And Another Metal Patents (Class 423/654)
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Patent number: 6713040Abstract: A method of producing a H2 rich gas stream includes supplying an O2 rich gas, steam, and fuel to an inner reforming zone of a fuel processor that includes a partial oxidation catalyst and a steam reforming catalyst or a combined partial oxidation and stream reforming catalyst. The method also includes contacting the O2 rich gas, steam, and fuel with the partial oxidation catalyst and the steam reforming catalyst or the combined partial oxidation and stream reforming catalyst in the inner reforming zone to generate a hot reformate stream. The method still further includes cooling the hot reformate stream in a cooling zone to produce a cooled reformate stream. Additionally, the method includes removing sulfur-containing compounds from the cooled reformate stream by contacting the cooled reformate stream with a sulfur removal agent.Type: GrantFiled: March 23, 2001Date of Patent: March 30, 2004Assignee: Argonne National LaboratoryInventors: Shabbir Ahmed, Sheldon H. D. Lee, John David Carter, Michael Krumpelt
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Publication number: 20030113258Abstract: A desulfurizing agent comprising a silica-alumina carrier having an Si/Al mole ratio of 10 or less and nickel carried thereon; a desulfurizing agent for hydrocarbons derived from petroleum which comprises a carrier and a metal component carried thereon and has a specific surface area of pores having a pore diameter of 3 nm or less of 100 m2/g or more; an Ni-Cu based desulfurizing agent comprising a carrier and, carried thereon, (A) nickel, (B) copper, and (C) an alkali metal or another metal; a desulfurizing agent for hydrocarbons derived from petroleum which comprises a carrier and a metal component carried thereon and has a hydrogen adsorption capacity of 0.4 mmol/g or more; and methods for producing these nickel-based and nickel-copper-based desulfurizing agents. The above desulfurizing agents are capable of adsorbing and removing with good efficiency the sulfur contained in hydrocarbons derived from petroleum to a content of 0.2 wt. ppm or less and have a long service life.Type: ApplicationFiled: September 23, 2002Publication date: June 19, 2003Inventors: Hisashi Katsuno, Satoshi Matsuda, Kazuhito Saito, Masahiro Yoshinaka
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Publication number: 20030099594Abstract: A new cost effective and thermally efficient process for converting nearly valueless resources, such as “static,” lower quality sour natural gas containing hydrogen sulfide, to useable fuels and chemicals, such as hydrogen, methanol and high cetane diesel fuel. The preferred method and apparatus can be used to treat conventional sour gas, i.e., gas having a ratio of H2S to CH4 of at least 0.1 moles and preferably of at least 0.33 moles/mole, using a reforming catalyst and a sulfur capture agent. The process nominally can be carried out using two reactors that repeatedly cycle reactants between two basic process steps—reforming, and air regeneration.Type: ApplicationFiled: November 26, 2001Publication date: May 29, 2003Inventor: Richard K. Lyon
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Publication number: 20030032554Abstract: The present invention relates to a modified &thgr;-Al2O3-supported nickel reforming catalyst and its use for producing synthesis gas from natural gas, more specifically to a nickel reforming catalyst expressed by the following formula 1, having improved coke resistance, high-temperature catalysis stability and catalytic activity, which is prepared by coating nickel or mixture of nickel and cocatalyst (M1—M2—Ni) on a &thgr;m-Al2O3 support modified with metal (M3—M4—ZrO2/&thgr;-Al2O3), and its use for producing synthesis gas from natural gas through steam reforming, oxygen reforming or steam-oxygen reforming,Type: ApplicationFiled: May 13, 2002Publication date: February 13, 2003Applicant: Korea Research Institute Of Chemical TechnologyInventors: Sang-Eon Park, Ki-Won Jun, Hyun-Seog Roh, Seung-Chan Baek, Young-Sam Oh, Young-Soon Baek, Ri-Sang Choi, Taek-Yong Song
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Publication number: 20030017105Abstract: The present invention provides a method of steam reforming a hydrocarbon over a catalyst at short residence times or short contact times. The present invention also provides spinel-containing catalysts. Surprisingly superior results and properties obtained in methods and catalysts of the present invention are also described.Type: ApplicationFiled: February 13, 2002Publication date: January 23, 2003Inventors: Yong Wang, Anna Lee Tonkovich, David P. Vanderwiel
