By Reacting Water With Carbon Monoxide Patents (Class 423/655)
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Patent number: 4324695Abstract: Transition metal carbonyl clusters intercalated with lamellar material such as graphite or smectites are prepared by reacting an intercalate of a transition metal halide with carbon monoxide at elevated temperature and at ambient to superatmospheric pressure. The intercalated complexes are useful in the catalysis of a variety of organic reactions including the water gas shift reaction, hydrogenation, hydroformylation, methanation, and so forth.Type: GrantFiled: November 17, 1980Date of Patent: April 13, 1982Assignee: National Distillers & Chemical Corp.Inventor: James A. Hinnenkamp
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Patent number: 4259312Abstract: An outer enclosed pressure container is formed of a simple steel material. An inner enclosed container is positioned within the pressure container such that there is an intermediate space therebetween. Catalyst layers are provided within the inner container. A gas containing a reducing component and water vapor are introduced into the inner container and are therein reacted by means of the catalyst to perform a desired reducing reaction. At least part of the water vapor is alone introduced into the intermediate space to thereby pressurize the intermediate space to substantially the same pressure as occurs within the inner container. The water vapor in the intermediate space operates to protect the wall of the pressure container from the temperatures occurring due to the catalytic reaction within the inner container. The water vapor is removed from the intermediate space and is at least partially added to the gas containing a reducing component before the introduction thereof into the inner container.Type: GrantFiled: October 3, 1979Date of Patent: March 31, 1981Assignees: Didier Engineering GmbH, Thyssengas GmbHInventors: Claus Flockenhaus, Erich Hackler
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Patent number: 4254094Abstract: Process for treating synthesis gas to recover a purified essentially sulfur-free hydrogen-rich stream. The novel sequence of operations employed comprises initially removing from the feed gas, such as from a synthesis gas derived from partial oxidation of coal or oil, the bulk of contained H.sub.2 S and a substantial part of the contained COS, by physical absorption in a suitable solvent. The gas from the initial absorption is then subjected to water-gas shift reaction over a sulfur-resistant shift catalyst under conditions such that in addition to the conversion of CO to CO.sub.2 most of the contained COS hydrolyzed to H.sub.2 S. The gaseous shift product is then subjected to a second treatment with suitable solvent to remove by physical absorption essentially all of the remaining sulfur, which is then present as H.sub.2 S. The thus desulfurized gas mixture is then sent to a CO.sub.2 absorber, from which a H.sub.2 -rich gas effluent is withdrawn. The H.sub.Type: GrantFiled: March 19, 1979Date of Patent: March 3, 1981Assignee: Air Products and Chemicals, Inc.Inventor: William P. Hegarty
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Patent number: 4233180Abstract: A process for the conversion of carbon monoxide in synthesis gas mixtures to hydrogen and CO.sub.2 utilizes a catalyst which is active in the presence of sulfur compounds, and which comprises the oxides or sulfides of cobalt and molybdenum, supported on a shaped, relatively high surface area aluminous carrier. The carrier is stabilized by admixture with one or more rare earth metal oxides while the alumina is in the hydrated condition. The mixture of hydrated alumina and rare earth metal oxide is formed into a desired shape and calcined to convert the hydrated alumina to the oxide. Thereafter, the calcined, high surface area alumina is impregnated with the desired salts of cobalt and molybdenum and the impregnated catalyst is thereafter calcined and placed into service. The stabilized catalyst exhibits good activity at relatively low temperatures with synthesis gas mixtures containing sulfur compounds and retains its surface area and the aluminous carrier is not converted over to the alpha phase.Type: GrantFiled: November 13, 1978Date of Patent: November 11, 1980Assignee: United Catalysts Inc.Inventors: Arthur L. Hausberger, Edward K. Dienes
