Elemental O Or S Acceptor With Extraneous Nonhydrocarbon Agent, E.g., Catalyst, Etc. Patents (Class 585/658)
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Patent number: 5922925Abstract: A process for dehydrogenating dehydrogenatable C.sub.2-30 hydrocarbons includes contacting the hydrocarbons under dehydrogenating conditions in one or more reaction zones with a solid catalyst. The solid catalyst includes at least a Group VIII noble metal, a Group IVA metal, and a carrier of a mixed oxide of magnesium and aluminum.Type: GrantFiled: May 18, 1998Date of Patent: July 13, 1999Assignee: Den norske stats oljeselskap a.s.Inventors: Duncan Akporiaye, Morten Ronnekleiv, Preben Hasselgard, Age Solbakken, deceased
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Patent number: 5905180Abstract: A process for the production of a mono-olefin from a gaseous paraffinic hydrocarbon having at least two carbon atoms or mixtures thereof comprising reacting said hydrocarbons and molecular oxygen in the presence of a platinum catalyst. The catalyst consists essentially of platinum modified with Sn or Cu and supported on a ceramic monolith.Type: GrantFiled: September 30, 1996Date of Patent: May 18, 1999Assignee: Regents of the University of MinnesotaInventors: Chikafumi Yokoyama, Sameer S. Bharadwaj, Lanny D. Schmidt
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Patent number: 5895829Abstract: In a process for preparing olefinically unsaturated compounds such as styrene by oxidative dehydrogenation of corresponding hydrocarbons using a previously oxidized oxygen transferer acting as catalyst in the absence of molecular oxygen and reoxidation of the oxygen transferer in at least two reactors, the dehydrogenation and regeneration takes place alternately in time in the two reactors and the reactors are connected to one another in terms of heat via heat exchangers and a common circuit for heat transfer medium.Type: GrantFiled: June 18, 1997Date of Patent: April 20, 1999Assignee: BASF AktiengesellschaftInventors: Wolfgang Jurgen Popel, Alfred Hagemeyer, Wolfgang Buchele, Axel Deimling, Wolfgang Hoffmann
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Patent number: 5877387Abstract: A preparation of a Pb-substituted hydroxyapatite catalyst for oxidative coupling of methane represented by the formula Ca.sub.10-x pb.sub.x (PO.sub.4).sub.6 (OH).sub.2 wherein 0<X<10 or preferably 0<X<3, includes dissolving calcium nitrate tetrahydrate ?Ca(NO.sub.3).sub.2 4H.sub.2 O!, lead nitrate ?Pb(NO.sub.3).sub.2 ! and monobasic ammonium phosphate ?NH.sub.4 H.sub.2 PO.sub.4 ! in a distilled water at room temperature to have over 0.01M concentration and pH 9 and maintaining a resultant precipitate for 5 to 20 hours for aging and then calcining the resultant. A method for producing C.sub.2 compounds using the thusly produced catalyst includes reacting a mixed gas composed of methane, oxygen and helium in the presence of 5.about.20 g.multidot.min/L of the Pb-substituted hydroxyapatite catalyst according to the present invention, at a high temperature of at least 600.degree. C.Type: GrantFiled: May 23, 1997Date of Patent: March 2, 1999Assignee: Korea Institute of Science and TechnologyInventors: Tae-Jin Park, Dong Jin Suh, Kwan-Young Lee
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Patent number: 5877381Abstract: The present invention provides a fluidized bed catalyst for the synthetic reaction of organic compounds which has a reduced catalyst loss. A fluidized bed catalyst for organic compound synthetic reaction, characterized in that 90% or more of the catalyst particles is in the range of 5-500 .mu.m on the weight-based particle size distribution and 90% or more of the 20-75 .mu.m particles has a crushing strength which satisfies the following equation:CS>A.multidot.d.sub..alpha.wherein CS represents a crushing strength ?g-weight/particle!,A represents a constant 0.001,d represents a particle diameter ?.mu.m!, and.alpha. represents a constant 2.Type: GrantFiled: July 1, 1996Date of Patent: March 2, 1999Assignee: Nitto Kagaku Kogyo Kabushiki KaishaInventors: Yutaka Sasaki, Hiroshi Yamamoto, Kiyoshi Moriya, Yoshimi Nakamura
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Patent number: 5866737Abstract: A process for the oxidation and oxidative dehydrogenation of hydrocarbons, in particular ethylbenzene, to form corresponding oxidized or olefinically unsaturated compounds, in particular styrene, over an oxygen-conferring, oxygen-regenerable catalyst involving a working period, a time-displaced regenerating period and at least one intermediate rinsing period comprises effecting a partial regeneration during the working period by time-displaced addition of a substoichiometric amount of oxygen.Type: GrantFiled: January 7, 1997Date of Patent: February 2, 1999Assignee: BASF AktiengesellschaftInventors: Alfred Hagemeyer, Jurgen Schweinzer, Otto Watzenberger
