Group Ib Metal Containing Catalyst Utilized For The Fischer-tropsch Reaction (i.e., Cu, Ag, Or Au) Patents (Class 518/713)
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Patent number: 4670474Abstract: Crystalline palladium or platinum ferrometallosilicate compositions are prepared from a silica-containing mixture by digesting a reaction mixture comprising (a) a tetraalkylammonium compound, (b) a sodium hydroxide, (c) a titanium compound, an aluminum compound, or a manganese compound, (d) an oxide of silicon, (e) an iron ion source, (f) optionally, a chelating agent and (g) water to provide a crystalline ferrometallosilicate which is then palladium or platinum ion-exchanged. Conversion of synthesis gas to low molecular hydrocarbons with high C.sub.2 -C.sub.3 alkanes selectivity employing these new ferrometallosilicates as catalysts is also disclosed.Type: GrantFiled: July 1, 1985Date of Patent: June 2, 1987Assignee: National Distillers and Chemical CorporationInventors: James A. Hinnenkamp, Vernon V. Walatka
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Patent number: 4670473Abstract: Conversion of syn gas to methanol and higher alkanols wherein alkanols are added to a syn gas reactor. Lower alkanols are homologated to higher alkanols. Liquid methanol is added as an interstage quench.Type: GrantFiled: August 9, 1985Date of Patent: June 2, 1987Assignee: Amoco CorporationInventors: Robert H. Walker, David A. Palmer, Donna M. Salvatore, Edward J. Bernier
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Patent number: 4668656Abstract: An alcohol mixture suitable for combining with gasoline is produced by contacting synthesis gas at elevated temperature and pressure with an oxide complex catalyst containing copper, thorium, an alkali metal and at least one other specific element.Type: GrantFiled: February 6, 1986Date of Patent: May 26, 1987Assignee: The Standard Oil CompanyInventors: Harley F. Hardman, Ronald I. Beach
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Patent number: 4666945Abstract: A catalyst composition comprising copper oxide, zinc oxide and zirconium oxide, the content of zirconium oxide being 30 to 70% by weight. This catalyst composition is useful for synthesis of methanol from carbon monoxide and/or carbon dioxide and hydrogen by a gas-liquid-solid phase fluidized bed method or a gas-solid phase fluidized bed method.Type: GrantFiled: September 11, 1985Date of Patent: May 19, 1987Assignee: Mitsubishi Gas Chemical Company, Inc.Inventors: Minoru Osugi, Makoto Takagawa, Tadasi Nakamura, Takashi Kojima, Kinya Tsuji
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Copper-zirconium-manganese-containing catalysts and processes for making alcohol mixtures using same
Patent number: 4666944Abstract: A catalylst is disclosed which has the formulaCu.sub.a ZrMn.sub.b Y.sub.c A.sub.d O.sub.xwhereinY is selected from the group consisting of Al, Zn, Ce, Cr, Co, Pd, Pt, Rh, Ag, Ru, Re, Os, Ta, Nb or a mixture of two or more thereof,A is an alkali or alkaline earth metal or a mixture of alkali and/or alkaline earth metals,a is from about 0.1 to about 3,b is from about 0.01 to about 3,c is from 0 to about 3,d is from about 0.02 to about 2.5, andx is the number of oxygens needed to fulfill the valence requirements of the other elements. A process for making alcohol mixtures is also disclosed which comprises contacting a gaseous reactant containing hydrogen and carbon monoxide (e.g., synthesis gas) with the foregoing catalyst.Type: GrantFiled: September 4, 1985Date of Patent: May 19, 1987Assignee: The Standard Oil CompanyInventors: Terry J. Mazanec, John G. Frye, Jr. -
Patent number: 4663355Abstract: The addition of an inert metal component, such as gold, silver or copper, to a Fischer-Tropsch catalyst comprising cobalt enables said catalyst to convert synthesis gas to liquid motor fuels at about 240.degree.-370.degree. C. with advantageously reduced selectivity of said cobalt for methane in said conversion. The catalyst composition can advantageously include a support component, such as a molecular sieve, co-catalyst/support component or a combination of such support components.Type: GrantFiled: May 21, 1986Date of Patent: May 5, 1987Assignee: Union Carbide CorporationInventor: Peter K. Coughlin
