary amine.Type: GrantFiled: October 23, 1991Date of Patent: January 19, 1993Assignee: E. I. du Pont de Nemours and CompanyInventor: Rocco A. Paciello
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Patent number: 5177278Abstract: Partial hydrogenation of 1,5,9-cyclododecatriene to form cyclododecene using ruthenium catalyst and a solvent selected from the group consisting of esters and ethers having a boiling point higher than 245 degrees C.Type: GrantFiled: October 23, 1991Date of Patent: January 5, 1993Assignee: E. I. Du Pont de Nemours and CompanyInventor: Kathryn M. Sanchez
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Patent number: 5171907Abstract: A cobalt carbonyl phosphine complex useful for hydrogenation of cyclic polyenes to corresponding cyclic monoenes is prepared by reaction of dicobalt carbonyl and a phosphine compound in at least one non-oxygenated aliphatic solvent. Selective hydrogenation of the cyclic polyenes comprises an induction period during which the polyenes are contacted with the cobalt carbonyl complex catlayst under hydrogen pressure followed by decreasing the reaction temperature and pressure for a period of time sufficient to complete the hydrogenation.Type: GrantFiled: July 1, 1991Date of Patent: December 15, 1992Assignee: Phillips Petroleum CompanyInventors: Michael S. Matson, Stan A. Zisman
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Patent number: 5149893Abstract: A catalytic hydrogenation process comprising contacting a catalyst effective to promote a hydrogenation reaction with a feed stream comprising gaseous hydrogen and an unsaturated hydrocarbon thereby hydrogenating at least some of said unsaturated hydrocarbon, said catalyst being prepared from a precursor comprising a calcium aluminate cement and at least one oxide of a metal selected from nickel and cobalt by reduction of said metal oxide, and wherein said precursor contains 10 to 70% by weight of said metal oxide (expressed as the divalent oxide, MO) and has a porosity in the range 25 to 50%, in which at least 30% of the pore volume is in the form of pores of size in the range 15 to 35 nm and less than 40% of the pore volume is in the form of pores of diameter greater than 35 nm.Type: GrantFiled: June 6, 1991Date of Patent: September 22, 1992Assignee: Imperial Chemical Industries PLCInventors: Frank King, Martin E. Fakley
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Patent number: 5138111Abstract: An eta phase composition in powder form, prepared in the absence of sulfur or sulfur bearing compounds, having a surface area greater than about 2m.sup.2 /g and consisting of X.sub.6 Y.sub.6 Z.sub.a wherein X is at least one element selected from the group consiting of Mo and W, Y is at least one element selected from the group consisting of Fe, Co. Ni, Mo and W, Z is at least one element selected from the group consisting of C, N and combinations thereof such that when Z is N, a is greater than or equal to 1 but less than or equal to 2 and when Z is C, a is greater than 1 but less than or equal to 2 except when Z is C and Y is Fe, then a is greater than or equal to 1 but less than or equal to 2. The eta phase may be a carbide, nitride or carbonitride. A method for producing the eta-phase composition includes providing a precursor compound including at least two eta-phase forming metals, and a ligand containing carbon, nitrogen or combinations thereof.Type: GrantFiled: September 16, 1991Date of Patent: August 11, 1992Assignee: Exxon Research and Engineering CompanyInventors: Edwin L. Kugler, Larry E. McCandlish, Allan J. Jacobson, Russell R. Chianelli
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Patent number: 5132270Abstract: Deactivated hydrogenation catalysts of ruthenium metal deposited on an aluminum oxide support are regenerated by treatment with ultrasound.Type: GrantFiled: July 5, 1991Date of Patent: July 21, 1992Assignee: Huels AktiengesellschaftInventors: Gerhard Wachholz, Gerhard Thelen, Heinz-Werner Voges
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Patent number: 5118837Abstract: A modified ruthenium catalyst can be used to selectively hydrogenate an olefinic double bond in the presence of another olefinic double bond in the same or in a different molecule. Modifiers are selected from compounds containing trivalent nitrogen, trivalent phosphorus and divalent sulfur.Type: GrantFiled: February 12, 1987Date of Patent: June 2, 1992Assignee: Givaudan CorporationInventors: Alan J. Chalk, Laszlo V. Wertheimer
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Patent number: 5081083Abstract: Alternate, successive high temperature oxidation and reduction treatments, in either order, of intermetallic alloy hydrogenation and intermetallic alloy oxidation catalysts unexpectedly improves the impurity poisoning resistance, regeneration capacity and/or activity of the catalysts. The particular alloy, and the final high temperature treatment given alloy (oxidation or reduction) will be chosen to correspond to the function of the catalyst (oxidation or hydrogenation).Type: GrantFiled: February 12, 1990Date of Patent: January 14, 1992Assignee: The United States of America as represented by the Secretary of the Department of EnergyInventor: Randy B. Wright