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Patent number: 4226845Abstract: In the water gas shift reaction,H.sub.2 O+CO.fwdarw.H.sub.2 +CO.sub.2and more particularly in hydroformylation of olefins, e.g. ethylene ##EQU1## and in hydrohydroxymethylation in which an alcohol, e.g. propanol, is produced, higher yields and/or fewer by-products and branched chain products and/or faster reactions are obtained using a combination of two or more Group VIII metal carbonyls one of which is ruthenium.Type: GrantFiled: December 6, 1978Date of Patent: October 7, 1980Assignee: S R I InternationalInventor: Richard M. Laine
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Patent number: 4223001Abstract: An improved process is described for producing hydrogen from carbon monoxide and water in which carbon monoxide is contacted under homogeneous conditions with an alkaline aqueous liquid phase containing a soluble rhodium-containing catalyst at a reaction temperature from about 100.degree. to 300.degree. C. and at a reaction pressure from about 1 to 300 atmospheres in the presence of a saturated paraffinic water-soluble alcohol.Type: GrantFiled: June 20, 1978Date of Patent: September 16, 1980Assignee: Allied Chemical CorporationInventors: Miroslav Novotny, Lowell R. Anderson
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Patent number: 4207167Abstract: A used hydrocarbon cracking catalyst having coke laydown thereon is regenerated under conditions to produce a gas rich in carbon monoxide which, together with steam, is subjected to a shift reaction to produce carbon dioxide and hydrogen, and oil cracked with said catalyst produces vapors which are fractionated to yield gases, cracked gasoline, a light-cycle oil, a heavy-cycle oil and bottoms, at least one of the light and heavy cycle oils is hydrocracked with the hydrogen earlier produced.Type: GrantFiled: March 21, 1978Date of Patent: June 10, 1980Assignee: Phillips Petroleum CompanyInventor: Ralph W. Bradshaw
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Patent number: 4161393Abstract: In a process for producing a fuel gas from a solid fuel by a gasification of solid fuel under a pressure of about 15-100 bars by a treatment with steam and a gas which contains free oxygen, cooling the raw gas to a temperature of about 150.degree.-200.degree. C. and saturating it with water vapor, removing condensate which has formed so that the raw gas contains hydrocarbons having a boiling range from about 20.degree. to 400.degree. C. in an amount of about 10-100 g per standard m.sup.3 of dry gas and has a CO:H.sub.2 O volume ratio of about 0.8-2, and subjecting the raw gas to a shift conversion, the improvement which comprises dividing the raw gas into first and second partial streams in a ratio of about 1:10 to 1:1, feeding the first partial stream with a surplus of water vapor to a first shift conversion stage at an inlet temperature of about 280.degree.-450.degree. C.Type: GrantFiled: March 1, 1978Date of Patent: July 17, 1979Assignee: Metallgesellschaft AktiengesellschaftInventors: Paul Rudolph, Uwe D. Marwig
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Patent number: 4152407Abstract: Exothermic reaction of a fluid stream is carried out with recycle and addition of hot reacted fluid to the colder feed fluid stream, so as to raise the feed fluid stream to operable reaction temperatures and produce optimum reaction rate. The addition of hot reacted fluid is carried out by reactor-internal ejector-effected aspiration of a portion of the hot reacted fluid discharged from the reaction zone into the cold feed fluid. The resulting combined fluid stream is passed to the reaction zone. The balance of the hot reacted fluid not aspirated into the cold feed fluid is passed to product recovery or utilization. The invention is especially applicable to exothermic catalytic reactions.Type: GrantFiled: February 2, 1977Date of Patent: May 1, 1979Inventor: Warren Fuchs
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Patent number: 4151107Abstract: The reaction of carbon monoxide and water to produce hydrogen and carbon dioxide is catalyzed by a rhodium or iridium component with an iodide promoter.Type: GrantFiled: May 31, 1977Date of Patent: April 24, 1979Assignee: Monsanto CompanyInventor: Thomas C. Singleton
