Rhodium Containing Catalyst Patents (Class 518/716)
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Publication number: 20040214905Abstract: The invention provides a process for the production of mainly C5+ hydrocarbons, which process involves contacting carbon monoxide and hydrogen at a temperature in the range of from about 180° C. to about 270° C. and elevated pressure in the presence of a catalyst composition having cobalt, manganese and at least one of rhenium and/or ruthenium on a titania carrier. The invention also relates to a catalyst composition having cobalt, manganese and rhenium on a titania carrier.Type: ApplicationFiled: May 21, 2004Publication date: October 28, 2004Inventors: Jacobus Johannes Cornelis Geerlings, Hans Michiel Huisman
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Publication number: 20040214904Abstract: A method for reducing catalyst attrition losses in hydrocarbon synthesis processes conducted in high agitation reaction systems; a method of producing an attrition-resistant catalyst; a catalyst produced by such method; a method of producing an attrition-resistant catalyst support; and a catalyst support produced by such method. The inventive method of reducing catalyst attrition losses comprises the step of reacting a synthesis gas in a high agitation reaction system in the presence of a catalyst. In one aspect, the catalyst preferably comprises a &ggr;-alumina support including an amount of titanium effective for increasing the attrition resistance of the catalyst. In another aspect, the catalyst preferably comprises a &ggr;-alumina support which has been treated, after calcination, with an acidic, aqueous solution. The acidic aqueous solution preferably has a pH of not more than about 5.Type: ApplicationFiled: May 21, 2004Publication date: October 28, 2004Applicant: Sasol Technology (UK) LimitedInventors: Alan H. Singleton, Rachid Oukaci, James G. Goodwin
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Patent number: 6800579Abstract: There is provided a process for regenerating the activity of used metal catalysts for the hydrogenation of carbon monoxide comprising decreasing the hydrocarbon content thereof, calcining under an oxidant-containing atmosphere, impregnating with a solution of at least one of a metal compound, calcining under an oxidant-containing atmosphere and activating by contacting with a hydrogen-contacting gas at elevated temperatures to form an active catalyst. The process regenerates and enhances both supported and dispersed active metal (DAM) catalysts. Used catalysts enhanced by the process are initially treated to decrease their hydrocarbon content. The treatment may be carried out in a single reactor, or by carrying out up to all steps after catalyst may be withdrawn from a reactor and returned to at least one reactor, both preferably during operation thereof. Up to all steps may be effected in a subsequent reactor, or in specialized apparatus.Type: GrantFiled: January 29, 2002Date of Patent: October 5, 2004Assignee: ExxonMobil Research and Engineering CompanyInventors: Michel Daage, Russell John Koveal, Min Chang
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Publication number: 20040192792Abstract: The present invention relates to improved catalyst compositions, as well as methods of making and using such compositions to prepare synthesis gas and ultimately C5+ hydrocarbons. In particular, preferred embodiments of the present invention comprise catalyst systems comprising a core and an outer region disposed on said core, wherein a substantial amount of the catalytic metal is located in the outer region of the catalyst support matrix. In addition, the catalyst systems are able to maintain high conversion and selectivity values with very low catalytically active metal loadings. The catalyst systems are appropriate for improved syngas, oxidative dehydrogenation and other partial oxidation reactions, including improved reaction schemes for the conversion of hydrocarbon gas to C5+ hydrocarbons.Type: ApplicationFiled: December 29, 2003Publication date: September 30, 2004Applicant: ConocoPhillips CompanyInventors: Rafael L. Espinoza, Kandaswamy Jothimurugesan, Tianyan Niu, Harold A. Wright, Shuibo Xie, Mary E. Wolf
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Publication number: 20040186188Abstract: A process for producing a clean wax product includes contacting, at an elevated temperature between 180° C. and 250° C. and at an elevated pressure between 10 bar and 40 bar, a synthesis gas comprising hydrogen and carbon monoxide with a cobalt slurry phase Fischer-Tropsch synthesis catalyst, in a slurry phase Fischer-Tropsch synthesis reaction. The catalyst is obtained from a successful catalyst support. A clean wax product containing less than 50 mass ppm submicron particulates of cobalt, is produced.Type: ApplicationFiled: May 11, 2004Publication date: September 23, 2004Inventors: Peter Jacobus Van Berge, Jan Van De Loosdrecht, Sean Barradas