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Patent number: 4659742Abstract: Process for manufacturing a mixture of methanol and higher alcohols by reacting carbon oxides with hydrogen in the presence of a catalyst containing simultaneously copper, cobalt, aluminum and at least one alkali or alkaline-earth metal A selected from lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium and barium, in respective atomic ratios of Cu/Co=0.1-5, Al/co=0.7-4, A metals/Co=0.05-3.5, the proportion by weight of each metal to the total metals weight being respectively: copper: 10-65%, cobalt: 5-50%, aluminum: 5-40%, metal A: 0.1-15%, the homogeneity of the catalyst being such that the atomic ratio cobalt/aluminum does not vary by more than 15% with respect to its average value, on a scale of 5 nanometers.Type: GrantFiled: July 1, 1985Date of Patent: April 21, 1987Assignee: Institut Francais du PetrolInventors: Philippe Courty, Daniel Durand, Andre Sugier, Edouard Freund
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Patent number: 4657887Abstract: A catalyst composition containing alkali metal or alkaline earth metal uranate suitable for the conversion of mixtures of carbon monoxide and hydrogen has the formulaCu.sub.a U M.sub.b A.sub.c O.sub.xwhere M is one or more metals selected from the group consisting of Th, Pd, Mn, Cr, Fe, Co, Zn, Ce, V, Ru, Rh, Al, Re, Os, Pt, Ir, Ag, Ti, La and Zr, A is an alkaline or alkali earth metal anda is from 0.01 to 5.0;b is from 0 to 5.0 with the proviso that when M is Th the value of b is less than 1;c is a number up to 5.0 selected so that the catalyst composition contains more than 2 percent by weight of Metal A;x is a number such that the valence requirements of the other elements for oxygen are satisfied.The catalyst composition can be used to prepare an alcohol composition containing at least 30 percent by weight of methanol, the remainder of said composition comprising higher alcohols, the distribution of which on a methanol-free basis isC.sub.2 -10 to 90 weight percentC.sub.3 -15 to 60 weight percentC.sub.Type: GrantFiled: July 15, 1985Date of Patent: April 14, 1987Assignee: The Standard Oil CompanyInventors: Harley F. Hardman, Terry J. Mazanec, John G. Frye, Jr.
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Patent number: 4657888Abstract: A process for the production of a catalyst containing metallic copper, silver, gold, platinum or palladium in finely divided form as basic metal and at least one metal of Group VIII of the Periodic System of Elements as active component on an inert, refractory support, the catalyst containing the basis metal being heated to a temperature above 100.degree. C. and one or more carbonyls of metals different from the basis metal and belonging to Group VIII of the Periodic System of Elements being allowed to act on the heated catalyst so that those metals are alloyed into the basis metal. The invention also refers to catalysts obtained by such process.Type: GrantFiled: December 21, 1984Date of Patent: April 14, 1987Assignee: VEG-Gasinstituut N.V.Inventors: Carolus M. A. M. Mesters, John W. Geus, Eugene G. M. Kuijpers, Onno L. J. Gijzeman
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Patent number: 4654321Abstract: A process is provided for the upgrading of synthesis gas to hydrocarbons and oxygenated hydrocarbons, particularly olefins and carboxylic acids by contacting synthesis gas with catalysts comprising the mixed oxides of ruthenium, copper, an alkali or alkaline earth metal, and optionally a metal selected from Ce, Cr, Fe, Mn, Mo, Th, Zn or mixtures thereof. The synthesis gas upgrading product may be contacted with a hydrogenation catalyst to provide alkanes, alcohols and esters, useful for fuels.Type: GrantFiled: July 23, 1984Date of Patent: March 31, 1987Assignee: The Standard Oil CompanyInventors: Frederick A. Pesa, Anne M. Graham
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Patent number: 4623668Abstract: Methanol is prepared by catalytic conversion of a synthesis gas mixture, containing hydrogen, carbon monoxide, carbon dioxide and/or water, at from 200.degree. to 320.degree. C. and under from 30 to 300 bar in adiabatic and/or isothermal reactions in the presence of a catalyst containing copper and zinc, by a process in which the fresh catalyst is reduced with a hydrogen-containing gas before the start-up of the process, and then the synthesis is started under conventional conditions and is continued until the formation of methanol in the reaction zone has declined substantially, after which the reaction is interrupted and the catalyst is regenerated.Type: GrantFiled: May 25, 1984Date of Patent: November 18, 1986Assignee: BASF AktiengesellschaftInventors: Franz J. Broecker, Gerd Duembgen, Wolfgang Pies, Gottfried Schlichthaerle, Guenter Weber