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Patent number: 5817904Abstract: A method for converting methane by an oxidative coupling reaction to longer chain hydrocarbons comprising cofeeding methane and oxygen simultaneously and continuously into a reaction zone to form a mixture, contacting said methane and oxygen mixture under oxidative coupling reaction conditions with a solid catalyst consisting essentially of manganese oxide and silicon oxide, promoted with an alkaline metal and non metal, to form longer chain hydrocarbons wherein the manganese, silicon oxide, alkali metal and non metal are present in a molar ratio 0-0.5:93.2-93.7:4.2:2.1.Type: GrantFiled: June 7, 1995Date of Patent: October 6, 1998Assignee: Repsol Petroleo S.A.Inventors: Sebastian Vic, Miguel A. Pena, Pilar Terreros, Juan P. Gomez, Jose L. Garcia-Fierro, Juan M. Jimenez
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Patent number: 5763722Abstract: An improved method for the oxidative conversion of methane into higher hydrocarbons in which methane and oxygen are continuously and simultaneously cofed into a reaction zone under effective oxidative coupling conditions and contacted with a solid catalyst consisting essentially of a catalyst having a composition of empirical formula Ce.sub.a Na.sub.b Ca.sub.100 O.sub.x wherein a is in the range 0.03 to 2.0, b is in the range of 0.7 to 7.0 and oxygen is present in a molar amount sufficient to fulfill the valence requirements of cerium, sodium and calcium.Type: GrantFiled: June 7, 1995Date of Patent: June 9, 1998Assignee: Repsol Petroleo S.A.Inventors: Sebastian Vic, Miguel A. Pena, Pilar Terreros, Juan P. Gomez, Jose L. Garcia-Fierro, Juan M. Jimenez
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Patent number: 5705728Abstract: The present invention provides an efficient process for the production of ethylene or a mixture of ethylene and vinyl chloride, in which some 1,2-dichloroethane (EDC) may also be produced, by reacting chlorine with ethane. The process is characterized by a conversion of ethane per pass through the reactor of at least about 50%, and a combined molar yield of ethylene and vinyl chloride of at least about 80% based on the ethane consumed. In accordance with this invention, there is provided a process for preparing ethylene or a mixture of ethylene and vinyl chloride by the reaction of ethane and chlorine which comprises:(a) providing a stream of ethane feed gas and a stream of chlorine feed gas;(b) preheating either said ethane stream only or both said ethane and chlorine streams;(c) thoroughly mixing said ethane and chlorine feed gases within about one second and at a molar ratio of ethane to chlorine of at least about 0.9:1.Type: GrantFiled: February 10, 1995Date of Patent: January 6, 1998Assignee: Occidental Chemical CorporationInventors: Krishnan Viswanathan, Hang-Chang Bobby Chen, Sidney W. Benson
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Patent number: 5663472Abstract: A process for reacting ethane with chlorine to produce a mixture of ethylene and vinyl chloride is disclosed. The process involves the intimate mixing of ethane and chlorine in an ethane to chlorine ratio of at least about 0.9:1 at a temperature such that ethane and chlorine do not react during mixing, and heating the mixture to a temperature above about 215.degree. C. to commence the reaction, allowing the reaction to proceed for a period of less than about 1 minute, and providing sufficient heat to the reacting mixture so that the reacted mixture will have a temperature between about 400.degree. C. and about 800.degree. C.Type: GrantFiled: February 7, 1995Date of Patent: September 2, 1997Assignee: University of Southern CaliforniaInventors: Sidney W. Benson, Maja A. Weissman
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Patent number: 5663473Abstract: A process for the conversion of a liquid paraffin-containing hydrocarbon which comprises the steps of (a) partially combusting a mixture of the liquid hydrocarbon and a molecular oxygen-containing gas in a reaction chamber with a catalyst capable of supporting combustion beyond the normal fuel rich limit of flammability. The mixture has a stoichiometric ratio of hydrocarbon to oxygen of greater than the stoichiometric ratio required for complete combustion to carbon dioxide and water. The process produces a product stream and a carbon deposit in the reaction chamber. Periodically, the liquid hydrocarbon and molecular oxygen-containing gas mixture in step (a) is replaced with a fuel-rich carbon containing gas stream for a period of time sufficient to effect substantial removal of the carbon deposit from the reaction chamber.Type: GrantFiled: June 7, 1995Date of Patent: September 2, 1997Assignee: BP Chemicals LimitedInventors: David C. Griffiths, Keith W. Palmer, Ian A B Reid