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Publication number: 20040157938Abstract: A method for producing hydrocarbons, comprising: (I) subjecting to a reduction treatment a catalyst comprising a carrier having provided thereon: 0.1 to 10% by mass of at least one metal selected from an alkali metal, an alkaline earth metal, a rare earth metal and the Group III in the periodic table and 1 to 30% by mass of ruthenium, each based on the catalyst weight, the carrier comprising an aluminum oxide and a manganese oxide having an average number of charges of manganese of exceeding Mn2+, and the catalyst having a specific surface area of from 60 to 350 m2/g and a bulk density of from 0.8 to 1.8 g/ml; (II) dispersing the catalyst in liquid hydrocarbons in a concentration of from 1 to 50 w/v %; and (III) bringing the catalyst into contact with a gas mixture comprising hydrogen and carbon monoxide at a pressure of from 1 to 10 MPa, and (i) at a reaction temperature of from 170 to 300° C.Type: ApplicationFiled: October 27, 2003Publication date: August 12, 2004Inventors: Osamu Iwamoto, Shigenori Nakashizu, Kinjiro Saito, Takashi Suzuki
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Publication number: 20040132832Abstract: The present invention relates to thermally stable, high surface area alumina supports and a method of preparing such supports with at least one modifying agent. The method includes adding an aluminum modifying agent to the alumina prior to calcining. The inventive support has thermal stability at temperatures above 800° C. A more specific embodiment of the invention is a catalyst having a high surface area, thermally stable alumina support with at least one group VIII metal or rhenium and an optional promoter loaded onto the support. The present invention further relates to gas-to-liquids conversion processes, more specifically for producing C5+ hydrocarbons.Type: ApplicationFiled: November 12, 2003Publication date: July 8, 2004Applicant: ConocoPhillips CompanyInventors: Rafael L. Espinoza, Dan Fraenkel, Kevin L. Coy
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Publication number: 20040048936Abstract: A process for the production of a liquid hydrocarbon oil from a gas feed containing a lower hydrocarbon and CO2, wherein the gas feed is mixed with H2O to obtain a mixed gas having specific CO2, H2O and lower hydrocarbon contents. The mixed gas is contacted with a Rh, Ru/MgO catalyst having a specific surface area of 5 m2/g or less to produce a synthesis gas with a carbon conversion efficiency Cf of at least 50%. The thus obtained synthesis gas having a H2/CO molar ratio of 1.5-2.5 is reacted in the presence of a Fischer-Tropsch catalyst to obtain a liquid hydrocarbon oil, while the synthesis gas having a H2/CO molar ratio of 0.5-1.5 is reacted in the presence of one or more catalysts having methanol synthesizing, dehydrating and CO shift reaction activities to obtain dimethyl ether.Type: ApplicationFiled: August 28, 2003Publication date: March 11, 2004Inventors: Yoshimi Shiroto, Kenichi Kawazuishi, Masato Tauchi, Mitsunori Shimura
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Publication number: 20030162849Abstract: A method of treating an untreated catalyst support includes contacting an untreated catalyst support which is partially soluble in an aqueous acid and/or a neutral aqueous solution with a modifying component precursor of the formula Me(OR)x where Me is a modifying component selected from Si, Zr, Ti, Cu, Zn, Mn, Ba, Co, Ni, Na, K, Ca, Sn, Cr, Fe, Li, TI, Mg, Sr, Ga, Sb, V, Hf, Th, Ce, Ge, U, Nb, Ta, and W, R is an alkyl or acyl group, and x is an integer having a value of from 1 to 5. The modifying component is thereby introduced onto and/or into the catalyst support to form a protected modified catalyst support which is less soluble in the aqueous acid and/or the neutral aqueous solution. No calcination of the protected modified catalyst support is effected.Type: ApplicationFiled: January 22, 2003Publication date: August 28, 2003Applicant: SASOL TECHNOLOGY (PROPRIETARY) LIMITEDInventors: Peter Jacobus Van Berge, Jan Van De Loosdrecht, Sean Barradas