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Patent number: 4621102Abstract: Slurried, high surface area, Cu and Group IA or IIA dual metal promoted Mn-Fe spinels which are fully reduced and carburized provide exceptionally high catalytic activity and selectivity in the conversion of CO/H.sub.2 to alpha-olefins, particularly when reduced and carbided in-situ. These copper and Group IA or IIA metal promoted iron-manganese catalysts maintain good activity and selectivity under low pressure reaction conditions.Type: GrantFiled: December 26, 1985Date of Patent: November 4, 1986Assignee: Exxon Research and Engineering Co.Inventors: Rocco A. Fiato, Stuart L. Soled
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Patent number: 4618723Abstract: Carbon monoxide and carbon dioxide are upgraded to valuable organic compounds, such as methanol, methane, propylene, and the like, by a thermochemical process comprising:(a) contacting the carbon monoxide and/or carbon dioxide with hydrogen sulfide to form carbonyl sulfide,(b) contacting the carbonyl sulfide with oxygen to form carbon monoxide and sulfur dioxide, and(c) hydrogenating at least one of carbon monoxide and carbonyl sulfide to the desired organic compound.Type: GrantFiled: December 10, 1982Date of Patent: October 21, 1986Assignee: The Standard Oil CompanyInventors: Daniel R. Herrington, Philip L. Kuch
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Patent number: 4617283Abstract: The addition of an inert metal component, such as gold, silver or copper, to a Fischer-Tropsch catalyst comprising cobalt enables said catalyst to convert synthesis gas to liquid motor fuels at about 240.degree.-370.degree. C. with advantageously reduced selectivity of said cobalt for methane in said conversion. The catalyst composition can advantageously include a support component, such as a molecular sieve, co-catalyst/support component or a combination of such support components.Type: GrantFiled: June 27, 1984Date of Patent: October 14, 1986Assignee: Union Carbide CorporationInventor: Peter K. Coughlin
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Patent number: 4617288Abstract: Synthesis gas (a mixture of hydrogen gas and carbon monoxide) is converted to hydrocarbons by flowing the gas first over iron-containing Fischer-Tropsch catalyst and then over a zeolite. The Fischer-Tropsch catalyst contains relatively little nitrogen as a result of its preparation by continuous precipitation at a pH ranging from about 6.6 to 6.9 and a temperature ranging from about 80.degree. to about 100.degree. C.Type: GrantFiled: December 31, 1984Date of Patent: October 14, 1986Assignee: Mobil Oil CorporationInventors: Weldon K. Bell, Werner O. Haag, Garry W. Kirker, Donald J. Klocke
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Patent number: 4616000Abstract: A ruthenium-free catalyst suitable for the conversion of carbon monoxide and hydrogen to alcohols, particularly methanol, comprises a mixture of metal oxides of the metals copper and beryllium where the atomic ratio of copper to beryllium is from about 0.01 to 1 to 20.0 to 1. A further metal M such as Th or Al may also be present, the atomic ratio of the metal M to beryllium being from about 0.1 to 1 to 7.5 to 1.The catalyst can be employed as convert carbon monoxide and hydrogen at elevated temperature and pressure, for example 100.degree. to 500.degree. C. and 150 to 4000 psig, to a product rich in alcohols and low in acids and hydrocarbons.Type: GrantFiled: August 9, 1985Date of Patent: October 7, 1986Assignee: The Standard Oil CompanyInventors: Terry J. Mazanec, John G. Frye, Jr., Harley F. Hardman
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Patent number: 4616040Abstract: A method is provided for preparing a mixture of lower aliphatic alcohols characterized by containing a substantial proportion of aliphatic alcohols having from 2 to 6 carbon atoms by reacting a mixture of carbon monoxide and hydrogen under suitable conditions of temperature and pressure in the presence of a catalyst comprising molybdenum, a metal from the group consisting of cobalt, iron and nickel, and copper, said catalyst being modified by the addition of a promoter from the class consisting of potassium, cesium and rubidium, said promoter being employed at a concentration ranging from about 1.8 to 13.0 micromoles of said alkali per square meter of surface area of said catalyst.Type: GrantFiled: July 22, 1985Date of Patent: October 7, 1986Assignee: Texaco Inc.Inventors: Michael V. Grazioso, Edwin R. Kerr, deceased, Richard F. Love, David A. Storm