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Patent number: 5639929Abstract: A process for the oxidative dehydrogenation of hydrocarbons is disclosed in which C.sub.2 -C.sub.6 alkanes are contacted with an oxygen containing gas in a fluidized catalyst bed of platinum, rhodium, nickel or platinum-gold supported on .alpha.-alumina or zirconia. Ethane is dehydrogenated to ethylene and higher alkanes are dehydrogenated to ethylene, propylene and iso-butylene.Type: GrantFiled: April 17, 1995Date of Patent: June 17, 1997Assignee: Regents of the University of MinnesotaInventors: Sameer S. Bharadwaj, Lanny D. Schmidt
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Patent number: 5530171Abstract: There is provided a process for the net catalytic oxidative dehydrogenation of alkanes to produce alkenes. The process involves simultaneous equilibrium dehydrogenation of alkanes to alkenes and combustion of the hydrogen formed to drive the equilibrium dehydrogenation reaction further to the product alkenes. In the present reaction, the alkane feed is passed into a reactor containing both an equilibrium dehydrogenation catalyst and a reducible metal oxide, whereby the alkane is dehydrogenated and the hydrogen produced is simultaneously and selectively combusted in oxidation/ reduction (REDOX) reaction with the reducible metal oxide. This particular mode of operation is termed a same reactor, REDOX mode. The equilibrium dehydrogenation catalyst may comprise platinum and the reducible metal oxide may contain bismuth, antimony, indium, or molybdenum, or a mixture thereof.Type: GrantFiled: April 17, 1995Date of Patent: June 25, 1996Assignee: Mobil Oil CorporationInventors: Pradyot A. Agaskar, Robert K. Grasselli, James N. Michaels, P. Thomas Reischman, David L. Stern, John G. Tsikoyiannis
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Patent number: 5527978Abstract: Methane is converted into higher hydrocarbon products by oxidative coupling, by bringing a gaseous mixture containing methane and oxygen into contact with a solid catalyst formed from calcium oxide, magnesium oxide, a lanthanide oxide plus possibly lithium oxide, wherein:the lithium content is between 0 and 0.20 wt %,the calcium/magnesium atomic ratio is between 0.08 and 0.7, andthe (calcium+magnesium)/lanthanide atomic ratio is between 0.8/1 and 8/1, and preferably between 2/1 and 4/1.Type: GrantFiled: October 28, 1993Date of Patent: June 18, 1996Assignee: Eniricerche S.p.A.Inventors: Giuseppe Fornasari, Giuseppe Bellussi
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Patent number: 5527979Abstract: There is provided a process for the net catalytic oxidative dehydrogenation of alkanes to produce alkenes. The process involves simultaneous equilibrium dehydrogenation of alkanes to alkenes and combustion of the hydrogen formed to drive the equilibrium dehydrogenation reaction further to the product alkenes. In the present reaction, the alkane feed is dehydrogenated over an equilbrium dehydrogenation catalyst in a first reactor, and the effluent from the first reactor, along with oxygen, is then passed into a second reactor containing a metal oxide catalyst which serves to selectively catalyze the combustion of hydrogen. This particular mode of operation is termed a separate reactor, cofed oxygen mode. The equilibrium dehydrogenation catalyst may comprise platinum and the selective metal oxide combustion catalyst may contain bismuth, antimony, indium, molybdenum, or a mixture thereof.Type: GrantFiled: April 17, 1995Date of Patent: June 18, 1996Assignee: Mobil Oil CorporationInventors: Pradyot A. Agaskar, Robert K Grasselli, James N. Michaels, P. Thomas Reischman, David L. Stern, John G. Tsikoyiannis
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Patent number: 5510558Abstract: Oxidative dehydrogenation of alkanes and alkylaromatic hydrocarbons is achieved by contact with an active carbon catalyst. In various aspects of the invention, the oxidative dehydrogenation is performed at a pressure above about 100 psia, and/or at a temperature in the range from about 500.degree. C. to about 800.degree. C., and/or the active carbon catalyst contains a metal, for example, molybdenum.Type: GrantFiled: December 29, 1993Date of Patent: April 23, 1996Assignee: Sun Company, Inc. (R&M)Inventors: Benjamin S. Umansky, Kevin A. Boyer, Chao-Yang Hsu