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Patent number: 4124629Abstract: Catalysts having a high degree of thermal stability, comprising alumina and one or more of the iron group metals are prepared from aqueous solutions containing a dissolved aluminum salt, a salt of at least one of the iron group metals and a delayed precipitant such as urea. The solution is heated to a temperature sufficient to hydrolyze the delayed precipitant with resultant liberation of ammonia and carbon dioxide homogeneously throughout the solution, until the pH of the solution rises sufficiently to effect coprecipitation of the metal salts as hydroxides and/or carbonates. The resulting coprecipitate is then recovered, washed, dried, shaped and calcined in conventional fashion to obtain a final product which, after hydrogen-reduction is very active, and displays much greater thermal stability than corresponding prior art catalysts prepared by non-homogeneous coprecipitation with alkaline, ionic reagents such as sodium carbonate, ammonium hydroxide, or ammonium carbonate.Type: GrantFiled: January 10, 1977Date of Patent: November 7, 1978Assignee: Union Oil Company of CaliforniaInventor: Rowland C. Hansford
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Patent number: 4107076Abstract: A method for carrying out the water gas shift reaction by use of a homogeneous catalyst system containing rhodium carbonyl iodide in a water/acetic acid solvent is described. The catalyst system can be formed from [RH (CO).sub.2 Cl].sub.2, aqueous HI and glacial acetic acid. When a reactor is charged under 250-400 torr of CO at 90.degree. C catalysis of the water gas shift reaction results.Type: GrantFiled: March 31, 1977Date of Patent: August 15, 1978Assignee: University of RochesterInventors: Richard Eisenberg, Chien-Hong Cheng
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Patent number: 4101645Abstract: A process for the production of hydrogen/deuterium-containing gas in which the enriched condensate obtained from the production of a hydrogen/deuterium-containing gas mixture is collected and subjected to a direct exchange of isotopes with the feedsteam admitted to the process. Such condensate can be brought into direct exchange of isotopes with the gas water vapor mixture within the process, viz. ahead of the CO conversion section. The exchange of isotopes may be performed according to the counter-current principle. If it is intended to maintain in the hydrogen/deuterium-containing gas a certain definite content of water vapor whose phase condition is superior to the condition achieved when using normal cooling water, this gas, at least 0.6 kg/m.sup.3 of gas, is subjected to an exchange of isotopes with the water fed additionally into the process.Type: GrantFiled: November 8, 1976Date of Patent: July 18, 1978Assignee: Friedrich Uhde GmbHInventors: Eberhard Nitschke, Arvind Desai, Hartmut Ilgner
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Patent number: 4081519Abstract: A process for the oxidation of carbon monoxide to carbon dioxide with an inorganic oxidizing agent selected from the group consisting of water, nitric oxide and sulfur dioxide, which comprises combining the carbon monoxide with a predetermined amount of said oxidizing agent to give at least a stoichiometric amount of the oxidizing agent for the oxidation of the carbon monoxide to carbon dioxide, and passing the mixture over a novel ceramic catalyst at an elevated temperature.Type: GrantFiled: August 5, 1976Date of Patent: March 28, 1978Assignee: University of Southern CaliforniaInventor: James M. Whelan
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Patent number: 4054644Abstract: Hydrogen is produced by reacting carbon monoxide with steam at a temperature of at least 200.degree. F. in the presence of a supported catalyst containing: (1) at least one alkali metal compound derived from an acid having an ionization constant below 1 .times. 10.sup.-3, (2) a metallic hydrogenation- dehydrogenation material, and (3) a halogen moiety. The ratio of metal component to alkali metal compound, each calculated on the basis of the oxide thereof, ranges from 0.0001 to about 10 parts by weight per part by weight of the alkali metal compound. The halide constituent is present in amounts in excess of about 0.01 weight %, based on total catalyst. A preferred catalyst composition comprises potassium carbonate, a mixture of cobalt and molybdenum oxides and combined chlorine contained on an alumina support.Type: GrantFiled: November 25, 1974Date of Patent: October 18, 1977Assignee: Exxon Research & Engineering Co.Inventors: Marnell A. Segura, Clyde L. Aldridge, Kenneth L. Riley, Lloyd A. Pine