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Publication number: 20030162848Abstract: A reactor comprising a packed bed of supported catalyst or supported catalyst precursor wherein the supported cata-lyst or the supported catalyst precursor comprise an external surface comprising a catalytically active metal or a precursor compound thereof, and the packed bed has a void content of more than 50% v and a specific surface area of more than 10 cm2/cm3, which is calculated as the total external surface area of the particles relative to the bed volume; the use of the said reactor in a chemical conversion process; a process for preparing hydrocarbons from syngas, which process comprises contacting a mixture of carbon monoxide and hydrogen in the said reactor, on the understanding that the catalytically active metal is a Group VIII metal which is at least in part present in metallic form; a packed bed of catalyst particles or catalyst precursor particles; and a catalyst particle or catalyst precursor particle.Type: ApplicationFiled: February 28, 2003Publication date: August 28, 2003Inventors: Frederik Willem Hendrik Gimpel, Robert Martijn Van Hardeveld, Carolus Matthias Anna Maria Mesters, Gerardus Petrus Lambertus Niesen, Franciscus Johannes Maria Schrauwen
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Publication number: 20030153633Abstract: The invention provides a process for the production or mainly C5+ hydrocarbons comprising contacting carbon monoxide and hydrogen at a temperature in the range of from 180 to 270° C. and elevated pressure in the presence of a catalyst composition comprising cobalt, manganese and at least one of rhenium and/or ruthenium on a titania carrier; a catalyst composition comprising cobalt, manganese and rhenium on a titania carrier.Type: ApplicationFiled: January 3, 2003Publication date: August 14, 2003Inventors: Jacobus Johannes Cornelis Geerlings, Hans Michael Huisman
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Publication number: 20030119923Abstract: The invention relates to a method for separating and recovering rhodium from reaction products of oxosynthesis, especially reaction products containing cobalt. The invention also relates to the reuse of rhodium as a catalyst for hydroformulation and to a catalyst for hydroformulation itself. The inventive method is characterized by the following: extraction of the organic solution with an aqueous phosphate solution or a phosphate solution, water washing, oxidative treatment of the organic phase, and extraction of the organic phase with an aqueous water-soluble arylphosphine solution.Type: ApplicationFiled: September 5, 2002Publication date: June 26, 2003Inventors: Hans-Willi Bohnen, Richard Fischer, Mark Hewlett, Wolfgang Zgorzelski, Norbert Schopper
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Publication number: 20030008929Abstract: A method a making a catalyst, preferably a Fischer-Tropsch catalyst, includes the use of a surfactant. The surfactant is preferably a non-ionic surfactant, or alternatively, a cationic surfactant. The catalyst includes support material and catalyst material. The catalyst material preferably includes at least one Fischer-Tropsch metal, more preferably cobalt. The surfactant is preferably added to a solution containing a catalyst material in an amount sufficient to improve a measure of the activity of a catalyst containing the catalyst material, such as the CO conversion, the methane selectivity, the C5+ productivity, or catalyst life. A method for producing hydrocarbons includes contacting a catalyst made as described above with hydrogen and carbon monoxide.Type: ApplicationFiled: May 31, 2002Publication date: January 9, 2003Applicant: Conoco Inc.Inventor: Joe D. Allison
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Patent number: 6368997Abstract: A process is disclosed for producing hydrocarbons. The process involves contacting a feed stream comprising hydrogen and carbon monoxide with a catalyst in a reaction zone maintained at conversion-promoting conditions effective to produce an effluent stream comprising hydrocarbons. In accordance with this invention the catalyst used in the process includes at least one catalytic metal selected for Fischer-Tropsch reactions (e.g., iron, cobalt, nickel and/or ruthenium); and a support selected from the group consisting of fluorides and fluorided oxides of at least one element selected from the elements of Groups 2 through 15 of the periodic table of elements and elements with atomic numbers 58 through 71 (e.g., zinc, magnesium, calcium, barium, chromium, yttrium, lanthanum, samarium, europium and/or dysprosium).Type: GrantFiled: May 19, 1999Date of Patent: April 9, 2002Assignee: Conoco Inc.Inventors: Norman Herron, Leo E. Manzer, Munirpallam A. Subramanian
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Publication number: 20020037938Abstract: In a process for preparing C2-oxygenates by reaction of CO and H2over a rhodium-containing supported catalyst, the catalyst comprises, based on the total weight,Type: ApplicationFiled: October 16, 2001Publication date: March 28, 2002Inventors: Hongyuan Luo, Huanwen Zhou
