Cr, Mo, Or W Patents (Class 585/662)
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Patent number: 6521808Abstract: The present invention includes a sol-gel supported catalyst for the dehydrogenation of lower alkanes, the catalyst comprising at least one active metal and at least one promoter metal attached to a sol-gel mixed oxide support. The sol-gel mixed oxide support arises from the polymerization of at least one precursor. The active metal and the promoter metal have been attached to the sol-gel mixed oxide support by the active metal and the promoter metal having been co-precipitated with the precursor of the sol-gel mixed oxide support. The invention also includes a method of making the above mentioned catalyst and a method of using the catalyst to dehydrogenate lower alkanes to produce lower alkenes.Type: GrantFiled: February 17, 2000Date of Patent: February 18, 2003Assignee: The Ohio State UniversityInventors: Umit S. Ozkan, Rick B. Watson
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Publication number: 20030032849Abstract: A chromium catalyst is disclosed for use in dehydrogenation and dehydrocyclization processes.Type: ApplicationFiled: August 23, 2002Publication date: February 13, 2003Inventors: Kostantinos Kourtakis, Leo E. Manzer
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Patent number: 6518476Abstract: The present invention provides methods for manufacturing olefins such as ethylene and propylene from lower alkanes, that is, methane, ethane and/or propane, by oxidative dehydrogenation at elevated pressure. The olefins are selectively recovered from unconverted lower alkane feed and reaction byproducts by using a complexation separation, such as an absorption separation that uses aqueous silver nitrate as the complexation agent. Catalysts are used that give high selectivity for oxidative dehydrogenation of lower alkanes to olefins at elevated pressure, such as a nonstoichiometric rare earth oxycarbonate catalyst.Type: GrantFiled: September 18, 2000Date of Patent: February 11, 2003Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Gary Lynn Culp, Vincent Joseph Stricker, James Russell Nelson, Madan Mohan Bhasin, Kenneth Andrew Nielsen
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Patent number: 6441264Abstract: A method for separating at least a benzothiophene compound from a hydrocarbon mixture is disclosed. The method includes contacting the mixture of a fraction obtained therefrom with a reagent including an acceptor complexing agent &pgr;, to obtain a donor-acceptor complex between the acceptor complexing agent and the benzothiophene compound; and separating the complex from the mixture, or from the fraction, to obtain a fraction depleted or purified in the benzothiophene compound.Type: GrantFiled: April 17, 2000Date of Patent: August 27, 2002Assignee: Total Raffinage Distribution S.A.Inventors: Marc Lemaire, Michéle Monnet, Michel Vrinat, Valérie Lamure, Emmanuelle Sanson, Alexandra Milenkovic
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Patent number: 6437210Abstract: A catalyst, method for preparing the catalyst, and method for using the catalyst having improved conversion and/or selectivity in the dehydrogenation of hydrocarbons. The catalyst being prepared by modifying and impregnating a mazzite zeolite. Modification of the original mazzite zeolite may include steps for ion-exchanging, dealuminating, physically mixing with chromic oxide, shaping, and calcining. Once modified, the mazzite zeolite may be impregnated with at least one metal selected from the group consisting of chromium, molybdenum, tungsten and oxides of these metals.Type: GrantFiled: August 3, 2000Date of Patent: August 20, 2002Assignee: Phillips Petroleum CompanyInventors: An-hsiang Wu, Charles A. Drake
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Patent number: 6362385Abstract: A process for obtaining light olefins by the dehydrogenation of corresponding paraffins, by reacting the paraffins with a catalytic system containing chromium oxide, tin oxide, at least one alkali metal oxide, and an alumina-silica carrier, and then regenerating the catalytic system in a regenerator by burning coke deposited on its surface at a temperature higher than the average temperature of the reactor.Type: GrantFiled: July 23, 1998Date of Patent: March 26, 2002Assignees: Siamprogetti S.p.A., Oao Nil YarsintezInventors: Rodolfo Iezzi, Andrea Bartolini, Franco Buonomo, Gueorgui Kotelnikov, Vladimir Bespalov