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Patent number: 6509000Abstract: A process for the continuous production of hydrogen from methane and/or natural gas and/or methane-rich hydrocarbons and steam at low temperature, using a solid catalyst comprising group VIII metal oxide(s) in two parallel reactors, comprising reducing the solid catalyst in both the reactors by contacting the catalyst with a gaseous feed comprising a reducing agent, contacting a first gaseous feed comprising methane and/or natural gas and/or methane rich hydrocarbons, simultaneously contacting a second gaseous feed comprising steam called Feed-B with the solid catalyst reduced in step-i in a second reactor. while regularly switching over the two feeds, Feed-A arid Feed-B, between the two parallel reactors to obtain a mixed product stream comprising hydrogen from the two reactors.Type: GrantFiled: August 31, 2000Date of Patent: January 21, 2003Assignee: Council of Scientific and Industrial ResearchInventors: Vasant Ramchandra Choudhary, Amarjeet Munshiram Rajput, Subhabrata Banerjee
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Publication number: 20020061277Abstract: The invention provides a process, catalyst and apparatus for carrying out the water-gas shift reaction comprising employing a low-pyrophoricity water-gas shift reaction catalyst; wherein the low-pyrophoricity water-gas shift reaction catalyst comprises a solid high heat capacity particulate support impregnated with: (i) a reducible metal oxide and (ii) a catalytic agent.Type: ApplicationFiled: January 29, 2001Publication date: May 23, 2002Applicant: ENGELHARD CORPORATIONInventors: Wolfgang F. Ruettinger, Olga Korotkikh, Robert J. Farrauto
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Patent number: 6328945Abstract: A process for producing carbon monoxide (CO) by reforming methane and steam in the presence of a reforming catalyst to produce a reformate product enriched in CO, carbon dioxide (CO2) and hydrogen. CO2 in the enriched reformate is shifted to CO in an integrated sorption enhanced reaction (SER) cycle which employs a series of cyclic steps to facilitate reaction of CO2 and hydrogen at high conversion and to produce a CO-enriched product obtained at reactor feed pressure and at essentially constant flow rate. A series of adsorbent regeneration step including depressurization, purging and product pressurization are used to desorb water which is selectively adsorbed by the adsorbent during the shift reaction and to prepare the reactor for a subsequent process cycle.Type: GrantFiled: April 8, 1996Date of Patent: December 11, 2001Assignee: Air Products and Chemicals, Inc.Inventors: Jeffrey Raymond Hufton, Shivaji Sircar, William Frederick Baade, Joseph Michael Abrardo, Madhu Anand
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Patent number: 6312658Abstract: The present invention is a process for producing an essentially pure carbon monoxide (CO) product and an essentially pure hydrogen product by reforming a hydrocarbon such as methane and steam in the presence of a reforming catalyst to produce a reformate product enriched in CO, carbon dioxide and hydrogen. The reformate is subjected to an integrated series of separation steps and carbon dioxide present in a portion of the waste effluent recovered from such series of spearation steps is shifted to CO in an integrated sorption enhanced reaction (SER) process.Type: GrantFiled: April 8, 1996Date of Patent: November 6, 2001Assignee: Air Products and Chemicals, Inc.Inventors: Jeffrey Raymond Hufton, Shivaji Sircar, William Frederick Baade, Joseph Michael Abrardo, Madhu Anand
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Patent number: 6293979Abstract: A process for catalytic conversion of methane or natural gas to syngas using a supported catalyst containing oxides of nickel and cobalt with of without noble metals. Efficiency of the catalytic process is increased by simultaneously carrying out an exothermic oxidation reaction and an endothermic steam and carbon dioxide reforming reaction over the supported catalyst. The catalyst is prepared by depositing oxides of nickel and cobalt, with or without noble metals, on a sintered low surface area porous inert support. Surface of the support is precoated with an oxide of Be, Mg, Ca or a mixture thereof so that a protective layer of alkaline earth oxide is formed between the oxides of nickel and cobalt and the support, and hence, direct chemical interactions between the oxides of nickel and cobalt and reactive components of the support, which leads to formation of catalytically inactive binary oxide phases, are avoided.Type: GrantFiled: February 6, 1998Date of Patent: September 25, 2001Assignee: Council of Scientific & Industrial ResearchInventors: Vasant Ramchandra Choudhary, Balu Shivaji Uphade, Ajit Singh Mamman, Amarjeet Munshiram Rajput