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Patent number: 6346555Abstract: In a process for preparing C2-oxygenates by reaction of CO and H2 over a rhodium-containing supported catalyst, the catalyst comprises, based on the total weight, from 0.01 to 10% by weight of rhodium, from 0.001 to 10% by weight of zirconium, from 0.01 to 5% by weight of iridium, from 0.01 to 10% by weight of at least one metal selected from among copper, cobalt, nickel, manganese, iron, ruthenium and molybdenum, from 0.01 to 10% by weight of at least one alkali metal or alkaline earth metal selected from among lithium, sodium, potassium, rubidium, magnesium and calcium, on an inert support.Type: GrantFiled: June 21, 2000Date of Patent: February 12, 2002Assignee: BASF AktiengesellschaftInventors: Hongyuan Luo, Huanwen Zhou
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Publication number: 20010007879Abstract: A process is disclosed for producing hydrocarbons by contacting a feed stream comprising hydrogen and carbon monoxide with a catalyst in a reaction zone maintained at conversion-promoting conditions effective to produce an effluent stream comprising hydrocarbons. The process is characterized by using a catalyst prepared by a method involving (1) forming a catalyst gel by destabilizing an aqueous colloid comprising (a) at least one catalytic metal for Fischer-Tropsch reactions (e.g., iron, cobalt, nickel and/or ruthenium), (b) colloidal cerium oxide, zirconium oxide, titanium oxide and/or aluminum oxide, and optionally (c) Al(OR)3, Si(OR)4, Ti(OR)4 and/or Zr(OR)4 where each R is an alkyl group having from 1 to 6 carbon atoms; and (2) drying the gel.Type: ApplicationFiled: February 21, 2001Publication date: July 12, 2001Inventors: Leo E. Manzer, Kostantinos Kourtakis
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Patent number: 6034031Abstract: A catalyst material produced is for use in producing a substitute natural gas from a source gas containing at least one of carbon dioxide and carbon monoxide, and a reducing gas. The catalyst material contains rhodium and palladium carried on a metal oxide carrier. In producing the substitute natural gas, the source gas containing at least one of carbon dioxide and carbon monoxide, and a reducing gas carried on the metal oxide carrier, are heated under the presence of the catalyst containing rhodium and palladium carried on the metal oxide carrier. It is possible to produce the substitute natural gas highly efficiently at a low temperature not only from carbon monoxide but also from carbon dioxide contained in the source gas.Type: GrantFiled: September 18, 1996Date of Patent: March 7, 2000Assignee: NEC CorporationInventor: Naoaki Sata
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Patent number: 5137924Abstract: Methanol synthesis over a catalyst derived from an alloy of copper and/or a platinum group metal and a highly oxidizable metal such as a rare earth metal can be carried out at unusually low temperatures such as 70.degree. C. and using synthesis gas deficient in hydrogen. The process life of the catalyst is no longer if the starting alloy contains a further metal such as aluminum or manganese. The synthesis gas should preferably be very pure and substantially free of carbon dioxide and water vapor. The process can be advantageously carried out using the catalyst suspended in an inert liquid.Type: GrantFiled: September 3, 1991Date of Patent: August 11, 1992Assignee: Imperial Chemical Industries PLCInventors: Glyn D. Short, James R. Jennings
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Patent number: 5116879Abstract: A process for converting synthesis gas, a mixture of hydrogen and carbon monoxide, into a mixture of predominately paraffinic hydrocarbons using a catalyst which includes catalytically active amounts of cobalt and a loading-insensitive second metal selected from the group consisting of platinum, iridium, rhodium and mixtures thereof, composited on an alumnia support. The finished catalyst exhibits a positive x-ray diffraction pattern. A metal oxide promoter may also be added.Type: GrantFiled: September 28, 1990Date of Patent: May 26, 1992Assignee: Den norske stats oljeselskap A.S.Inventors: Sigrid Eri, James G. Goodwin, Jr., George Marcelin, Trygve Riis
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Patent number: 5102851Abstract: A catalyst for converting synthesis gas, a mixture of hydrogen and carbon monoxide, into a mixture of predominately paraffinic hydrocarbons. The catalyst includes catalytically active amounts of cobalt and a loading-insensitive second metal selected from the group consisting of platinum, iridium, rhodium and mixtures thereof, composited on an aluminia support. The finished catalyst exhibits a positive x-ray diffraction pattern. A metal oxide promoter may also be added.Type: GrantFiled: December 28, 1988Date of Patent: April 7, 1992Assignee: Den norske stats oljeselskap a.s.Inventors: Sigrid Eri, James G. Goodwin, Jr., George Marcelin, Trygve Riis