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Publication number: 20020004624Abstract: A catalyst and a process employing such catalyst for the dehydrogenation of paraffinic hydrocarbons are disclosed, wherein the catalyst comprises a platinum group metal component, a zinc component and a magnesium component on a support comprising ZSM or borosilicate.Type: ApplicationFiled: January 16, 2001Publication date: January 10, 2002Inventors: Bruce D. Alexander, George A. Huff
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Patent number: 6326523Abstract: Process for the dehydrogenation of a hydrocarbon feed comprising a step of dehydrogenating the hydrocarbon feed and a step of removing hydrogen being formed by dehydrogenation reactions, wherein the dehydrogenation and hydrogen removal steps are performed simultaneously in presence of a dehydrogenation catalyst being combined with a metal compound being reduced in presence of hydrogen.Type: GrantFiled: March 28, 2000Date of Patent: December 4, 2001Assignee: Haldor Topsoe A/SInventors: Anni Stahl, Niels Jørgen Blom, Jens Perregaard, Poul Erik Højlund Nielsen
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Publication number: 20010046942Abstract: A chromium catalyst is disclosed for use in dehydrogenation and dehydrocyclization processes.Type: ApplicationFiled: March 15, 2001Publication date: November 29, 2001Inventors: Kostantinos Kourtakis, Leo E. Manzer
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Publication number: 20010025129Abstract: Processes for oxidative dehydrogenation of alkane to one or more olefins, exemplified by ethane to ethylene, are disclosed using novel catalysts. The catalysts comprise a mixture of metal oxides having as an important component nickel oxide (NiO), which give high conversion and selectivity in the process. For example, the catalyst can be used to make ethylene by contacting it with a gas mixture containing ethane and oxygen. The gas mixture may optionally contain ethylene, an inert diluent such as nitrogen, or both ethylene and an inert diluent.Type: ApplicationFiled: March 22, 2001Publication date: September 27, 2001Applicant: Symyx Technologies, Inc.Inventor: Yumin Liu
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Patent number: 6239325Abstract: The invention provides process for oxidative dehydrogenation of lower alkanes, by vapor phase oxidative dehydrogenation of C2-C5 lower alkanes in the presence of a catalyst and molecular oxygen to produce the corresponding olefins, in which the catalyst has a composition expressed by a general formula (1) below: A&agr;Sb&bgr;W&ggr;D&dgr;Ox (1) in which A is at least one metal selected from the group consisting of molybdenum and chromium; Sb is antimony; W is tungsten; O is oxygen; and D is at least one metal selected from the group consisting of V, Nb, Ta, Fe, Co, Ni, Cu, Ag, Zn, B, Tl, Sn, Pb, Te, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce and Sm; &agr;, &bgr;, &ggr;, &dgr; and x denote atomic numbers of A, Sb, W, D and O, respectively, where when &agr;=1, &bgr;=0.5-10, &ggr;=0.1-10 and &dgr;=0-3; and x is a numerical value determined by the state of oxidation of those elements other than oxygen.Type: GrantFiled: May 18, 1999Date of Patent: May 29, 2001Assignee: Nippon Shokubai Co LtdInventors: Nobuji Kishimoto, Etsushige Matsunami
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Patent number: 6159358Abstract: A process and apparatus produces reaction products by indirectly preheating and heating reactants by indirect heat exchange. The use of the preheating step simplifies the reaction zone design by eliminating the need for external exchangers and is particularly suited for an arrangement of plates that defines narrow channels for indirect heat exchange. The narrow channels are preferably defined by corrugated plates. The primary reaction channels will contain a catalyst for the promotion of the desired reaction product from the principal reactants. The heating fluid passes through adjacent heating channels defined by shared partition plates to provide indirect heating. At least a portion of the heating channels exchange heat with a non-catalytic portion of the reaction channels to preheat the reactants ahead of a catalytic section of the reaction channels. Catalytic combustion within the heating channels may provide in-situ heat input for the heating medium.Type: GrantFiled: September 8, 1998Date of Patent: December 12, 2000Assignee: UOP LLCInventors: Robert C. Mulvaney, III, Hemant W. Dandekar