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Publication number: 20010009653Abstract: A reformer is disclosed for converting a hydrocarbon fuel into hydrogen gas and carbon dioxide, the reformer having a first tube, a second tube annularly disposed about the first tube, and a third tube annularly disposed about the second tube. The first tube includes a first catalyst, a first tube outlet, and is adapted for receiving a first mixture of steam. The second tube is adapted for receiving a second mixture of an oxygen-containing gas and a second fuel. The third tube is adapted for receiving a first reaction reformate from the first tube and a second reaction reformate from the second tube, and for producing a third reaction reformate.Type: ApplicationFiled: February 2, 2001Publication date: July 26, 2001Inventors: Lawrence G. Clawson, William L. Mitchell, Jeffrey M. Bentley, Johannes H.J. Thijssen
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Patent number: 6238816Abstract: A process and apparatus for steam reforming of hydrocarbons, using a sulfur-tolerant catalyst comprising an active phase and a support phase, and optionally a promoter, which provides substantially complete conversion of the hydrocarbon to a mixture of hydrogen, carbon monoxide, and carbon dioxide. The process comprises introducing steam and a hydrocarbon feed containing at least about 2 ppm sulfur species into the apparatus, and reacting said steam and hydrocarbon feed in the catalyst bed.Type: GrantFiled: January 13, 1999Date of Patent: May 29, 2001Assignee: Technology Management, Inc.Inventors: Thomas L. Cable, Adam B. Brakas, Robert C. Ruhl, Christopher E. Milliken
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Patent number: 6207122Abstract: A hydrocarbon fuel reforming method is disclosed suitable for producing synthesis hydrogen gas from reactions with hydrocarbons fuels, oxygen, and steam. A first mixture of an oxygen-containing gas and a first fuel is directed into a first tube 108 to produce a first reaction reformate. A second mixture of steam and a second fuel is directed into a second tube 116 annularly disposed about the first tube 108 to produce a second reaction reformate. The first and second reaction reformates are then directed into a reforming zone 144 and subject to a catalytic reforming reaction. In another aspect of the method, a first fuel is combusted with an oxygen-containing gas in a first zone 108 to produce a reformate stream, while a second fuel under steam reforming in a second zone 116. Heat energy from the first zone 108 is transferred to the second zone 116.Type: GrantFiled: November 2, 1998Date of Patent: March 27, 2001Assignee: Arthur D. Little, Inc.Inventors: Lawrence G. Clawson, William L. Mitchell, Jeffrey M. Bentley, Johannes H. J. Thijssen
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Patent number: 6048508Abstract: The present invention is directed to a process for simultaneously obtaining pure carbon monoxide and pure hydrogen in a steam reformer plant for hydrogen or ammonia generation, having a primary reformer, a secondary reformer and downstream thereof, a CO conversion stage. A part gas stream of the synthesis gas stream, which is discharged from the secondary reformer having a CO content of between 2 and 20 mol. % and is at a temperature of from 200 to 500.degree. C. and a pressure between 15 and 50 bar, is removed between the secondary reformer and the CO conversion stage. The part gas stream is then is cooled to a temperature below 100.degree. C., thereby condensing out the major part of the steam contained in the gas stream. The remaining raw synthesis gas stream is then guided by way of a multistage gas separation plant in which the gas components H.sub.2, residual steam, CH.sub.4, CO.sub.2 and optionally N.sub.2 are separated, either individually or together, from the CO.Type: GrantFiled: June 18, 1997Date of Patent: April 11, 2000Assignee: Bayer AktiengesellschaftInventors: Hans-Ulrich Dummersdorf, Hans-Joachim Muller, Dieter Grenner, Gerhard Moormann