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Patent number: 4863971Abstract: A process for synthesis gas conversion utilizing perovskite catalysts is disclosed herein. The perovskites utilized in the process have a carbon selectivity of about eight mol percent or more for oxygenated compounds containing one to six carbon atoms. The process comprises reacting synthesis gas in the presence of a perovskite catalyst in the temperature range of about 200.degree. C. to about 400.degree. C.Type: GrantFiled: March 20, 1987Date of Patent: September 5, 1989Assignee: Hoechst Celanese CorporationInventors: Jerry A. Broussard, Leslie E. Wade
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Patent number: 4861802Abstract: Improved process for the catalytic gas phase preparation of low molecular weight (C.sub.2-6) olefinic hydrocarbons from mixtures of H.sub.2 and CO, the improvement consisting of contacting and reacting a mixture of H.sub.2 and CO, at a H.sub.2 /CO molar ratio within the range 0.3 to 1.5, at a space velocity of 1 to 100 minutes.sup.-1, at a pressure of 1 to 2000 psia (6.894 kPa to 13.788 MPa), at a temperature within the range 200.degree. to 400.degree. C., in the presence of the catalyst of the empirical formula AB.sub.1-a Fe.sub.a O.sub.3, wherein A, B and a are defined herein, for example, LaFeO.sub.3.Type: GrantFiled: February 17, 1988Date of Patent: August 29, 1989Assignee: E. I. Du Pont de Nemours and CompanyInventor: Elrey L. McCann
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Patent number: 4758600Abstract: Ethanol is prepared with high selectivity by the catalytic reaction of carbon monoxide and hydrogen.Type: GrantFiled: December 12, 1986Date of Patent: July 19, 1988Assignee: Agency of Industrial Science and TechnologyInventors: Satoshi Arimitsu, Katsumi Yanagi, Hitomi Hosono, Toshihiro Saito, Kazuaki Tanaka, Yuji Onda, Kazuo Takada, Keiji Mitarai, Nobuyuki Taniguchi, Yoshimitsu Ishii, Takakazu Fukushima
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Patent number: 4619947Abstract: A method for the preparation of hydrocarbons and oxygenated hydrocarbons which comprises contacting a gaseous mixture of carbon monoxide, hydrogen and oxygen with a catalyst comprising a metal of Group VII or Group VIII of the Periodic Table, the amount of oxygen not exceeding 10% by volume based on the volume of hydrogen.Type: GrantFiled: July 17, 1985Date of Patent: October 28, 1986Assignee: Imperial Chemical Industries PLCInventor: Samuel D. Jackson
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Patent number: 4596831Abstract: There is disclosed a resin-metal (complex) catalyst, a method for its preparation, activation and use in carrying out Fischer-Tropsch reactions. The complex is a resin which has attached to it a coordination compound(s) and a metal(s). The complex has utility as a Fischer-Tropsch catalyst. More specifically, the complex is useful for the gaseous conversion of synthesis gas (carbon monoxide and hydrogen) to hydrocarbons.Type: GrantFiled: September 9, 1985Date of Patent: June 24, 1986Assignee: The Goodyear Tire & Rubber CompanyInventors: Wen-Liang Hsu, Richard J. Kurr, Neil A. Maly, Dane K. Parker, Robert W. Strozier
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Patent number: 4590217Abstract: A method for making a mixture containing acetic acid, acetaldehyde, and ethanol as the pricipal products, which process comprises reacting carbon monoxide and hydrogen at an elevated temperature and at an elevated pressure in the presence of a supported catalyst prepared by impregnating a carrier with a salt or complex of rhodium and, as a promotor, with at least one non-oxidic compound of an element having an atomic number of 21, 39, or 58 to 71.Type: GrantFiled: November 6, 1984Date of Patent: May 20, 1986Assignee: Hoechst AktiengesellschaftInventors: Ernst I. Leupold, Hans-Joachim Schmidt, Friedrich Wunder
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Patent number: 4568699Abstract: A catalyst comprising a combination of rhodium, iridium and lithium supported on a carrier having a specific surface area of more than 150 m.sup.2 /g is disclosed for producing two carbon atom oxygenerated compounds from carbon monoxide. The catalyst has high catalytic activity and high selectivity to acetic acid.Type: GrantFiled: May 30, 1985Date of Patent: February 4, 1986Assignee: Agency of Industrial Science and TechnologyInventors: Ken-ichi Sano, Yukimitsu Mita, Shinya Matsuhira, Tetsuo Nakajo, Hitoshi Iijima