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Patent number: 6084145Abstract: A dehydrogenation catalyst is produced by a process comprising the steps of: mixing an L-zeolite, chromium(VI) oxide, a binder, and an acid to form a mixture; and calcining the mixture at a temperature of about 200-800.degree. C. A paraffin having 2-7 carbon atoms per molecule can be contacted with the above-described catalyst under dehydrogenation conditions to produce olefins having the same number of carbon atoms per molecule as the paraffin.Type: GrantFiled: April 7, 1998Date of Patent: July 4, 2000Assignee: Phillips Petroleum CompanyInventors: An-Hsiang Wu, Charles A. Drake
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Patent number: 6031143Abstract: Process for the production of styrene which comprises:a) feeding to an alkylation unit a stream of benzene and a stream of recycled product containing ethylene;b) mixing the stream at the outlet of the alkylation unit, containing ethylbenzene, with a stream consisting of ethane;c) feeding the mixture thus obtained to a dehydrogenation unit containing a catalyst capable of contemporaneously dehydrogenating ethane and ethylbenzene;d) feeding the product leaving the dehydrogenation unit to a separation section to produce a stream essentially consisting of styrene and a stream containing ethylene;e) recycling the stream containing ethylene to the alkylation unit.Type: GrantFiled: September 1, 1998Date of Patent: February 29, 2000Assignee: Snamprogetti S.p.A.Inventors: Franco Buonomo, Gianni Donati, Emilio Micheli, Lorenzo Tagliabue
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Patent number: 6028027Abstract: Catalysts comprising iron and potassium and, if desired, further elements, which catalysts are suitable for dehydrogenating hydrocarbons to give the corresponding olefinically unsaturated hydrocarbons, are prepared by calcining a finely divided dry or aqueous mixture of an iron compound with a potassium compound and, if desired, compounds of further elements in a first step that agglomerates having a diameter of from 5 to 50 .mu.m and formed from smaller individual particles are obtained and, in a second step, preferably after shaping, calcining it at from 300 to 1000.degree. C., with the maximum calcination temperature in the second step preferably being at least 30.degree. below the calcination temperature in the first step. The catalysts thus prepared are useful, in particular, for dehydrogenating ethylbenzene to give styrene.Type: GrantFiled: March 17, 1998Date of Patent: February 22, 2000Assignee: BASF AktiengesellschaftInventors: Michael Baier, Christopher William Rieker, Otto Hofstadt, Wolfgang Buchele, Wolfgang Jurgen Popel, Hermann Petersen, Norbert Neth
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Patent number: 5962757Abstract: Dehydrogenation catalysts are prepared by a predoping process comprising, mixing iron oxide materials with a predopant to form a blend of iron oxide and predopant and heating the blend to the predoping conditions and thereafter forming a catalyst. The catalysts so prepared are useful in the dehydrogenation of a composition having at least one carbon--carbon double bond. Such catalytic uses include the conversion of ethylbenzene to styrene.Type: GrantFiled: April 17, 1997Date of Patent: October 5, 1999Assignee: Shell Oil CompanyInventors: Stanley Nemec Milam, Brent Howard Shanks
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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: 5672801Abstract: The present invention concerns a regeneration process for a catalyst containing at least one metallic element selected from the group formed by platinum, palladium, ruthenium, rhodium, osmium, iridium and nickel, preferably platinum, on a refractory oxide based support, which has been deactivated by coke deposition. The regeneration process is characterised in that said regeneration consists of treatment with a gas containing at least chlorine and molecular oxygen, at a temperature between 20.degree. C. and 800.degree. C. and a total gas flow rate, expressed in litres of gas per hour and per gram of catalyst, of between 0.05 and 20. The process at least restores the initial catalytic properties of the catalyst.Type: GrantFiled: August 6, 1996Date of Patent: September 30, 1997Assignee: Institut Francais Du PetroleInventor: Blaise Didillon