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Patent number: 6007699Abstract: A process for oxidizing fuel and transferring the heat produced to a particular use in a combustion system such as fuels conversion. A bed of a mixture of materials forming an unmixed combustion catalyst, which in an oxidized state is readily reducible and in a reduced state is readily oxidizable, is placed in efficient thermal contact with a heat receiver for use in the combustion system. Fuel and air are alternately contacted with the bed, whereby the fuel is oxidized, the air is depleted of oxygen, and heat is liberated. The heat is efficiently transferred to the heat receiver by careful selection of the materials of the bed such that the temperatures produced when the fuel is oxidized and when the air is depleted of oxygen are advantageous to the particular use in the combustion system.Type: GrantFiled: August 21, 1996Date of Patent: December 28, 1999Assignee: Energy and Environmental Research CorporationInventor: Jerald A. Cole
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Patent number: 5997835Abstract: Process for catalytical steam reforming a carbonaceous feedstock without any carbon formation, wherein the feedstock is contacted with a nickel catalyst further including gold in an amount of 0.01 to 30% by weight calculated on the amount of nickel in the catalyst.Type: GrantFiled: June 10, 1998Date of Patent: December 7, 1999Assignee: Haldor Topsoe A/SInventors: Jens Hyldtoft, Jens Kehlet N.o slashed.rskov, Bjerne Steffen Clausen
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Patent number: 5800798Abstract: A process of producing a fuel gas for fuel cells, which comprises the steps of: a) treating kerosine having a sulfur content not higher than 5 ppm with a desulfurizing agent to reduce the sulfur content of said treated kerosine to 0.2 ppm or less and b) contacting said treated kerosine from step a) with a steam reforming catalyst to provide a fuel gas mainly composed of hydrogen, said desulfurizing agent in step a) comprising a copper-nickel alloy having a copper to nickel ratio by weight of 80:20 to 20:80 and at least one carrier selected from the group consisting of Al.sub.2 O.sub.3, ZnO and MgO, and the total content of copper and nickel in terms of metals in said desulfurizing agent being in the range of 40 to 70% by weight.Type: GrantFiled: June 25, 1996Date of Patent: September 1, 1998Assignees: Nippon Oil Co., Ltd, Petroleum Energy CenterInventors: Takashi Ino, Tadashi Seike
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Patent number: 5752995Abstract: A rare earth oxide stabilized, cobalt promoted nickel catalyst supported on refractory material, and a process employing said catalyst for the production of hydrogen-containing gases, such as synthesis gas, reducing gas or town's gas, or for the production of methane-enriched gases, such as pipe-line gas at low steam-to-carbon ratio not above 3.5 from various hydrocarbon feedstocks.Type: GrantFiled: June 30, 1994Date of Patent: May 19, 1998Inventor: Chia-chen Chu Kang
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Patent number: 5599517Abstract: A process for the production of hydrogen and/or carbon monoxide rich gases by steam reforming of a hydrocarbon feedstock, the process comprising the step of contacting the hydrocarbon feedstock and steam with a catalyst comprising nickel as a main catalytic component, a refractory carrier material for the nickel, and at least one catalytic element for the steam reforming of the hydrocarbon feedstock, the element being selected from the group consisting of germanium, tin, lead, arsenic, antimony and bismuth.Type: GrantFiled: December 13, 1995Date of Patent: February 4, 1997Assignee: Haldor Tops.o slashed.e A/SInventors: Israr Ul-Haque, David L. Trimm
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Patent number: 5595719Abstract: A process for the production of hydrogen and/or carbon monoxide rich gases by steam reforming of a hydrocarbon feedstock, the process comprising the step of contacting the hydrocarbon feedstock and steam with a catalyst comprising nickel as a main catalytic component, a refractory carrier material for the nickel, and at least one catalytic element for the steam reforming of the hydrocarbon feedstock, the element being selected from the group consisting of germanium, tin, lead, arsenic, antimony and bismuth.Type: GrantFiled: May 22, 1992Date of Patent: January 21, 1997Assignee: Haldor Topsoe A/SInventors: Israr Ul-Haque, David L. Trimm
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Patent number: 5556603Abstract: An apparatus is provided which is capable of removing impurities from an impurity-containing hydrogen gas without generating methane. A bed of particulate nickel in an amount of at least 5% by weight as elemental nickel at a temperature of from 0.degree. C. to 50.degree. C. removes all impurities except nitrogen. Then a bed of getter material, a zirconium, vanadium and iron alloy at a temperature of from 200.degree. C. to 800.degree. C. removes the nitrogen impurity thus producing purified hydrogen with an impurity content of less than 20 ppb.Type: GrantFiled: June 6, 1995Date of Patent: September 17, 1996Assignee: SAES Getters S.p.A.Inventors: Marco Succi, D'Arcy Lorimer