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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: 4559364Abstract: A catalyst composition comprising a catalytic metal and a support, the support being prepared by depositing a metal alkoxide salt on a core support, then calcining the support.Type: GrantFiled: September 28, 1984Date of Patent: December 17, 1985Assignee: The Dow Chemical CompanyInventors: Clayton D. Wood, Philip E. Garrou, Iwao Kohatsu, Edward F. Gleason
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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: 4539334Abstract: A Fischer-Tropsch process comprises contacting hydrogen and carbon monoxide in the presence of a conventional Fischer-Tropsch catalyst in combination with an amount of phosphorus effective to selectively poison the Fischer-Tropsch catalyst so as to improve the selectivity of said catalyst to C.sub.2 -C.sub.4 olefins.Type: GrantFiled: November 14, 1983Date of Patent: September 3, 1985Assignee: The Dow Chemical CompanyInventor: Craig B. Murchison
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Patent number: 4525481Abstract: Acetaldehyde is prepared by contacting hydrogen and carbon monoxide with a catalyst system comprising an iodide-free ruthenium powder, an iodide-free quaternary phosphonium or ammonium base or salt and a halide-free cobalt-containing compound, such as cobalt(III) acetylacetonate or dicobalt octacarbonyl. Conducting the reaction in a substantially inert solvent such as p-dioxane is preferred.Type: GrantFiled: February 27, 1984Date of Patent: June 25, 1985Assignee: Texaco Inc.Inventors: Jiang-Jen Lin, John F. Knifton
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Patent number: 4514336Abstract: A process for homologating alcohols and/or acids to a mixture of higher acids by reaction with syngas in the presence of a ruthenium-rhodium-iodide-titanium(IV) catalyst.Type: GrantFiled: May 28, 1982Date of Patent: April 30, 1985Assignee: Shell Oil CompanyInventors: Robert C. Ryan, Lynn H. Slaugh
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Patent number: 4506033Abstract: In a process for producing an oxygen-containing hydrocarbon compound having 1 or 2 carbon atoms which comprises reacting a gaseous mixture of a carbon oxide and hydrogen in the presence of a hydrogenation catalyst, the improvement wherein said hydrogenation catalyst is a catalyst composition comprising(A) substantially metallic rhodium and(B) an oxide of a metal selected from the group consisting of metals of Groups IIa, IIIa, IVa and Va of the periodic table of short form,or(i) substantially metallic rhodium,(ii) an element selected from the group consisting of niobium, tantalum, chromium, manganese and rhenium, and(iii) an oxide of a metal selected from the group consisting of metals of Groups IIIa, IVa and Va of the periodic table of short form.Type: GrantFiled: July 29, 1983Date of Patent: March 19, 1985Assignee: Sagami Chemical Research CenterInventor: Masaru Ichikawa
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Patent number: 4492773Abstract: C.sub.1 to C.sub.4 oxygenated hydrocarbons are produced by contacting synthesis gas at a temperature in the range 150.degree. C. to 450.degree. C. and a pressure in the range of 1 to 700 bars with a catalyst comprising a supported mixture of a rhodium component and a silver component. The preferred support is silica. Other metal components which may be incorporated on the support are iron, manganese, molybdenum, tungsten, ruthenium, chromium, thorium and zirconium. Furthermore the support can be activated prior to incorporation of the metal components.Type: GrantFiled: December 8, 1982Date of Patent: January 8, 1985Assignee: The British Petroleum Company LimitedInventors: William J. Ball, Leonard Cotton, David G. Stewart
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Patent number: 4492772Abstract: An oxygenated hydrocarbon product comprising methanol and ethanol is produced by hydrogenating carbon monoxide at a temperature in the range 150.degree. to 450.degree. C. and a pressure in the range 1 to 700 bars in the presence as catalyst of a supported mixture of the metals rhodium, silver, zirconium and molybdenum and optionally also one or more of the metals iron, manganese, rhenium, tungsten, ruthenium, chromium, thorium and potassium. The preferred support is silica.Type: GrantFiled: October 13, 1982Date of Patent: January 8, 1985Assignee: The British Petroleum Company LimitedInventors: William J. Ball, Leonard Cotton, David G. Stewart