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Patent number: 5498816Abstract: Process for the dehydrogenation of a hydrocarbon feed stream comprising steps of contacting the feed stream with a dehydrogenation catalyst in at least one dehydrogenation zone and reacting the feed stream to a hydrogen containing effluent stream;admixing to the effluent stream an oxygen containing atmosphere in at least one mixing zone;removing hydrogen from the effluent stream by reaction with oxygen in the oxygen containing atmosphere by contact with a hydrogen oxidation catalyst in at least one hydrogen removing zone,the improvement of which comprises employing massive forms of noble metals or alloys thereof as catalyst in the hydrogen removal zone.Type: GrantFiled: November 30, 1994Date of Patent: March 12, 1996Assignee: Haldor Topsoe A/SInventors: Poul E. H. Nielsen, Peter Lehrmann
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Patent number: 5476981Abstract: Solid superacid catalyst, for example sulfated zirconia, is used in the oxidative dehydrogenation of saturated or partially saturated hydrocarbons, for example the conversion of isobutane to isobutylene in the presence of an oxygen-containing oxidizing agent at reaction conditions typically including temperatures from 500 to 1,000 degrees Fahrenheit, superatmospheric pressures, and oxygen/alkane molar ratios from 0.2 to 20. Performance of a metal-oxide or metal-hydroxide oxidative dehydrogenation catalyst may be enhanced by pretreating a solid superacid or other catalyst containing metal oxides or hydroxides at a carbonizing temperature with an organic material, for example an oxygen-containing organic material, to form a carbonaceous layer on the surface thereof prior to use of the catalyst in oxidative dehydrogenation.Type: GrantFiled: December 29, 1993Date of Patent: December 19, 1995Assignee: Sun Company, Inc. (R&M)Inventors: Benjamin S. Umansky, Chao-Yang Hsu
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Patent number: 5436383Abstract: Process for the dehydrogenation of a charge incorporating saturated aliphatic hydrocarbons essentially having 3 to 5 carbon atoms per molecule, in which the charge, previously heated to the reaction temperature and without premixing with the hydrogen, is introduced at the inlet of at least one reactor, where the dehydrogenation reaction is performed in the presence of a catalyst, preferably incorporating a support having at least one oxide of an element chosen from among the groups IIA, IIB, IIIA, IIIB, IVA and IVB of the periodic classification of elements, at least one noble metal from the platinum family, at least one promotor metal and at least one alkali metal or alkaline earth metal.Type: GrantFiled: August 31, 1994Date of Patent: July 25, 1995Assignee: Institut Francais du PetroleInventors: Fabienne Le Peltier, Sylvie Robert, Jean Paul Boitiaux, Gerard Leger, Jean Pierre Burzynski
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Patent number: 5430219Abstract: Disclosed is an integrated process for producing olefins by starting from methane containing gas mixture, which process essentially comprises the following steps:converting methane into higher hydrocarbons by oxidative coupling carried out in the presence of air and/or oxygen;dehydrogenating, with the aid of a catalyst, said higher hydrocarbons, with an olefin-rich mixture being obtained;removing H.sub.2 O, CO.sub.2, CO and H.sub.2 from the resulting olefinic mixture;removing from said olefinic mixture any not converted methane, and recycling it upstream from the oxidating coupling;separating ethylene from the olefinic mixture;separating any not dehydrogenated ethane from the olefinic mixture.Type: GrantFiled: September 30, 1993Date of Patent: July 4, 1995Assignees: Snamprogetti S.p.A., Eniricerche S.p.A.Inventors: Domenico Sanfilippo, Stefano Rossini
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Patent number: 5414181Abstract: Disclosed is a method which combines catalytic cracking and olefin production using a coked catalytic cracking catalyst to dehydrogenate an alkane feed stream and form an olefin rich product stream. Preferably, the coked catalytic cracking catalyst has a carbon content of about 0.2-10 wt. %. The catalyst preferably comprises a crystalline tetrahedral framework oxide component.Type: GrantFiled: November 19, 1993Date of Patent: May 9, 1995Assignee: Exxon Research and Engineering CompanyInventors: Roby Bearden, Jr., Michael C. Kerby, Stephen M. Davis
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Patent number: 5406017Abstract: A method for converting methane to higher hydrocarbon products and coproduct water wherein a gas comprising methane and a gaseous oxidant are contacted with a nonacidic catalyst at temperatures within the range of about 700.degree. to 1200.degree. C. A preferred catalyst comprises an alkali component associated with a support material. Results obtained over alkali-promoted solids are enhanced when the contacting is conducted in the presence of halogen promoters.Type: GrantFiled: October 25, 1990Date of Patent: April 11, 1995Assignee: Atlantic Richfield CompanyInventor: Howard P. Withers, Jr.