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Patent number: 5597944Abstract: The dehydrogenation of n-parrofins to n-olefins is catalyzed by novel synthetic manganese oxide octahedral molecular sieves such as OMS-1 and OMS-2.Type: GrantFiled: November 7, 1994Date of Patent: January 28, 1997Assignee: Texaco Inc.Inventors: Chi-Lin O'Young, Robert A. Sawicki, Yuan-Gen Yin, Wen-Qing Xu, Steven L. Suib
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Patent number: 5585530Abstract: A process for the production of olefins comprises dehydrogenating at least one hydrogen-donor hydrocarbon that is essentially free from olefinic unsaturation, e.g. a paraffin, in the presence of a dehydrogenation catalyst and in the presence of at least one hydrogen-acceptor hydrocarbon that is more highly unsaturated than a mono-olefin, e.g. a diene and/or acetylene, under conditions effective to cause at least part of said hydrogen-donor hydrocarbon to be dehydrogenated and at least part of the hydrogen-acceptor to be hydrogenated. The amount of hydrogen-acceptor is such that there are 0.5 to 20 moles of said hydrogen-donor for each mole of hydrogen-acceptor. Preferably the amount of said hydrogen-acceptor hydrocarbon hydrogenated is such that the heat of hydrogenation of said hydrogen-acceptor hydrocarbon provides at least 25% of the heat required for dehydrogenation of said hydrogen-donor hydrocarbon. In a preferred form of the invention, a hydrocarbon stream containing a hydrogen-acceptor is a C.sub.Type: GrantFiled: June 8, 1994Date of Patent: December 17, 1996Assignee: Institut Francais Du PetroleInventors: Arthur Gough, Stephen K. Turner
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Patent number: 5563314Abstract: 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 is then passed into a second reactor containing a reducible metal oxide which serves to selectively combust hydrogen in an oxidation/reduction (REDOX) reaction. This particular mode of operation is termed a separate reactor, REDOX mode.Type: GrantFiled: May 25, 1995Date of Patent: October 8, 1996Inventors: 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: 5482616Abstract: This invention relates to a catalyst for hydrogenation and/or dehydrogenation having an improved resistance against deactivation by sulfur compounds, comprising at least one hydrogenation component, at least one metal-oxide containing component and at least one component acting as a support material, in which at least a part of the hydrogenation component and a part of the metal-oxide containing component are present on said support material as separate particles, the particles of the hydrogenation component and the particles of the metal-oxide containing component being homogeneously distributed in the catalyst.Type: GrantFiled: May 26, 1992Date of Patent: January 9, 1996Assignee: Engelhard De Meern B. V.Inventors: Nilanjan Brahma, John W. Geus, Eugene G. M. Kuijpers
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Patent number: 5315056Abstract: In a dehydrogenation process wherein catalyst is regenerated off-stream by use of heated air, at least two reactors are in the regeneration cycle, with regeneration air being heated to regeneration catalyst temperature for introduction into the first reactor, and thereafter being reheated to catalyst regeneration temperature and introduced into the second reactor. Such air may also be employed for preheating feed to the dehydrogenation reactor and/or for steam generation by heating such air to the temperature required for such procedure.Type: GrantFiled: February 14, 1992Date of Patent: May 24, 1994Assignee: ABB Lummus Crest Inc.Inventors: Robert J. Feldman, Joseph M. Dufallo, William A. Schwartz, Theodore S. Williams
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Patent number: 5304694Abstract: Catalytic conversion of a C.sub.2 -C.sub.5 alkane, e.g., isobutane and/or isopentane, to isoalkenes, e.g., isobutene and/or isopentene, respectively, is undertaken in the presence of an aromatic recycle stream which provides the heat of reaction for the conversion which is endothermic, in the absence of hydrogen.Type: GrantFiled: May 15, 1992Date of Patent: April 19, 1994Assignee: Mobil Oil CorporationInventors: Ralph M. Dessau, Quang N. Le