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Patent number: 4614750Abstract: A catalyst is disclosed which comprises a ruthenium-copper-containing complex of the formulaM.sub.a A.sub.b RuCu.sub.c N.sub.z O.sub.xwhereinM is selected from the group consisting of Ce, Cr, Fe, Mn, and mixtures thereof,A is an alkali metal, alkaline earth metal or mixture thereof,a is from 0 to about 1,b is from about 0.002 to about 10,c is from about 0.2 to about 20,z is from 0 to about 1% by weight,x is the number of oxygens needed to fulfill the valence requirements of the other elements, said complex being supported by an activated carbon support having a surface area of at least about 300 square meters per gram.A process for converting mixtures of hydrogen and carbon monoxide, particularly synthesis gas, to alcohol with minimal levels of hydrocarbon by-products being formed is also disclosed.Type: GrantFiled: September 23, 1985Date of Patent: September 30, 1986Assignee: The Standard Oil CompanyInventors: Thomas G. Attig, Anne M. Graham, Frederick Pesa
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Patent number: 4609678Abstract: An alcohol mixture suitable for combining with gasoline is produced by contacting synthesis gas at elevated temperature and pressure with an oxide complex catalyst containing copper, thorium, an alkali metal and at least one other specific element.Type: GrantFiled: June 13, 1985Date of Patent: September 2, 1986Assignee: The Standard Oil CompanyInventors: Harley F. Hardman, Ronald I. Beach
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Patent number: 4607055Abstract: A method is provided for preparing a mixture of lower aliphatic alcohols characterized by containing a substantial proportion of aliphatic alcohols having from 2 to 6 carbon atoms by reacting a mixture of carbon monoxide and hydrogen under suitable conditions of temperature and pressure in the presence of a catalyst comprising molybdenum, a metal from the group consisting of cobalt, iron and nickel, and silver, said catalyst being modified by the addition of a promoter from the class consisting of potassium, cesium and rubidium, said promoter being employed at a concentration ranging from about 1.8 to 13.0 micromoles of said alkali per square meter of surface area of said catalyst.Type: GrantFiled: July 3, 1985Date of Patent: August 19, 1986Assignee: Texaco Inc.Inventors: Michael V. Grazioso, David A. Storm
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Patent number: 4607020Abstract: Slurried, high surface area, Cu promoted Fe-Co spinels which are fully reduced/carburized provide exceptionally high activity and selectivity in the conversion of CO/H.sub.2 to alpha-olefins, particularly when carbided in-situ in the reactor. These copper iron-cobalt catalysts maintain good activity and selectivity under low pressure reaction conditions.Type: GrantFiled: May 20, 1985Date of Patent: August 19, 1986Assignee: Exxon Research and Engineering Co.Inventors: Stuart L. Soled, Rocco A. Fiato
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Patent number: 4605639Abstract: A catalyst is described for the synthesis of hydrocarbons from CO+H.sub.2 utilizing a porous Al.sub.2 O.sub.3 support impregnated with iron and copper and optionally promoted with an alkali metal. The use of an Al.sub.2 O.sub.3 support results in the suppression of heavy waxes (C.sub.26 + hydrocarbons), particularly in slurry phase operation, when compared to unsupported or co-precipitated catalysts.Type: GrantFiled: July 17, 1985Date of Patent: August 12, 1986Assignee: Air Products and Chemicals, Inc.Inventors: Paul N. Dyer, Ronald Pierantozzi
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Patent number: 4598061Abstract: Catalyst for the synthesis of alcohol mixtures containing methanol and higher aliphatic alcohols from CO and H.sub.2, which contains, as an oxide precursor,(a) copper oxide and zinc oxide, which can be transformed into the catalytically active state by reduction with hydrogen;(b) aluminum oxide as a thermostabilizing substance and(c) at least one alkali carbonate or alkali oxide,the oxidic precursor comprising from 20 to 70% of the total volume of pores having a diameter between 14 and 7.5 nm, the alkali content being 13-130.times.10.sup.-6 gram atom alkali metal per gram of the oxidic precursor, and the aluminum oxide component having been obtained from a colloidally dispersed aluminum hydroxide gel or sol.Type: GrantFiled: January 25, 1985Date of Patent: July 1, 1986Assignee: Sud-Chemie AktiengesellschaftInventors: Michael Schneider, Karel Kochloefl, Ortwin Bock