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Patent number: 4029754Abstract: A closed cycle process produces hydrogen and oxygen from water by use of manganese chloride and carbon dioxide. The four reactions of the cycle are:1. MnCl.sub.2 + CO.sub.2 .fwdarw. MnO + CO + Cl.sub.22. CO + H.sub.2 O .fwdarw. CO.sub.2 + H.sub.23. mnO + 2 HCl .fwdarw. MnCl.sub.2 + H.sub.2 O4. cl.sub.2 + H.sub.2 O .fwdarw. 2HCl + 1/2 O.sub.2.Type: GrantFiled: July 11, 1975Date of Patent: June 14, 1977Assignee: Japan Atomic Energy Research InstituteInventors: Shoichi Sata, Yasumasa Ikezoe
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Patent number: 4025612Abstract: Hydrogen is produced by the combustion of carbon with air to produce a combustion gas effluent containing carbon dioxide and nitrogen. The carbon dioxide is separated and reacted with carbon to produce carbon monoxide. The resulting produced carbon monoxide is then reacted with steam to produce carbon dioxide and hydrogen and the resulting produced hydrogen separated. The carbon utilized for the production of hydrogen may be obtained by the thermal decomposition of hydrocarbons to yield carbon and gaseous hydrogen or the carbon utilized in this process may be obtained from a solid carbonaceous fuel, such as coal or coke or the like.Type: GrantFiled: December 13, 1974Date of Patent: May 24, 1977Assignee: Texaco Inc.Inventor: Everett M. Barber
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Patent number: 4021366Abstract: This is a continuous process for producing hydrogen-rich gas. Successive beds of water-gas shift conversion catalysts of differing properties are employed in a shift converter to achieve an economical balance between catalyst activity and catalyst life. For example, a comparatively small fixed bed of highly active low temperature water-gas shift conversion catalyst may be loaded on top of a fixed bed of rugged low cost moderately active high temperature water-gas shift catalyst. A CO-rich gas and H.sub.2 O are introduced into the bed of low temperature shift catalyst where reaction takes place. The partially reacted gas stream leaves the bed of low temperature shift catalyst and is introduced into the bed of high temperature catalyst at a suitable temperature for triggering off therein the water gas shift reaction without the additon of heat from an external source. By this means it may be possible to produce hydrogen-rich gas with high conversions of CO to CO.sub.Type: GrantFiled: June 30, 1975Date of Patent: May 3, 1977Assignee: Texaco Inc.Inventors: Allen M. Robin, Edward T. Child
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Patent number: 4021298Abstract: Hydrocarbons are formed of coal and water. The water is converted or dissociated separately into hydrogen and oxygen in a first chemical reactor by thermochemical and/or electrolytic processing. The resulting hydrogen is then reacted with the coal in a second reactor to produce the hydrocarbons. Residual carbon from the second reactor is reacted in a third reactor with oxygen derived from the first reactor to produce carbon monoxide. The carbon monoxide is reacted with residual hydrogen from the second reactor or hydrogen from the first reactor to produce additional hydrocarbons. The energy for the endothermic and/or electrolytic processing in the reactors and for auxiliary equipment of the apparatus is supplied by a very high-temperature, gas-cooled, nuclear reactor by heat interchange with the cooling gas, helium. The cooling gas operates through heat-exchange means which isolates the cooling gas from the processing apparatus.Type: GrantFiled: January 29, 1974Date of Patent: May 3, 1977Assignee: Westinghouse Electric CorporationInventor: Andrew R. Jones
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Patent number: 4008163Abstract: Methods of preparing fluid mixtures in a chamber under close temperature and pressure controls in which liquid water is introduced into the chamber along with gases selected from the group consisting of oxidizing and reducing gases for providing in the liquid water a mixture of carbon dioxide, hydrogen and carbon monoxide, and of oxidizing and carburizing gases for providing in the liquid water a mixture of carbon dioxide, methane, hydrogen and carbon monoxide under reaction conditions. The liquid water in the chamber is maintained under close temperature control of from about 32.degree. F. to about 160.degree. F. and gases in the chamber are maintained under control pressures from ambient atmospheric up to 218.5 atmospheres so that a saturated fluid mixture is generated having predetermined properties as determined by the controlled temperatures and pressures.Type: GrantFiled: March 13, 1972Date of Patent: February 15, 1977Inventor: Glenn R. Ingels