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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: 5227565Abstract: Barium peroxide oxidizer, together with a transition metal from Group I, III, IV, V, VII or VIII or compound thereof is used as stoichiometric reagent in the oxidative dimerization of hydrocarbons having three or four carbon atoms. Barium peroxide oxidizer, together with a transition metal from Group I, III, IV, V, VI, VII or VIII or compound thereof is used as stoichiometric reagent in the dehydrogenation of hydrocarbons having three or four carbon atoms.Type: GrantFiled: June 29, 1992Date of Patent: July 13, 1993Assignee: Sun Company, Inc. (R&M)Inventors: Vincent A. Durante, James E. Lyons
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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: 5191131Abstract: A paraffin having 5 to 10 carbon atoms is catalytically cracked in the presence of a catalytically cracking catalyst having a strong acidity, especially a rare earth metal ion-exchanged mordenite or a dealuminized mordenite, to form a paraffin having 3 or 4 carbon atoms. The formed paraffin is contacted with a dehydrogenation catalyst to obtain an olefin having 3 or 4 carbon atoms.Type: GrantFiled: December 4, 1989Date of Patent: March 2, 1993Assignee: Research Association for Utilization of Light OilInventors: Kazunori Takahata, Toshihiro Murashige, Yukimasa Shigemura, Hiroshi Takaki, Akihiko Okano
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Patent number: 5105044Abstract: There is provided a catalyst and a process for the direct partial oxidation of methane with oxygen, whereby hydrocarbons having at least two carbon atoms are produced. The catalyst used in this reaction is a spinel oxide, such as MgMn.sub.2 O.sub.4 or CaMn.sub.2 O.sub.4, modified with an alkali metal, such as Li or Na.Type: GrantFiled: October 15, 1990Date of Patent: April 14, 1992Assignee: Mobil Oil Corp.Inventors: Scott Han, Lorenzo C. DeCaul, Robert E. Palermo, Dennis E. Walsh
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Patent number: 5095161Abstract: Methane is upgraded to higher molecular weight hydrocarbons in a process using a novel catalyst comprising oxides of boron, tin and zinc. The feed admixture also comprises oxygen. The novel catalyst may comprise one or more Group I-A or II-A elements, preferably potassium and is characterized by its method of manufacture.Type: GrantFiled: August 6, 1990Date of Patent: March 10, 1992Assignee: UOPInventors: Hayim Abrevaya, Tamotsu Imai, Lisa M. Lane
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Patent number: 5053580Abstract: Metal oxide powders comprised of Cr(III) oxide, Ti(IV) oxide, V(V) oxide, or mixtures of these, or metal mixed oxides comprised of Cr(III) oxide and Ti(IV) oxide and V(V) oxide, or their mixtures. They have BET surfaces of 5-50m.sup.2 /g and mean particle diameters of 25-350 nm and are useful to increase conversion and selectivity in the manufacture of mono-olefins by catalytic dehydrogenation of saturated hydrocarbons. The metal oxide powders are produced from mixtures of the vaporized metal compounds chromyl chloride, titanium tetrachloride, and vanadyl chloride, in the presence of certain gases by laser pyrolysis.Type: GrantFiled: May 7, 1990Date of Patent: October 1, 1991Assignee: Veba Oel AktiengesellschaftInventors: Bernhard Schramm, Jurgen Kern, Harald Schwahn, August-Wilhelm Preuss, Klaus Gottlieb, Hartmut Bruderreck
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Patent number: 5025109Abstract: There is provided a process for the direct partial oxidation of methane with oxygen, whereby hydrocarbons having at least two carbon atoms are produced. The catalyst used in this reaction is a spinel oxide such as ZnMn.sub.2 O.sub.4.Type: GrantFiled: December 29, 1989Date of Patent: June 18, 1991Assignee: Mobil Oil CorporationInventors: Lorenzo C. DeCaul, Scott Han, Robert E. Palermo, Dennis E. Walsh
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Patent number: 5008481Abstract: There is provided a process for the aromatization of non-aromatic hydrocarbons having at least six carbon atoms. The non-aromatic feed is contacted with a catalyst which includes a base metal or noble metal which is incorporated into or onto a pillared layered silicate. A preferred pillared layered silicate is kenyaite containing interspathic silica, and a preferred base metal or noble metal is chromium.Type: GrantFiled: December 29, 1989Date of Patent: April 16, 1991Assignee: Mobil Oil CorporationInventors: Ivy D. Johnson, Pochen Chu, Charles T. Kresge