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Patent number: 5396007Abstract: A process for producing dimethylnaphthalene by the dehydrogenation of dimethyl-tetrahydronaphthalene which comprises carrying out the dehydrogenation reaction in a gaseous state at a temperature of 200.degree. to 350.degree. C. in the presence of a diluting medium and by the use of a platinum and/or palladium catalyst supported on an activated carbon carrier. The process is capable of producing industrially useful dimethylnaphthalene with a high yield and a high selectivity and minimized side reactions, over a long stabilized period.Type: GrantFiled: July 1, 1993Date of Patent: March 7, 1995Assignee: Mitsubishi Gas Chemical Company, Inc.Inventors: Yoichi Kyuko, Shinji Ozawa, Makoto Takagawa, Kenji Inamasa
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Patent number: 5386074Abstract: Barium peroxide in which has been incorporated a transition metal compound is used as a catalyst for the oxidative dehydrogenation of organic compounds in the presence of terminal oxidants.Type: GrantFiled: July 30, 1993Date of Patent: January 31, 1995Assignee: Sun Company, Inc. (R&M)Inventors: Vincent A. Durante, James E. Lyons, Darrell W. Walker
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Patent number: 5382742Abstract: There is provided a gallium-containing MCM-22 zeolite. There are also provided methods for making this zeolite and processes for using this zeolite as a catalyst for the conversion of organic molecules. Particular conversions are reforming and the dehydrogenation of methylcyclohexane to form toluene.Type: GrantFiled: September 16, 1993Date of Patent: January 17, 1995Assignee: Mobil Oil Corp.Inventors: Roger A. Morrison, Mae K. Rubin
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Patent number: 5382741Abstract: A process for the production of mono-olefins from a paraffin-containing hydrocarbon feed having at least two carbon atoms which comprises a first step of partially combusting a mixture of the hydrocarbon feed and a molecular oxygen-containing gas in contact with a catalyst capable of supporting combustion beyond the normal fuel rich limit of flammability, the first step being carried out under a total pressure of greater than 5 bar absolute and at a temperature of greater than 650.degree. C.; and a second step of cooling the mono-olefinic products to 600.degree. C. or less within less than 50 milliseconds of formation.Type: GrantFiled: July 13, 1992Date of Patent: January 17, 1995Assignee: The British Petroleum Company p.l.c.Inventors: Christopher J. Astbury, David C. Griffiths, Mark J. Howard, Ian A. B. Reid
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Patent number: 5371309Abstract: There is provided a vacancy titanate intercalated with a cationic hydroxy aluminum complex, such as a Keggin ion. A method for making this material and a process for using this material as a catalyst are also provided.Type: GrantFiled: June 4, 1993Date of Patent: December 6, 1994Assignee: Mobil Oil Corp.Inventor: Ahmad Moini
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Patent number: 5365006Abstract: An alkane-containing feedstream is passed through one or more tubes, which may contain alkane-dehydrogenation catalyst, immersed in a bed of fluidized particles. The bed is at an elevated temperature which maintains the temperature within the tube(s) at an alkane-dehydrogenation temperature. The particles may be inert, chemically active and/or catalytically active. In one embodiment, cracking catalyst particles are circulated between a reaction zone wherein they contact a cracker feedstock which is converted to cracked hydrocarbon products and a regenerator (22) wherein carbonaceous deposits on the catalyst particles are exothermically removed by contact with an oxygen-containing gas (24). Hot regenerated particles from the regenerator (22) are recirculated (27) to the reaction zone for re-use therein.Type: GrantFiled: December 31, 1992Date of Patent: November 15, 1994Assignee: Exxon Research and Engineering CompanyInventor: Willibald Serrand
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Patent number: 5354936Abstract: A method for preparing ethane and ethylene by reacting methane or a methane-containing natural gas in the presence of oxygen or an oxygen-containing gas, i.e., by partially oxidizing, at a temperature of 500.degree. through 1000.degree. C. using shellfishes or shells as a catalyst is disclosed. The oxidation coupling reaction of methane is controlled so as to remarkably increase the conversion ratio of methane and the selectivity of C.sub.2.sup.+ compounds. The waste matter abundantly released from food industries as well as easily accessible natural resources is used as a raw material of a catalyst for the reaction. The present method is extremely useful from the viewpoint of the recycling of waste as well.Type: GrantFiled: March 26, 1993Date of Patent: October 11, 1994Assignee: Sekiyushigen Kaihatsu Kabushiki KaishaInventors: Masami Yamamura, Hideo Okado, Naohide Tsuzuki, Kazutoshi Chaki, Toshiya Wakatsuki
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Patent number: 5336826Abstract: Higher hydrocarbons are produced from methane by reacting the methane at elevated temperature, suitably in the range from 600.degree. to 800.degree. C., with an oxygen-containing gas having a ratio of methane to oxygen of greater than the stoichiometric ratio for complete combustion in the presence as catalyst of a lithium-doped material which under the reaction conditions is a physically base-stable, non-melting, oxygen-stable compound of an element of Groups III to VIII of the Periodic Table of the Elements including the rare earth elements.Type: GrantFiled: December 22, 1986Date of Patent: August 9, 1994Assignee: The British Petroleum Company p.l.c.Inventors: John H. Brophy, Steven R. Wade