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Patent number: 5072069Abstract: The invention relates to cycloolefinic complexes of platinum, processes for preparing the same from platinum(II) compounds and cyclolefins having at least 12 ring carbon atoms and at least two aliphatic non-cumulated carbon-carbon double bonds and their use as a catalyst for the addition of Si-bonded hydrogen to an aliphatic multiple bond.Type: GrantFiled: February 27, 1990Date of Patent: December 10, 1991Assignee: Consortium Fur Elektrochemische Ind.Inventors: Guido Wenski, Ludwig Maier, Hans-Jurgen Eberle
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Patent number: 5030779Abstract: A hydrogenation catalyst prepared by combining one or more Group VIII metal compounds with one or more alkylalumoxanes and one or more alkyls or hydrides of a metal selected from the group consisting of the Group Ia, IIa, and IIa metals and a hyrogenation process wherein said catalyst is used to hydrogenate compounds containing ethylenic and/or aromatic unsaturation. Preferably, the one or more Group VIII metal compounds will be contacted sequentially with the one or more alkylalumoxanes and the one or more alkyls or hydrides, first with the one or more alkylalumoxanes and then with one or more alkyls and/or hydrides. The one or more Group VIII metal compounds is selected from the group of compounds consisting of carboxylates, chelates, alkoxides, salts of acids containing sulfur, salts of partial esters of acids containing sulfur and salts of aliphatic and aromatic sulfonic acids. Nickel and cobalt compounds are preferred for use in the hydrogenation catalysts.Type: GrantFiled: August 29, 1990Date of Patent: July 9, 1991Assignee: Shell Oil CompanyInventors: Ronald J. Hoxmeier, Lynn H. Slaugh
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Patent number: 4995963Abstract: A crystalline, galliosilicate molecular sieve having the zeolite L type structure and the following composition expressed in terms of oxide mole ratios in the anhydrous state:Ga.sub.2 O.sub.3 :xSiO.sub.2 :yM.sub.2 O:zK.sub.2 Owhere M is an alkali metal other than potassium, preferably sodium, x equals at least 3.0, preferably 4 to 10, y equals 0 to 0.9, z equals 0.1 to 1.0, and y+z equals about 1.0. The crystalline, galliosilicate molecular sieve of the invention may be employed, after reducing its alkali metal content, as a component of a catalyst which can be used in a variety of chemical conversion processes, preferably hydrocarbon conversion processes, and most preferably hydrocracking and isomerization processes.Type: GrantFiled: January 16, 1990Date of Patent: February 26, 1991Assignee: Union Oil Company of CaliforniaInventor: Mario L. Occelli
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Patent number: 4990710Abstract: Group VIII metal modified non-acidic tin containing microporous crystalline materials which in catalysis exhibit high selectively for dehydrogenation and dehydrocyclization are described.Type: GrantFiled: June 24, 1988Date of Patent: February 5, 1991Assignee: Mobil Oil CorporationInventors: Ralph M. Dessau, Ernest W. Valyocsik, James C. Vartuli
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Patent number: 4985567Abstract: New chiral phosphinopyrrolidine compounds of the general formula: ##STR1## wherein R.sup.1 is hydrogen or --COA.sup.1, --COOA.sup.2, --CONHA.sup.3, --SO.sub.2 A.sup.4 or --PO(A.sup.5).sub.2, A.sup.1, A.sup.2, A.sup.3, A.sup.4 and A.sup.5 each represents independently alkyl or aryl, R.sup.2 is phenyl, di(lower-alkyl)aminophenyl, lower-alkoxyphenyl or 3,5-dimethyl-4-methoxyphenyl, and R.sup.3 is phenyl, lower-alkylphenyl, di(lower-alkyl)aminophenyl, lower-alkoxyphenyl or 3,5-dimethyl-4-methoxyphenyl, with the proviso that R.sup.2 and R.sup.3 may not simultaneously by phenyl, p-di(lower-alkyl)-aminophenyl or p-lower-alkoxyphenyl, as well as the use of these compounds as ligand for a metal complex catalyst for asymmetric synthesis of optically active compounds. The new chiral phosphinopyrrolidine compounds are useful ligands which attain both of high optical yield and high reaction efficiency in catalytic asymmetric reduction.Type: GrantFiled: March 6, 1989Date of Patent: January 15, 1991Assignees: Kazuo Achiwa, Fuji Yakuhin Kogyo Kabushiki KaishaInventors: Kazuo Achiwa, Hideo Takeda
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Patent number: 4982028Abstract: Non-acid microporous crystalline indium containing materials are combined with Group VIII metal such as platinum to produce catalysts which exhibit high selectivity for dehydrocyclization of C.sub.5.sup.+ paraffins and which exhibit little, if any, cracking activity for hexane and heptane.Type: GrantFiled: September 5, 1989Date of Patent: January 1, 1991Assignee: Mobil Oil CorporationInventors: Ralph M. Dessau, Ernest W. Valyocsik
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Patent number: 4980331Abstract: A hydrogenation catalyst prepared by combining one or more Group VIII metal compounds with one or more alkylalumoxanes and one or more alkyls or hydrides of a metal selected from the group consisting of the Group Ia, IIa, and IIa metals and a hydrogenation process wherein said catalyst is used to hydrogenate compounds containing ethylenic and/or aromatic unsaturation. Preferably, the one or more Group VIII metal compounds will be contacted sequentially with the one or more alkylalumoxanes and the one or more alkyls or hydrides, first with the one or more alkylalumoxanes and then with the one or more alkyls and/or hydrides. The one or more Group VIII metal compounds is selected from the group of compounds consisting of carboxylates, chelates, alkoxides, salts of acids containing sulfur, salts of partial esters of acids containing sulfur and salts of aliphatic and aromatic sulfonic acids. Nickel and cobalt compounds are preferred for use in the hydrogenation catalysts.Type: GrantFiled: June 8, 1989Date of Patent: December 25, 1990Assignee: Shell Oil CompanyInventors: Ronald J. Hoxmeier, Lynn H. Slaugh