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Patent number: 4595672Abstract: Self-promoted molybdenum and tungsten sulfide hydrotreating catalysts are prepared by heating one or more water soluble catalyst precursors in a non-oxidizing atmosphere in the presence of sulfur at a temperature of at least about 200.degree. C. The precursors will be one or more compounds of the formula ML(Mo.sub.y W.sub.1-y O.sub.4) wherein M is one or more promoter metals selected from the group consisting essentially of Mn, Fe, Co, Ni, Cu, Zn and mixtures thereof, wherein O.ltoreq.y.ltoreq.1 and wherein L is a nitrogen containing, neutral multidentate, chelating ligand. In a preferred embodiment the ligand L will comprise one or more chelating alkyl di or triamines and the non-oxidizing atmosphere will comprise H.sub.2 S.Type: GrantFiled: December 11, 1984Date of Patent: June 17, 1986Assignee: Exxon Research and Engineering Co.Inventors: Teh C. Ho, Larry E. McCandlish
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Patent number: 4595702Abstract: This invention provides a process for converting synthesis gas to hydrocarbon fuels in the C.sub.5 -C.sub.24 (gasoline and distillate) range. The conversion proceeds with minimal formation of by-product fractions. The conversion is accomplished with a low nitrogen content iron catalyst intimately mixed with a selected zeolite.Type: GrantFiled: April 3, 1985Date of Patent: June 17, 1986Assignee: Mobil Oil CorporationInventors: Yung F. Chu, James A. Brennan, Arthur W. Chester
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Patent number: 4590176Abstract: A catalyst for the production of dimethyl ether from syngas, which comprises mixing a dehydration catalyst with a methanol synthesis catalyst comprising copper, zinc, chromium and/or aluminum which has been prepared by low-temperature co-precipitation from an aqueous solution containing specified amounts of the metals concerned.Type: GrantFiled: April 5, 1985Date of Patent: May 20, 1986Assignee: Shell Oil CompanyInventors: Arend Hoek, Martin F. M. Post, Johannes K. Minderhoud
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Patent number: 4584323Abstract: Slurried, high surface area, copper promoted Fe-Co spinels which are fully reduced/carburized provide exceptionally high activity and selectivity in the conversion of CO/H.sub.2 to alpha-olefins. These copper promoted iron-cobalt catalysts maintain good activity and selectivity under low pressure reaction conditions.Type: GrantFiled: May 20, 1985Date of Patent: April 22, 1986Assignee: Exxon Research and Engineering Co.Inventors: Stuart L. Soled, Rocco A. Fiato
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Patent number: 4582858Abstract: A process for producing a mixed alcohol by contacting a synthesis gas with a catalyst, wherein the catalyst is a solid substance prepared by:calcining a mixture of (A) a copper compound, (B) a nickel compound, and (C) a compound of at least one metal selected from the metals belonging to Groups II-VII of the Periodic Table;impregnating the above-calcined product with (D) an alkali metal compound and/or an alkaline earth metal compound;calcining the resulting mixture; andreducing the thus-calcined product.The selectivity of the mixed alcohol is high in the process of the present invention. This is one of the advantages of the present invention. Furthermore the proportion of alcohols other than methanol in the mixed alcohol is relatively high, and thus the mixed alcohol is suitable for use as an alcohol component to be compounded to gasoline.Type: GrantFiled: June 7, 1985Date of Patent: April 15, 1986Assignee: Research Association for Petroleum Alternatives DevelopmentInventors: Masatoshi Shibata, Yoshinobu Aoki, Tsutomu Uchiyama
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Patent number: 4576968Abstract: A catalyst composition suitable for use in the production of alcohols from synthesis gas comprises as essential elements:(a) cobalt(b) one or more of copper, silver, gallium, zirconium, zinc and thorium(c) one or more of palladium, platinum and nickel, and(d) one or more alkali metals,in the atomic ratio of component (a): component (b): component (c) of 100:1 to 400:1 to 500, the alkali metal or metals forming up to 5% by weight of the composition. A suitable catalyst composition has the empirical formula:.sup.(a) 100 .sup.(b) 1 to 400 .sup.(c) 1 to 500 .sup.(d) x.sup.Oywherein (a), (b), (c) and (d) are as above, the value of x is such that (d) forms up to 5% by weight of the composition and y is a number such that the valence requirements of the other elements for oxygen is satisfied.Type: GrantFiled: October 9, 1984Date of Patent: March 18, 1986Assignee: The British Petroleum Company P.L.C.Inventors: Barry Nay, David G. Stewart