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Patent number: 4487851Abstract: Process for conversion of synthesis gas to hydrocarbons in general and to aromatics rich gasoline in particular by contacting the gas with a catalyst composition comprising gallium oxide and/or indium oxide and at least one additional oxide of a metal from Group IB-VIIB or VIII of the Periodic Table. Cerium, thorium, and uranium are the preferred additional metals. The catalyst composition may optionally contain a further component e.g. a zeolite which in some cases can also act as a support. The present process (i) results in a low make of C.sub.1 to C.sub.2 hydrocarbons, (ii) is capable of using synthesis gas which has a low H.sub.2 :CO ratio, and (iii) gives a higher conversion of CO than achieved hitherto under similar conditions.Type: GrantFiled: February 22, 1983Date of Patent: December 11, 1984Assignee: British Petroleum Company, p.l.c.Inventors: Malcolm P. Heyward, Dennis Young
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Patent number: 4471075Abstract: A process for selectively preparing a mixture of two-carbon atom oxygenated hydrocarbons, namely, acetic acid, ethanol and acetaldehyde, by continuously contacting a gaseous reaction mixture containing hydrogen and carbom monoxide with a solid catalyst comprising rhodium in combination with sodium at reaction conditions correlated so as to favor the formation of a substantial proportion of such two-carbon atom products.Type: GrantFiled: June 16, 1983Date of Patent: September 11, 1984Assignee: Union Carbide CorporationInventors: William J. Bartley, Thomas P. Wilson
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Patent number: 4463105Abstract: In a process for producing an oxygen-containing hydrocarbon compound having 1 or 2 carbon atoms which comprises reacting a gaseous mixture of a carbon oxide and hydrogen in the presence of a hydrogenation catalyst, the improvement wherein said hydrogenation catalyst is a catalyst composition comprising(A) substantially metallic rhodium,(B) an oxide of a metal selected from the group consisting of metals of Groups, IIa, IIIa, IVa and Va of the periodic table of short form, and(C) silica or(i) substantially metallic rhodium,(ii) an element selected from the group consisting of niobium, tantalum, chromium, manganese and rhenium,(iii) an oxide of a metal selected from the group consisting of metals of Groups IIIa, IVa and Va of the periodic table of short form, and(iv) silica.Type: GrantFiled: June 9, 1982Date of Patent: July 31, 1984Assignee: Sagami Chemical Research CenterInventors: Masaru Ichikawa, Kohichi Shikakura, Kazuhiko Sekizawa, Kazuaki Tanaka
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Patent number: 4446251Abstract: A process for selectively preparing a mixture of two-carbon atom oxygenated hydrocarbons, namely, acetic acid, ethanol and acetaldehyde, by continuously contacting a gaseous reaction mixture containing hydrogen and carbon monoxide with a solid catalyst comprising rhodium in combination with sodium at reaction conditions correlated so as to favor the formation of a substantial proportion of such two-carbon atom products.Type: GrantFiled: March 17, 1982Date of Patent: May 1, 1984Assignee: Union Carbide CorporationInventors: William J. Bartley, Thomas P. Wilson
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Patent number: 4444909Abstract: The conversion of synthesis gas comprising hydrogen and carbon oxides to form oxygenate-containing mixtures which are limited compositionally in being virtually free of C.sub.11 + compounds, with a zeolite which is virtually free of acid sites and characterized by a silica to alumina mole ratio of at least about 12 and a constraint index within the range of 1 to 12, having intimately combined therewith a metal selected from the group consisting of rhodium, platinum, palladium and iridium.Type: GrantFiled: January 27, 1982Date of Patent: April 24, 1984Assignee: Mobil Oil CorporationInventors: Clarence D. Chang, William H. Lang
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Patent number: 4442228Abstract: Ethanol is manufactured by reaction of carbon monoxide with hydrogen on a supported rhodium catalyst containing as cocatalyst at least one of the elements zirconium, hafnium, lanthanum, platinum, chromium and mercury.Type: GrantFiled: November 19, 1982Date of Patent: April 10, 1984Assignee: Hoechst AktiengesellschaftInventors: Ernst I. Leupold, Hans-Joachim Schmidt, Friedrich Wunder, Hans-Jurgen Arpe, Horst Hachenberg