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Patent number: 5004856Abstract: There is provided a process for the direct partial oxidation of methane with oxygen, whereby hydrocarbons having at least two carbon atoms are produced. The catalyst used in this reaction is a cadmium-manganese oxide catalyst.Type: GrantFiled: December 29, 1989Date of Patent: April 2, 1991Assignee: Mobil Oil CorporationInventors: Lorenzo C. DeCaul, Scott Han, Robert E. Palermo, Dennis E. Walsh
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Patent number: 4956517Abstract: There is provided a process for the dehydrogenation of saturated hydrocarbons having from 2 to 5 carbon atoms. The feed is contacted with a catalyst which includes a base metal or noble metal which is incorporated into or onto a pillared layered silicate. A preferred pillared layered silicate is kenyaite containing interspathic silica, and a preferred base metal or noble metal is chromium.Type: GrantFiled: December 29, 1989Date of Patent: September 11, 1990Assignee: Mobil Oil CorporationInventors: Ivy D. Johnson, Pochen Chu, Charles T. Kresge
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Patent number: 4899003Abstract: A process for the oxydehydrogenation of ethane to ethylene in a reaction system of open series connected stages, includes changing the total water and acetic acid content in the output gaseous stream after at least one stage other than the last stage of the series.Type: GrantFiled: July 11, 1985Date of Patent: February 6, 1990Assignee: Union Carbide Chemicals and Plastics Company Inc.Inventors: Robert M. Manyik, Jonathan L. Brockwell, John E. Kendall
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Patent number: 4886931Abstract: A multi-component oxide catalyst comprising zinc and an alkali metal is described which is useful particularly for converting methane and/or natural gas to higher molecular weight hydrocarbon products such as ethane and ethylene. The catalyst is characterized by the formulaZn.sub.a A.sub.b M.sub.c M'.sub.d O.sub.xwhereinA is Li, Na, K, or mixtures thereof;M is Al, Ga, Cr, La, Y, Sc, V, Nb, Ta, Cu or mixtures thereof;M' is Cs, Rb, Mg, Ca, Sr, Ba, Sm, Pb, Mn, Sb, P, Sn, Bi, Ti, Zr, Hf, or mixtures thereof;a is from about 1 to about 20;b is from about 0.1 to about 20;c is from about 0 to about 5;d is from about 0 to about 20; andx is a number needed to fulfill the valence requirements of the other elements; provided that(i) at least one of c and d is at least 0.1; and(ii) when M' is Sn, c must be at least 0.1.Type: GrantFiled: June 4, 1987Date of Patent: December 12, 1989Assignee: The Standard Oil CompanyInventors: Joseph P. Bartek, James F. Brazdil, Jr., John M. Hupp, Robert K. Grasselli
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Patent number: 4806624Abstract: A process for the catalytic dehydrogenation of a dehydrogenatable C.sub.2 -plus feed hydrocarbon which comprises the steps of: (a) passing a feed stream comprising the C.sub.2 -plus feed hydrocarbon into a dehydrogenation zone and through at least one bed of dehydrogenation catalyst maintained at dehydrogenation conditions and producing a dehydrogenation zone effluent stream comprising hydrogen, the C.sub.2 -plus feed hydrocarbon and a C.sub.2 -plus product hydrocarbon; (b) forming an oxidation catalyst bed feed stream by admixing an oxygen-containing stream with the dehydrogenation zone effluent stream; (c) passing the oxidation catalyst bed feed stream through a bed of hydrogen selective oxidation catalyst maintained at selective oxidation conditions and producing an oxidation zone effluent stream having a reduced concentration of hydrogen; and (d) recovering the product hydrocarbon from the oxidation zone effluent stream without contacting the oxidation zone effluent stream with dehydrogenation catalyst.Type: GrantFiled: June 17, 1987Date of Patent: February 21, 1989Assignee: UOP Inc.Inventors: Raymond R. Herber, Gregory J. Thompson
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Patent number: 4717779Abstract: Dehydrogenatable hydrocarbons may be subjected to a dehydrogenation reaction in which the hydrocarbons are treated with a dehydrogenation catalyst comprising a modified iron catalyst in the presence of steam in a multicatalyst bed system. The reaction mixture containing unconverted hydrocarbons, dehydrogenated hydrocarbons, hydrogen and steam is then contacted with an oxidation catalyst whereby hydrogen is selectively oxidized. The selective oxidation catalyst which is used will comprise a noble metal of Group VIII of the Periodic Table, a metal of Group IVA and, if so desired, a metal of Group IA or IIA composited on a porous inorganic support. The inorganic support will comprise an alumina precursor which possesses and ABD less than about 0.6 g/cc, a pore volume greater than about 0.5 cc/g, and a pore distribution such that between 10% and 70% of the pore volume is present as pores whose diameters are greater than about 300 Angstroms. After peptizing and calcination at a temperature of about 900.degree.Type: GrantFiled: August 6, 1986Date of Patent: January 5, 1988Assignee: UOP Inc.Inventors: Jeffery C. Bricker, Tamotsu Imai, David E. Mackowiak