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Patent number: 4007015Abstract: Hydrogen is produced by the combustion of carbon with air to produce a combustion gas effluent containing carbon dioxide and nitrogen. The carbon dioxide is separated and reacted with carbon to produce carbon monoxide. The resulting produced carbon monoxide is then reacted with steam to produce carbon dioxide and hydrogen and the resulting produced hydrogen separated. The carbon utilized for the production of hydrogen may be obtained by the thermal decomposition of hydrocarbons to yield carbon and gaseous hydrogen or the carbon utilized in this process may be obtained from a solid carbonaceous fuel, such as coal or coke or the like.Type: GrantFiled: December 17, 1975Date of Patent: February 8, 1977Assignee: Texaco Inc.Inventor: Everett M. Barber
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Patent number: 3970745Abstract: A method for producing hydrogen from water in which hydrogen is produced by reducing water using metallic germanium and the by-product, germanium monoxide, is reduced with a reducing agent to metallic germanium which is recycled and reused. In this case, it is necessary to regulate the oxidation of metallic germanium so as to stop at the germanium monoxide stage since the reduction of germanium dioxide to metallic germanium is difficult. Therefore, water vapor is advantageously reduced by using not less than 1 mole of metallic germanium to 1 mole of water vapor or it is indirectly reduced with an intermediate of carbon dioxide.Type: GrantFiled: March 24, 1975Date of Patent: July 20, 1976Assignee: Director-General of the Agency of Industrial Science and TechnologyInventor: Norio Takeuchi
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Patent number: 3965253Abstract: A process for supplying hydrogen to a hydrogen-consuming process including catalytically partially oxidizing hydrocarbon to produce a carbon monoxide- and hydrogen-containing gas, catalytically reacting water with the carbon monoxide- and hydrogen-containing gas to produce a carbon dioxide- and hydrogen-containing gas, centrifugally compressing the carbon dioxide- and hydrogen-containing gas to at least 180 psia carbon dioxide partial pressure and contacting it with an absorbing liquid containing diisopropanolamine and a cyclotetramethylene sulfone, catalytically reacting the absorber effluent gas at conditions to react hydrogen with carbon oxides to produce methane and passing the resultant hydrogen-containing gas to the hydrogen-consuming process.Type: GrantFiled: May 7, 1975Date of Patent: June 22, 1976Assignee: Shell Oil CompanyInventors: Donald W. Miller, Keith E. Zarker
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Patent number: 3957962Abstract: There is disclosed a process for the preparation of hydrogen-rich gas by passing a gas mixture containing carbon monoxide and water vapor over a sulfided catalyst which includes nickel and/or cobalt, molybdenum and aluminum with the aluminum being present in an amount of from 0.1 to 1.0 part of aluminum per part of nickel and/or cobalt on a weight basis. The catalyst is prepared by impregnating an alumina carrier with one or more solutions of compounds of the catalysts in which at least 40%w of the aluminum that is used is added to the carrier by co-impregnation with the nickel and/or cobalt.Type: GrantFiled: March 22, 1974Date of Patent: May 18, 1976Assignee: Shell Oil CompanyInventor: John Ramsbotham
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Patent number: 3932599Abstract: A method of obtaining hydrogen from water in a multi-stage circulatory process avoids the need to use solid inorganic salts as auxiliary products by using only gases and liquids in the reaction stages. Carbon monoxide is reacted catalytically with steam producing carbon dioxide and hydrogen; the carbon dioxide is reacted with steam and sulphur dioxide to give sulphuric acid and carbon monoxide; the sulphuric acid is split into sulphur trioxide and steam; the sulphur trioxide is dissociated into oxygen and sulphur dixoide. The CO and SO.sub.2 are fed back into the process, and hydrogen and oxygen obtained as end products.Type: GrantFiled: February 25, 1975Date of Patent: January 13, 1976Assignee: Rheinische Braunkohlenwerke AktiengesellschaftInventors: Rudolf Schulten, Johannes Teggers, Roland Schulze Bentrop