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Patent number: 5336822Abstract: 4-Vinylcyclohexene is converted to styrene in the presence of a catalyst comprising tin, antimony, and oxygen. The feed stream to be contacted with the catalyst comprises water, 4-vinylcyclohexene, and oxygen. A ratio of water to 4-vinylcyclohexene above about 12:1, preferably above about 14:1, significantly increases the half-life of the catalyst. The catalyst is prepared by coprecipitating a tin chloride and an antimony chloride followed by calcination of the precipitate at a temperature in the range from 850.degree. C. to 1000.degree. C.Type: GrantFiled: June 14, 1993Date of Patent: August 9, 1994Assignee: The Dow Chemical CompanyInventor: Dennis A. Hucul
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Patent number: 5336828Abstract: A process is described for carrying out the dehydrogenation or hydrogenation, including hydrogenolysis, of a hydrocarbon in the presence of one or more soluble fullerene catalysts which have been dissolved in the hydrocarbon (when the hydrocarbon is a liquid capable of dissolving the fullerene catalyst) or dissolved in a solvent which is also a solvent for the hydrocarbon (when the hydrocarbon either is not a liquid or is not a liquid which is a solvent for the fullerene catalyst). The use of a liquid catalyst, i.e., a dissolved fullerene catalyst, inhibits coking reactions to thereby inhibit formation of coke on a solid catalyst or catalyst support by elimination of nucleation points or growth regions for such coke formation.Type: GrantFiled: March 3, 1993Date of Patent: August 9, 1994Assignee: SRI InternationalInventors: Ripudaman Malhotra, Doris S. Tse, Donald F. McMillen
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Patent number: 5336825Abstract: This invention discloses an improved integrated two step process for conversion of methane to liquid hydrocarbons of gasoline range. The invention particularly comprises catalytic oxidative conversion of methane with free oxygen to ethylene and higher olefins containing gaseous product in the first step and catalytic conversion of the olefins from the product stream of the first step without separating them to liquid hydrocarbons of gasoline range in the second step, for the conversion of methane to liquid hydrocarbons. The process of the present invention could be used in the petroleum industry for the production of gasoline and liquid hydrocarbon fuels and aromatic hydrocarbons.Type: GrantFiled: July 10, 1992Date of Patent: August 9, 1994Assignee: Council of Scientific & Industrial ResearchInventors: Vasant R. Choudhary, Subhash D. Sansare, Sopan T. Chaudhari
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Patent number: 5321187Abstract: A method for preparing a catalyst for conversion of methane to higher hydrocarbons, discloses the steps of: forming a mixture of a manganese aqueous solution and an oxidative agent aqueous solution in an inorganic oxide support material; varying a pH value of the mixture between acidic and basic values to obtain a precipitate of manganese oxide; drying the manganese oxide precipitate; impregnating the dried manganese oxide precipitate with a promoter to obtain an impregnated solid; drying the impregnated solid; and calcining the impregnated solid until a surface atomic ratio of promoter to manganese is at least 5. The catalyst so acquired may be contacted with a methane gas to obtain stable conversion values over extended reaction times.Type: GrantFiled: January 25, 1993Date of Patent: June 14, 1994Assignee: Intevep, S.A.Inventors: Cesar Ovalles, Nora Urbano, Francisco Rosa
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Patent number: 5321188Abstract: Methane is converted into higher hydrocarbon products, and especially into ethane and ethylene, by oxidative coupling, by bringing a gaseous mixture containing methane and oxygen into contact at high temperature for a short contact time with a solid catalyst formed from lithium oxide, an alkaline earth metal oxide (preferably of magnesium) and a lanthanide oxide (preferably of neodymium or lanthanum), in which the lithium content is less than 0.20% by weight and the atomic ratio of the alkaline earth metal to the lanthanide varies from 0.8/1 to 8/1, said catalyst being obtained by:preparing a mixture of lithium, alkaline earth metal and lanthanide oxides in which the lithium content exceeds 1% by weight; andreducing the lithium content of the mixture to less than 0.20% by weight by high temperature thermal treatment conducted at least partly in an oxidizing atmosphere.Type: GrantFiled: March 1, 1993Date of Patent: June 14, 1994Assignees: Eniricerche S.p.A., Snamprogetti S.p.A.Inventors: Giuseppe Fornasari, Stefano Palmery, Giampiero Piro, Giuseppe Bellussi
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Patent number: 5321186Abstract: A method for preparing an unsaturated compound mainly comprising monoolefins, or a mixture of .alpha., .beta.-unsaturated nitriles and monoolefins comprises coming a mixed gas which comprises paraffins and oxygen, or paraffins, oxygen and ammonia in contact with a catalyst which comprises (1) an oxide of phosphorus and (2) at least one oxide selected from the group consisting of indium oxide and tin oxide or comprises, in addition to the foregoing catalytic components, (3) at least one oxide selected from the group consisting of vanadium oxide, tungsten oxide and molybdenum oxide. The method makes it possible to prepare monoolefins, or a mixture of .alpha., .beta.-unsaturated nitriles and monoolefins in high yield and high selectivity from cheap starting materials, parafins.Type: GrantFiled: November 17, 1992Date of Patent: June 14, 1994Assignee: Mitsui Toatsu Chemicals, Inc.Inventors: Tadatoshi Honda, Kazuhiro Terada