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Patent number: 4568698Abstract: Catalysts comprising a medium to large port zeolite modified by the oxide or acid of an element selected from the group consisting of Group IIIA to VIIA elements and, a Fischer-Tropsch catalyst wherein the ratio of zeolite to Fischer-Tropsch component is from about 0.1 to 50:1 can be employed to produce fuel grade saturated gaseous hydrocarbons from synthesis gas. A process is employed which includes the step of contacting synthesis gas over the foregoing catalyst at a reaction temperature of from about 100.degree. C. to 500.degree. C. and at a pressure of from about one atmosphere (0.1 MPa) to about 200 atmospheres (20 MPa) and at a gas hourly space velocity of from about 10 to 100,000. A method is also provided for the preparation of the combination catalyst. The catalyst and process for its use results in a small liquid aromatic product also being formed which is suitable for forming gasoline. Olefins and oxygenates are essentially eliminated.Type: GrantFiled: September 21, 1984Date of Patent: February 4, 1986Assignee: The Standard Oil CompanyInventors: Michael J. Desmond, Marc A. Pepera
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Patent number: 4565803Abstract: A catalyst composition for the conversion of syngas to methanol which comprises copper, zinc and a modifier selected from the group consisting of yttrium, a lanthanide element, an actinide element and mixtures thereof supported on a zinc-aluminum oxide spinel carrier.Type: GrantFiled: December 16, 1983Date of Patent: January 21, 1986Assignee: Shell Oil CompanyInventors: Galeon W. Schoenthal, Lynn H. Slaugh
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Patent number: 4562174Abstract: The inclusion of salts of rubidium or cesium or mixtures thereof in a catalyst comprised of copper and zinc oxides and optionally manganese oxide or manganese and cobalt oxides and a stabilizer such as chromic, ceric, magnesium or aluminum oxides results in higher yields of C.sub.1 to C.sub.6 alkanols and lower production of hydrocarbons in the effluent from the catalytic reaction environment. The reactant gases passing over the catalyst comprises hydrogen and carbon monoxide and optionally carbon dioxide if economically advantageous.Type: GrantFiled: May 21, 1984Date of Patent: December 31, 1985Assignee: Alberta Gas Chemicals Ltd.Inventor: Alvin B. Stiles
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Patent number: 4560672Abstract: A catalyst is disclosed which comprises a ruthenium-copper-containing complex of the formulaM.sub.a A.sub.b RuCu.sub.c N.sub.z O.sub.xwhereinM is selected from the group consisting of Ce, Cr, Fe, Mn, and mixtures thereof,A is an alkali metal, alkaline earth metal or mixture thereof,a is from 0 to about 1,b is from about 0.002 to about 10,c is from about 0.2 to about 20,z is from 0 to about 1% by weight,x is the number of oxygens needed to fulfill the valence requirements of the other elements, said complex being supported by an activated carbon support having a surface area of at least about 300 square meters per gram. A process for converting mixtures of hydrogen and carbon monoxide, particularly synthesis gas, to alcohol with minimal levels of hydrocarbon by-products being formed is also disclosed.Type: GrantFiled: June 4, 1984Date of Patent: December 24, 1985Assignee: The Standard Oil CompanyInventors: Thomas G. Attig, Anne M. Graham, Frederick Pesa
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Patent number: 4559316Abstract: A catalyst is disclosed which has the formulaCu.sub.a ZrMn.sub.b Y.sub.c A.sub.d O.sub.xwhereinY is selected from the group consisting of Al, Zn, Ce, Cr, Co, Pd, Pt, Rh, Ag, Ru, Re, Os, Ta, Nb or a mixture of two or more thereof,A is an alkali or alkaline earth metal or a mixture of alkali and/or alkaline earth metals,a is from about 0.1 to about 3,b is from about 0.01 to about 3,c is from 0 to about 3,d is from about 0.02 to about 2.5, andx is the number of oxygens needed to fulfill the valance requirements of the other elements. A process for making alcohol mixtures is also disclosed which comprises contacting a gaseous reactant containing hydrogen and carbon monoxide (e.g., synthesis gas) with the foregoing catalyst.Type: GrantFiled: September 21, 1984Date of Patent: December 17, 1985Assignee: The Standard Oil CompanyInventors: Terry J. Mazanec, John G. Frye, Jr.