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Patent number: 4399233Abstract: Low molecular weight oxygenated compounds, and particularly ethylene glycol and methanol, are prepared from syngas in good yield by contacting a mixture of carbon monoxide and hydrogen with a catalyst system comprising a rhodium-containing compound, an organic ligand and a sulfonium salt, preferably dissolved in a suitable solvent, and heating the resulting mixture at an elevated temperature and pressure for sufficient time to produce the desired low molecular weight oxygenated compounds, and then recovering the same from the reaction mixture.Type: GrantFiled: March 11, 1982Date of Patent: August 16, 1983Assignee: Texaco Inc.Inventor: Roger G. Duranleau
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Patent number: 4351908Abstract: The invention provides a process for the manufacture of acetic acid, acetic aldehyde and ethanol by reaction in the gaseous phase of carbon monoxide and hydrogen in the presence of catalysts containing rhodium and optionally promoters, at elevated temperature and pressure. In this process, the temperature is raised in the starting phase, where the catalyst is heated to the working temperature T.sub.R intended for continuous operation, in a range of from T.sub.O to T.sub.R, T.sub.O being 75.degree. to 125.degree. C. below T.sub.R, continuously or in steps of 10.degree. C. at most, in a period of time of from 100 to 1,000 hours; the temperature being raised by 10.degree. C. at most within any 10 hour interval.Type: GrantFiled: October 9, 1981Date of Patent: September 28, 1982Assignee: Hoechst AktiengesellschaftInventors: Hans-Joachim Schmidt, Ernst I. Leupold
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Patent number: 4338089Abstract: A process is disclosed for the preparation of a hydrocarbon mixture by contacting in a first stage a feed mixture of hydrogen and carbon monoxide with an H.sub.2 /CO molar ratio of less than 1.0 with a trifunctional catalyst combination containing (a) at least one metal component having catalytic activity for conversions of a H.sub.2 /CO mixture into acyclic hydrocarbons, and/or acyclic oxygen-containing hydrocarbons, (b) at least one metal component for the conversion of an H.sub.2 O/CO mixture into an H.sub.2 /CO mixture, and (c) a certain crystalline silicate containing at least one trivalent metal selected from aluminum, iron, gallium, rhodium, chromium and scandium, wherein the molar ratio of the trivalent metal oxide to silica is less than 0.1; adjusting the H.sub.2 /CO molar to at least 1.5 by adding H.sub.2 O, if necessary; followed by contacting in a second stage at least the C.sub.Type: GrantFiled: July 31, 1980Date of Patent: July 6, 1982Assignee: Shell Oil CompanyInventors: Lambert Schaper, Swan T. Sie
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Patent number: 4327190Abstract: Oxygenated hydrocarbon compounds containing from one to four carbon atoms, e.g. acids, alcohols and/or aldehydes are produced by reacting carbon monoxide with hydrogen in the presence of a supported mixture of a rhodium component and a chromium component, optionally incorporating also iron, manganese, molybdenum, tungsten or ruthenium at elevated temperature and generally at elevated pressure. A preferred support is silica which may be activated by the addition of metal and non-metal activators followed by calcination, prior to incorporation of the rhodium and chromium components.Type: GrantFiled: April 18, 1980Date of Patent: April 27, 1982Assignee: The British Petroleum Company LimitedInventors: William J. Ball, Leonard Cotton, David G. Stewart
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Patent number: 4312955Abstract: Lanthanum rhodate, or metal substituted lanthanum rhodate, having a perovskite structure is a highly active catalyst for the production of methanol from hydrogen and carbon monoxide. The lanthanum rhodate displays excellent stability and excellent selectivity to methanol.Type: GrantFiled: December 1, 1980Date of Patent: January 26, 1982Assignee: Union Carbide CorporationInventor: William J. Bartley
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Patent number: 4288558Abstract: Acetic acid, ethanol, acetaldehyde and possibly secondary products thereof are prepared by the catalytic reaction of carbon monoxide and hydrogen. The catalyst contains, applied onto a carrier, salts or complex compounds of rhodium with a valence below 3, halide ions and salts or complex compounds of magnesium.Type: GrantFiled: April 1, 1980Date of Patent: September 8, 1981Assignee: Hoechst AktiengesellschaftInventors: Hans-Joachim Schmidt, Friedrich Wunder, Hans-Jurgen Arpe, Ernst I. Leupold
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Patent number: 4276395Abstract: Novel polymer-supported metal complexes of the formulaPS -R Me(CO).sub.n H.sub.Type: GrantFiled: April 29, 1980Date of Patent: June 30, 1981Assignee: The United States of America as represented by the United States Department of EnergyInventors: Kurt P. C. Vollhardt, Patrick Perkins