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Patent number: 5321185Abstract: A method of producing an oxidative coupling catalyst is disclosed by mixing particles of Fe.sub.2 O.sub.3, with a particle size in the range from 100 to 150 .mu.m, and silica, with a particle size in the range from about 150 to about 215 .mu.m. The particles are heated to a temperature of at least about 800.degree. C., after which the silica particles impregnated with Fe.sub.2 O.sub.3 are separated from the remaining iron particles. The catalyst can be utilized for the oxidative coupling of methane with water molecules on the surface of the silica substrate, with the silica having a particle size in the range from about 150 to about 215.ltoreq..mu.m. The silicate catalyst substrate is essentially non-porous and has an average geometrical surface on the order of about 0.004 .mu.m.sup.2 /g and a surface concentration of iron on the order of about 2% by weight.Type: GrantFiled: July 8, 1992Date of Patent: June 14, 1994Assignee: Virginia Tech Intellectual PropertiesInventor: Donald R. van der Vaart
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Patent number: 5306858Abstract: Disclosed is a process for oxidizing a paraffin hydrocarbon containing 2 to 5 carbon atoms and no quaternary carbon atom to an olefin having the same number of carbon atoms as said paraffin by contacting said paraffin in a reaction zone with molecular oxygen and a VAPO-5 microporous molecular sieve as catalyst.Type: GrantFiled: November 20, 1992Date of Patent: April 26, 1994Assignee: The Standard Oil CompanyInventors: George F. Salem, Charles J. Besecker, Susan M. Kenzig, Walter J. Kowlaski, Larry M. Cirjak
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Patent number: 5302773Abstract: A process for preparing olefins and diolefins in high productivity which involves contacting an aliphatic hydrocarbon, such as butane, with a heterogeneous catalyst composition containing reactive oxygen under reaction conditions sufficient to produce a more highly unsaturated aliphatic hydrocarbon, such as 1,3-butadiene. The catalyst composition contains a glassy silica matrix of specified surface area and macro-porosity into which are encapsulated domains of a catalyst component containing oxides of magnesium and molybdenum. The catalyst has high crush strength and is useful in transport reactors.Type: GrantFiled: November 26, 1991Date of Patent: April 12, 1994Assignee: The Dow Chemical CompanyInventors: G. Edwin Vrieland, Stephen J. Doktycz, Bijan Khazai
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Patent number: 5288935Abstract: The invention concerns a method of producing liquid hydrocarbons from natural gas, characterized in that:a) the natural gas is separated in (2) into at least two fractions, a first fraction of gas enriched with methane and a second fraction enriched with C2+ alkanesb) the methane is selectively oxidised in (7a) by molecular oxygen in the presence of a catalyst for oxidizing linkage of methanec) the fraction enriched with C2+ alkanes is at least partly mixed with the effluent from selective oxidation, when at least 80% of the molecular oxygen introduced at stage (b) has already been consumed at stage (b)d) the mixture resulting from stage (c) is pyrolysed in (7b)e) when the temperature of the mixture from stage (d) has been brought to a temperature from 300.degree. to 750.degree. C. and more particularly from 420.degree. to 550.degree. C.Type: GrantFiled: May 21, 1992Date of Patent: February 22, 1994Assignee: Institut Francais du PetroleInventors: Fabio Alario, Charles Cameron, Jean-Francois Joly
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Patent number: 5276237Abstract: A membrane of an oxidative conversion contact material of a mixed oxide of aluminum and at least one multivalent activator metal with the membrane permitting selective conveyance of a form of oxygen therethrough, as well as methods for the oxidative conversion of a gaseous hydrocarbon reactant using such membranes are provided.Type: GrantFiled: December 20, 1991Date of Patent: January 4, 1994Assignee: Amoco CorporationInventor: Rodney L. Mieville
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Patent number: 5258347Abstract: A process for the production of olefins and diolefins, such as 1,3-butadiene, comprising contacting an aliphatic hydrocarbon, such as butane, with a heterogeneous catalyst composition containing reactive oxygen under reaction conditions such that a more highly unsaturated aliphatic hydrocarbon is selectively formed in a high productivity. The catalyst is a composition comprising (a) a support component of magnesia and alumina and/or magnesium aluminate spinel, and (b) a catalyst component of magnesia, an oxide of molybdenum, a Group IA metal oxide promoter, and optionally vanadium oxide. Catalysts of high surface area and high attrition resistance are claimed.Type: GrantFiled: May 29, 1992Date of Patent: November 2, 1993Assignee: The Dow Chemical CompanyInventors: Bijan Khazai, Craig B. Murchison, G. Edwin Vrieland
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Patent number: 5258567Abstract: This invention relates to a process for the dehydrogenation of C.sub.2 -C.sub.10 hydrocarbons at dehydrogenation conditions with a pillared mica catalyst which contains an active metal selected from the group consisting of Pt, Cr and mixtures thereof, and a first modifier metal selected from the group consisting of Sn, Ga and mixtures thereof. The micas may also contain a second modifier metal selected from the group consisting of alkali metals, alkaline earth metals, and rare earth metals, and mixtures thereof.Type: GrantFiled: August 26, 1992Date of Patent: November 2, 1993Assignee: Exxon Research and Engineering CompanyInventors: Michael C. Kerby, Kenneth L. Riley, Fred M. Long, Jack W. Johnson, John F. Brody