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Patent number: 4559207Abstract: A reactor is provided for producing methanol by the reaction of synthesis gases containing carbon oxides and hydrogen in contact with a copper containing catalyst positioned in the reactor in catalyst tubes surrounded by boiling water under pressure. The catalyst tubes are made from a metallic material which is catalytically inactive with respect to the methanol synthesis gas and have approximately the same coefficient of thermal expansion as the shell of the reactor. The catalyst tubes are made of a steel composed of mixed austeniticferritic structure and containing 10-30% by weight chromium.Type: GrantFiled: November 28, 1983Date of Patent: December 17, 1985Assignee: Metallgesellschaft AGInventors: Heinz Hiller, Emil Supp, Friedemann Marschner, Hans Kupfer, Lutz Weidemann
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Patent number: 4555526Abstract: Contacting a mixture of hydrogen, carbon monoxide and/or carbon dioxide with an intimate mixture of a carbon monoxide and/or carbon dioxide reducing catalyst such as a Fischer-Tropsch catalyst, and a catalyst carrier comprising a metal oxide having a very narrow pore size distribution in the micropores within the range of between 10 and 100 Angstroms, to produce hydrocarbon mixtures useful in the manufacture of gasoline kerosene and light oil.Type: GrantFiled: July 13, 1984Date of Patent: November 26, 1985Assignee: Daido Sanso K. K.Inventors: Tadahiro Wakui, Tadahiko Handa
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Patent number: 4547273Abstract: Disclosed is a method of carrying out a mobile atom insertion reaction, such as a hydrogen insertion reaction, for the synthesis of reduced, hydrogenated compounds. Such reactions include the production of ammonia and hydrazine from nitrogen, formic acid and methanol from carbon dioxide, and hydrogen peroxide from oxygen. The insertion reactions are carried out at a bipolar mobile atom transmissive membrane comprising a membrane formed of a mobile atom pump material, as a hydrogen pump material, conductive atom transmissive means on one surface of the membrane and conductive atom transmissive means on the opposite surface of the membrane. The mobile atom, such as hydrogen, diffuses across the membrane, to provide a source of hydrogen on the insertion reaction side of the membrane. The insertion reaction side of the membrane is positively biased with respect to a counterelectrode so that a reactant molecule, such as carbon dioxide, is electrosorbed on that surface of the membrane.Type: GrantFiled: June 7, 1984Date of Patent: October 15, 1985Assignee: Energy Conversion Devices, Inc.Inventor: William Ayers
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Patent number: 4547482Abstract: A catalyst composition comprising copper oxide, zinc oxide and an oxyacid of phosphorus or its salt; and a method for producing methanol by reacting carbon monoxide and/or carbon dioxide with hydrogen in the vapor phase in the presence of a catalyst, wherein the catalyst is the aforesaid catalyst composition which has been activated by reduction with a hydrogen-containing gas.Type: GrantFiled: July 20, 1983Date of Patent: October 15, 1985Assignee: Mitsubishi Gas Chemical Company, Inc.Inventors: Minoru Osugi, Tadasi Nakamura, Shuji Ebata
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Patent number: 4547525Abstract: Methane production in catalytic Fischer-Tropsch hydrocarbon synthesis reactions is reduced by adding olefins to the H.sub.2 and CO feed mixture. Alpha olefins of ten carbon atoms or less are particularly preferred.Type: GrantFiled: December 19, 1983Date of Patent: October 15, 1985Assignee: Exxon Research and Engineering Co.Inventor: Chang J. Kim
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Patent number: 4544673Abstract: Low molecular weight hydrocarbons are produced by contacting carbon monoxide and hydrogen at elevated temperatures and pressures with a catalyst comprising oxides of chromium, molybdenum and/or tungsten, copper, thorium or uranium and at least one alkali or alkaline earth metal. Catalysts are provided which are prepared by the procedure of adding an alkali or alkaline earth metal carbonate to an aqueous solution or slurry containing decomposable salts of thorium or uranium and copper chromate, copper tungstate and/or copper molybdate to form a precipitate. The precipitate is heated, neutralized, dried and thereafter calcined and reduced.Type: GrantFiled: March 30, 1984Date of Patent: October 1, 1985Assignee: Standard Oil CompanyInventors: Michael F. Lemanski, Wayne R. Kliewer
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Patent number: 4540713Abstract: An alcohol mixture suitable for combining with gasoline is produced by contacting synthesis gas at elevated temperature and pressure with an oxide complex catalyst containing copper, thorium, an alkali metal and at least one other specific element.Type: GrantFiled: August 7, 1984Date of Patent: September 10, 1985Assignee: The Standard Oil CompanyInventors: Harley F. Hardman, Ronald I. Beach
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Patent number: 4537909Abstract: The preparation of alcohols from synthesis gas has been beneficiated by the use of a novel five-component catalyst system comprising an iron group metal and an activity improving amount of a precious metal such as rhodium.Type: GrantFiled: February 28, 1984Date of Patent: August 27, 1985Assignee: Phillips Petroleum CompanyInventors: Fan-Nan Lin, Filippo Pennella