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Patent number: 4658081Abstract: Feed hydrocarbons comprising propane and butanes are cracked to selectively maximize the production of ethylene or propylene by contacting the feed hydrocarbons with a cracking catalyst, adapted to convert the feed hydrocarbons to less saturated hydrocarbons, under conditions sufficient to thus crack the feed hydrocarbons, to thereby selectively maximize the production of ethylene, and, at least intervally, hydrogen sulfide or a hydrogen sulfide precursor is added to the feed hydrocarbons to thereby maximize the production of propylene. Preferred catalysts which may be utilized in the process and which are highly selective to the production of ethylene, as opposed to propylene, (in the absence of hydrogen sulfide or hydrogen sulfide precursor) include mixed oxides of manganese and magnesium, mixed oxides of manganese and Lanthanum Series metal and/or niobium, mixed oxides of iron and magnesium and mixed oxides of iron and Lanthanum Series metal and/or niobium.Type: GrantFiled: July 25, 1985Date of Patent: April 14, 1987Assignee: Phillips Petroleum CompanyInventor: John H. Kolts
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Patent number: 4652687Abstract: Unsaturated hydrocarbons may be prepared by subjecting dehydrogenatable hydrocarbon to dehydrogenation in the presence of a dehydrogenation catalyst. The effluent stream from this step, comprising unconverted hydrocarbons, dehydrogenated hydrocarbons, hydrogen and steam, may then be passed to a selective oxidation step in which the hydrogen is selectively oxidized in the presence of an oxygen-containing gas to the substantial exclusion of the oxidation of the hydrocarbons. The oxidation catalyst which is employed will comprise a Group VIII noble metal, a Group IVA metal and a Group IA or IIA metal composited on a metal oxide support. The metal oxide support such as alumina will possess a particular configuration such as a polylobular particle containing from 3 to about 8 lobes and having a ratio of exterior surface to catalyst volume greater than [4D+2L] in which D is the largest representative diameter and L is the length of the particle.Type: GrantFiled: July 7, 1986Date of Patent: March 24, 1987Assignee: UOP Inc.Inventors: Tamotsu Imai, Jeffery C. Bricker
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Patent number: 4581339Abstract: A method for reheating of a catalytic reactor by successive oxidations and reductions of a multiple oxidation state catalyst.Heat is added to the catalyst bed by a series of successive oxidation and reduction reactions occurring on the catalyst. Both catalyst oxidation and catalyst reduction are exothermic reactions, and both reactions generate heat to increase the temperature of the catalyst bed.Type: GrantFiled: March 18, 1985Date of Patent: April 8, 1986Assignee: Air Products and Chemicals, Inc.Inventors: Bharat L. Bhatt, John F. Kirner, Pradip Rao, William A. Schwartz
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Patent number: 4568790Abstract: A process for the low temperature oxydehydrogenation of ethane to ethylene uses a calcined oxide catalyst containing Mo, V, Nb, and Sb.Type: GrantFiled: June 28, 1984Date of Patent: February 4, 1986Assignee: Union Carbide CorporationInventor: James H. McCain
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Patent number: 4560824Abstract: This invention relates to an improvement in a process for producing isobutylene by the cyclic, adiabatic dehydrogenation of isobutane. The improvement resides in diluting an isobutane feed stream with n-butane in an amount from about 3-7% by volume and recycling unreacted products plus nC.sub.4 unsaturates from the dehydrogenation zone. Additional coke is made by virtue of the use of n-butane and recycle to permit lower feed input temperature.Type: GrantFiled: May 7, 1985Date of Patent: December 24, 1985Assignee: Air Products and Chemicals, Inc.Inventors: David C. Spence, William A. Schwartz