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Patent number: 5254779Abstract: A catalyst of the following formulaNi.sub.a MoO.sub.x (I)in which:a is a number from 0.6 to 1.3, andx is a number determined by the valency requirements of nickel and of molybdenum.The manufacture of this catalyst comprises the preparation of a solvated precursor and the thermal decomposition of the solvated precursor over a period of from 1 to 4 hours and at a temperature T.sub.1 of from 520.degree. to 600.degree. C. The catalyst is utilized in the oxidative dehydrogenation of propane at a temperature of from 400.degree. to 700.degree. C.Type: GrantFiled: October 1, 1991Date of Patent: October 19, 1993Inventors: Carlo Mazzocchia, Ezio Tempesti, Chafic Aboumrad
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Patent number: 5254778Abstract: An improved method for preparing a catalyst which is superior for converting methane to ethane and ethylene is described. The method involves mixing a solution of a magnesium alkoxide in alcohol with a solution of a lithium compound in alcohol. Preferably, chlorine is introduced into the mixture. A solution of an aluminum alkoxide in an alcohol may also be added to the mixture. The magnesium alkoxide is hydrolyzed to produce a gel, and the gel is then calcined to produce the catalyst. Catalysts prepared by this method are superior for converting methane to ethane and ethylene, and have superior selectivities for ethylene and ethane over conventional lithium carbonate/magnesium oxide catalysts.Type: GrantFiled: June 6, 1991Date of Patent: October 19, 1993Assignee: The Texas A & M University SystemInventors: Jack H. Lunsford, Paul G. Hinson
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Patent number: 5214225Abstract: A process for making ethylenically unsaturated hydrocarbons from a saturated C.sub.3 -C.sub.5 hydrocarbon feed with improved heat recovery. The feed is partially vaporized against hot discharge gases from product compressors, completely vaporized with low pressure steam and preheated against hot reactor effluent, before being heated by a process heater to reaction temperature and catalytically dehydrogenated in an adiabatic reactor. The process is controlled by regulating the low pressure steam supplied to the vaporizer, the heat input to the process heater, and cooling water flow to the process coolers.Type: GrantFiled: December 5, 1991Date of Patent: May 25, 1993Inventors: Stephen G. Hall, Robert B. Armstrong
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Patent number: 5214226Abstract: The present invention teaches an apparatus and method for commercial conversion of methane in the absence of a catalyst to higher hydrocarbons that are generally in short supply, e.g., butane, ethylene, propene, etc. The production of these higher molecular weight hydrocarbons aids in justifying the cost of the conversion process. The inventive conversion technique utilizes small amounts, generally 1% or less, of a low-cost initiator, plus air, which allows for the commercial viability of the process.Type: GrantFiled: March 13, 1992Date of Patent: May 25, 1993Assignee: Cornell Research Foundation, Inc.Inventors: Simon H. Bauer, Huy-Zu Cheng
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Patent number: 5210358Abstract: Solid solution catalyst in particulate form consisting of attrition resistant .alpha.-Al.sub.2 0.sub.3 particles with 0.5 to 10% by weight, expressed as the oxide, of iron cations substituted for aluminum cations in said catalyst support stabilized with 0.5 to 10% by weight, expressed as the oxide, of lanthanum and modified with at least two, preferably three, metal cations selected from the metals consisting of chromium, cobalt, magnesium, manganese, and barium; wherein one of said metal cations is barium and said catalyst has X-ray diffraction pattern with peak positions different than that of the .alpha.-Al.sub.2 0.sub.3 structure. A process is disclosed which produces ethylene from ethane while producing reduced amounts of vinyl chloride from said ethane to ethylene process.Type: GrantFiled: February 27, 1992Date of Patent: May 11, 1993Assignee: The B.F. Goodrich CompanyInventor: Angelo J. Magistro
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Patent number: RE35632Abstract: In an improved method for converting methane to at least one higher hydrocarbon product and coproduct water which comprises contacting a gas comprising methane and at least one added gaseous oxidant with nonacidic solid, the improvement comprising conducting at least a portion of said contacting in the presence of added water.Type: GrantFiled: January 19, 1993Date of Patent: October 14, 1997Assignees: Atlantic Richfield Company, Phillips Petroleum CompanyInventor: David W. Leyshon
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Patent number: RE35633Abstract: In an improved method for converting methane to at least one higher hydrocarbon product and coproduct water which comprises contacting a gas comprising methane and at least one added gaseous oxidant with nonacidic solid, the improvement comprising conducting at least a portion of said contacting in the presence of added water.Type: GrantFiled: January 19, 1995Date of Patent: October 14, 1997Assignee: Atlantic Richfield CompanyInventor: David W. Leyshon