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Patent number: 4535071Abstract: Catalyst for methanol synthesis, containing(a) as catalytically active substances copper oxide and zinc oxide, which, if desired, may be at least partially reduced, and(b) as thermostabilizing substance aluminum oxide.The proportion of pores with a diameter of 20 to 75 .ANG. (mesopores) is at least 20% and the proportion of pores with a diameter of more than 75 .ANG. (macropores) is at most 80%. The desired pore distribution can be obtained by using colloidally dispersed aluminum oxide or hydroxide in the production of the catalyst.Type: GrantFiled: May 16, 1984Date of Patent: August 13, 1985Assignee: Sud Chemie AktiengesellschaftInventors: Michael Schneider, Karel Kochloefl, Jurgen Ladebeck
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Patent number: 4529738Abstract: Improved process for manufacturing methanol by reacting carbon monoxide and/or carbon dioxide with hydrogen. The reactant gases circulate downwardly in admixture with a liquid phase of inert diluent through a methanol synthesis fixed bed catalyst. The superficial velocities of the gas phase and of the liquid phase are at least 1.5 cm per second, under the reaction conditions.Type: GrantFiled: May 25, 1983Date of Patent: July 16, 1985Assignee: Institut Francais du PetroleInventors: Andre Sugier, Francois Audibert, Hugo Van Landeghem, deceased
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Patent number: 4525482Abstract: This invention provides an improved, simple and energy saving process for producing a gas containing methane, which process utilizes a reactor having a catalyst bed of a structure wherein a synthesis gas is allowed to pass perpendicularly to the longitudinal directions of a plurality of cooling tubes installed vertically within the catalyst bed. Within the cooling tubes, a liquid coolant at its boiling temperature is flowed upwardly under pressure. A portion of the reaction product gas leaving the catalyst bed is mixed, without cooling, with fresh feed gas and is recirculated to the catalyst bed. The amount of the recycled gas is less than 5 times the amount of fresh feed gas. The foregoing process produces a product gas containing methane from a feed gas containing carbon monoxide and hydrogen.Type: GrantFiled: March 22, 1984Date of Patent: June 25, 1985Assignee: Toyo Engineering CorporationInventors: Kozo Ohsaki, Katsutoshi Kikuchi, Yoshitsugu Hirota
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Patent number: 4522938Abstract: Catalysts for the production of methanol from mixtures of carbon monoxide and hydrogen are prepared by dispersing in water a co-precipitate of zinc and at least one of chromium and aluminum together with a co-precipitate of copper, zinc and optionally at least one of chromium and aluminum, followed by spray drying of the dispersion, and calcining the spray dried material.Type: GrantFiled: November 22, 1983Date of Patent: June 11, 1985Assignee: Shell Oil CompanyInventors: Arend Hoek, Johannes K. Minderhoud, Martin F. M. Post
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Patent number: 4521394Abstract: Processes for the conversion of gases into useable products as exemplified by the reaction of carbon monoxide and hydrogen to form paraffinic hydrocarbons, hydrogen and nitrogen to form ammonia, and water and carbon monoxide to form carbon dioxide and hydrogen may be effected at reaction conditions which include temperatures in the range of from about 200.degree. to about 700.degree. C. and pressures ranging from atmospheric to about 1000 atmospheres. The catalyst system which is to be employed to effect these reactions will comprise an iron-containing compound admixed with elemental copper, and potassium-, aluminum- and vanadium-containing compounds.Type: GrantFiled: March 21, 1984Date of Patent: June 4, 1985Assignee: UOP Inc.Inventors: Hassan Windawi, Gene R. Grieger, Warren R. Oakdale
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Patent number: 4518715Abstract: This invention concerns a process for preparing ethylene glycol and lower monohydric alcohols comprising contacting a mixture of carbon monoxide and hydrogen with a catalyst comprising a ruthenium-containing compound and a copper- or silver-containing compound, both dispersed in a low-melting quaternary phosphonium salt and heating the resulting mixture at an elevated temperature and moderate pressure for sufficient time to produce the desired ethylene glycol.Type: GrantFiled: March 22, 1984Date of Patent: May 21, 1985Assignee: Texaco Inc.Inventor: John F. Knifton
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Patent number: 4513100Abstract: A catalytic system and process for producing mixtures of methanol and higher alcohols from synthesis gas, the catalytic system comprising zinc, chromium, copper, one or more alkaline metals, and possibly one or more metals chosen from molybdenum, manganese, lanthanum, cerium, aluminum, titanium and vanadium, either all or only part of said elements being chemically bonded to oxygen and/or together.Type: GrantFiled: October 28, 1982Date of Patent: April 23, 1985Assignee: Snamprogetti S.p.A.Inventors: Vittorio Fattore, Bruno Notari, Alberto Paggini, Vincenzo Lagana
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Patent number: 4507403Abstract: In a process for preparing methanol which comprises reacting a gaseous mixture containing hydrogen and either one or both of carbon monoxide and carbon dioxide in the gaseous phase in the presence of a catalyst, the improvement wherein said catalyst comprises(A) a substantially catalytically inert carrier, and(B) supported thereon, from 0.005 to 1 g in total, per gram of the carrier, of catalyst components comprising (i) a copper component, (ii) a zinc component, and optionally (iii) at least one metal component selected from aluminum, chromium, vanadium, magnesium and manganese.Type: GrantFiled: September 6, 1983Date of Patent: March 26, 1985Assignee: Mitsubishi Gas Chemical Company, Inc.Inventor: Kazuo Asakawa