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Patent number: 4967031Abstract: A process for the non-catalytic hydrogenation of organic compounds, which contain at least one reducible functional group, which comprises reacting the organic compound, a hydride complex, preferably a transition metal hydride complex or an organosilane, and a strong acid in a liquid phase.Type: GrantFiled: December 13, 1989Date of Patent: October 30, 1990Assignee: The United States of America as represented by the United States Department of EnergyInventor: R. Morris Bullock
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Patent number: 4950386Abstract: It has now been discovered that hydrocarbon feeds containing a polycyclic aromatic compound or mixtures thereof can be selectively hydrogenated by contacting the feed with a transition metal catalyst and hydrogen in the presence of an acid to provide a hydrocarbon mixture in which the aromatic content consists substantially of mono- and di-aromatic compounds. Useful acids include Lewis acids and acids having a pKa in the range of 0 to about -10.Type: GrantFiled: August 15, 1988Date of Patent: August 21, 1990Assignee: Exxon Research and Engineering CompanyInventor: Manuel A. Francisco
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Patent number: 4950820Abstract: Olefinic hydrocarbons present in mixtures containing tert.-alkyl alkyl ethers and, if appropriate, other saturated aliphatic or aromatic hydrocarbons can be hydrogenated with substantial preservation of the ethers if the catalyst used has an active component for hydrogenation on a catalyst support having a specific surface area of more than 50 m.sup.2 /g and a pore diameter of, in the main, <1,000 nm.Type: GrantFiled: July 14, 1986Date of Patent: August 21, 1990Assignee: EC Erdolchemie GmbHInventors: Bernhard Schleppinghoff, Horst Reinhardt, Hans-Joachim Kramer
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Patent number: 4895994Abstract: Catalysts made by the Raney process (e.g., Raney process nickel) pelletized in matrix of polymer and plasticizer are activated by either (a) removal of plasticizer (e.g., by solvent extraction) followed by leaching out Al with caustic solution, leaving an active catalyst made by the Raney process in a polymer matrix; or (b) removal of plasticizer, then calcining to remove polymer, followed by leaching with caustic. The activated catalyst pellets have sufficient strength and attrition resistance for efficient use in fixed beds and packed columns for superior hydrogenation of toluene, heptene, butyraldehyde, and other conventional feedstockers used with catalysts made by the Raney process.Type: GrantFiled: October 18, 1988Date of Patent: January 23, 1990Assignee: W. R. Grace & Co.-Conn.Inventors: Wu-Cheng Cheng, Christian B. Lundsager, Robert M. Spotnitz
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Patent number: 4885410Abstract: The invention relates to a novel supported catalyst comprising a combination of metals with nickel as component (a), a metal having an atomic number greater than 43 from Groups VIIB and VIII of the Periodic Table as component (b) and rhenium as component (c) in a weight ratio of (a):(b):(c) of about 10-90:0.05-5:0.03-10 and to the use of the catalyst for high pressure hydrogenation reactions, particularly for the hydrogenation of butanediol product containing aldehyde, butynediol and color forming impurities.Type: GrantFiled: August 17, 1988Date of Patent: December 5, 1989Assignee: GAF CorporationInventor: Waldo De Thomas
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Patent number: 4874504Abstract: A method is disclosed which provides improved control over the noble-metal exchange of zeolite catalyst by using bulky organic bases to control pH during the metal loading step.Type: GrantFiled: March 20, 1989Date of Patent: October 17, 1989Assignee: Mobil Oil CorporationInventors: Roland von Ballmoos, Francis X. Ryan
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Patent number: 4804796Abstract: Improved, heterogeneous, refractory catalysts are in the form of gas-impervious, hollow, thin-walled spheres (10) suitable formed of a shell (12) of refractory such as alumina having a cavity (14) containing a gas at a pressure greater than atmospheric pressure. The wall material may be itself catalytic or a catalytically active material coated onto the sphere as a layer (16), suitably platinum or iron, which may be further coated with a layer (18) of activator or promoter. The density of the spheres (30) can be uniformly controlled to a preselected value within .+-.10 percent of the density of the fluid reactant such that the spheres either remain suspended or slowly fall or rise through the liquid reactant.Type: GrantFiled: April 8, 1987Date of Patent: February 14, 1989Assignee: California Institute of TechnologyInventors: Taylor G. Wang, Daniel D. Elleman, Mark C. Lee, James M. Kendall, Jr.