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Patent number: 4554393Abstract: A process for the production of aromatic compounds from low-molecular weight predominantly paraffinic feedstock which comprises contacting the feedstock in a first reactor with a dehydrogenation catalyst to produce a first reaction product containing alkenes; contacting said first reaction product in a second reactor with a crystalline aluminosilicate catalyst to produce a second reaction product containing aromatics; and separating an aromatic-rich fraction therefrom. In a preferred embodiment the feedstock consists essentially of propane and/or butane.Type: GrantFiled: April 18, 1983Date of Patent: November 19, 1985Assignees: The Broken Hill Proprietary Company Limited, Commonwealth Scientific and Industrial Research OrganisationInventors: Sandra Liberts, Jack G. Creer, Thomas Mole
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Patent number: 4546204Abstract: The invention concerns a process for the manufacture of methyl t-butyl ether in which: a hydrocarbon feedstock is cracked to give an ethylene-rich stream; an isobutane-rich stream is separated from C.sub.4 -hydrocarbon stream; the ethylene-rich stream and the isobutane-rich stream are contacted over a transhydrogenation catalyst to give a mixture comprising ethane and isobutene; the isobutene is reacted with methanol to give methyl t-butyl ether; and the residual C.sub.4 -hydrocarbon stream is recycled either to the C.sub.4 -hydrocarbon stream or to the cracker and the ethane is recycled to the cracker.It has been found that combining and interconnecting a hydrocarbon cracker, a transhydrogenation reactor and an etherification reactor results in an integrated, economic process for the production of methyl t-butyl ether.Type: GrantFiled: October 29, 1984Date of Patent: October 8, 1985Assignee: Imperial Chemical Industries Australia LimitedInventor: David Parris
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Patent number: 4476344Abstract: An oxidative dehydrogenation process for a paraffin or mixture of paraffins having from 2 to 5 carbon atoms employing a catalyst composition comprising lithium, titanium and a promoter selected from the group consisting of molybdenum, tin and antimony.Type: GrantFiled: October 14, 1983Date of Patent: October 9, 1984Assignee: Phillips Petroleum CompanyInventor: James B. Kimble
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Patent number: 4447665Abstract: A method is disclosed for dehydrogenating a parafinic or naphthenic compound and for dehydrocyclizing a paraffinic compound comprising a straight chain of at least 5 carbon atoms, comprising: contacting an aforesaid compound under dehydrogenation conditions comprising a temperature in the range of from about 465.degree. C. to about 650.degree. C. with an active carbon catalyst having a cage-like structure and a BET surface area of at least 800 square meters per gram and a bulk density of at least 0.1 gram per cubic centimeter and comprising a substantially uniform dispersion of a metal, metal-containing material, or both in a porous carbon matrix, wherein the dispersed metal and metal in the dispersed metal-containing material are each a transition metal and wherein the total concentration of dispersed metal and dispersed metal-containing material is from about 0.001 to about 30 weight percent, calculated as the elemental metal and based on the weight of the catalyst.Type: GrantFiled: March 30, 1983Date of Patent: May 8, 1984Assignee: Standard Oil Company (Indiana)Inventor: Arnold N. Wennerberg
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Patent number: 4395579Abstract: The preparation of a compound of formula R.sup.1 --C(R.sup.2).dbd.CH.sub.2 (R.sup.1 and R.sup.2 are a phenyl, alkyl or alkenyl group or a hydrogen atom) by contacting a mixture of steam and a compound of formula R.sup.1 --C(R.sup.2)(H)--CH.sub.3 at elevated temperature under non-oxidative dehydrogenation conditions with a catalyst having a spinel structure allows lower ratios steam to compound of formula R.sup.1 --C(R.sup.2)(H)--CH.sub.3, a higher selectivity to the compound of formula R.sup.1 --C(R.sup.2).dbd.CH.sub.2 and a lower temperature when lithium is present in the spinel structure.Type: GrantFiled: November 4, 1982Date of Patent: July 26, 1983Assignee: Shell Oil CompanyInventors: Gilbert R. Germaine, Jean P. Darnanville