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Patent number: 5554351Abstract: Process for the high temperature steam reforming of hydrocarbons in the presence of a steam reforming catalyst arranged as fixed bed in a reforming reactor, wherein the catalyst bed comprises at least an upper and a lower layer, the upper layer being provided with catalyst particles having reduced activity in the steam reforming of hydrocarbons.Type: GrantFiled: May 17, 1994Date of Patent: September 10, 1996Assignee: Haldor Topsoe A/SInventor: Ivar I. Primdahl
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Patent number: 5498404Abstract: Process for catalytical steam reforming of a nitrogen containing carbonaceous feedstock with reduced formation of ammonia, wherein the feedstock is contacted with a supported nickel catalyst further including copper in an amount of 0.01-10% by weight calculated on the amount of nickel in the catalyst.Type: GrantFiled: August 24, 1994Date of Patent: March 12, 1996Assignee: Haldor Topsoe A/SInventors: Jens-Henrik B. Hansen, Leif Storgaard, Poul E. Jensen
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Patent number: 5496531Abstract: High surface purity heat transfer solids are formed, suitably by washing and treating particulate refractory inorganic solids, notably alumina, which contains as impurities up to about 0.5 wt. % silicon and/or up to about 500 wppm boron, with an acid, or dilute acid solution sufficient to reduce the concentration of silicon and boron in the outer peripheral surface layer of the particles, e.g., as measured inwardly toward the center of a particle to a depth of about 50 .ANG. using X-ray photoelectron spectroscopy, to no greater than about 5 atom percent silicon and boron, preferably about 2 atom percent silicon and boron, based on the total number of cations within said outer peripheral surface layer, thereby reducing the tendency of said particles to sinter and agglomerate in the conversion of said hydrocarbon to hydrogen and carbon monoxide in a fluidized bed synthesis gas operation vis-a-vis particles otherwise similar except that the particles are not treated with the acid.Type: GrantFiled: July 15, 1994Date of Patent: March 5, 1996Assignee: Exxon Research and Engineering CompanyInventors: Stephen M. Davis, LeRoy R. Clavenna, Geoffrey R. Say, Rocco A. Fiato
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Patent number: 5348717Abstract: A process utilizing a particulate catalyst, or particulate catalyst admixed with particulate heat transfer solids for conducting high temperature fluidized bed syn gas operations. Hydrogen and carbon monoxide are produced from a low molecular weight hydrocarbon by contact thereof, at high temperature in the presence of oxygen, or steam and oxygen, with a fluidized bed comprising said particulate solids. In one of its forms, barium hexaluminate is employed as a heat transfer solid, in concentrations ranging generally from about 10 wt. % to about 99.9 wt. %, in admixture with a particulate catalyst containing a metal, or metals, component catalytic for the production of hydrogen and carbon monoxide from low molecular weight hydrocarbons contacted with a fluidized bed of the catalyst at high temperature hydrothermal conditions. The catalyst, suitably one having a barium hexaluminate carrier component, is employed in concentration ranging generally from about 0.1 wt. % to about 90 wt. %.Type: GrantFiled: May 11, 1993Date of Patent: September 20, 1994Assignee: Exxon Research & Engineering Co.Inventors: LeRoy R. Clavenna, Stephen M. Davis, Geoffrey R. Say, Rocco A. Fiato
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Patent number: 5177303Abstract: A process for the conversion of hydrocarbons using an alumina-based catalyst which is prepared by(a) selecting an alumina catalyst having a bulk density of at least 0.6 g/ml and a pore volume of less than 0.6 ml/g;(b) heating the alumina of (a) to a temperature of at least 1000.degree. C. in the presence of a sintering agent containing at least one metal selected from nickel, chromium, cobalt and platinum; and(c) recovering a sintered alumina-based catalyst having a bulk density and an attrition resistance greater than that of the alumina of (a). Catalysts prepared by this process are useful in hydrocarbon conversion processes.Type: GrantFiled: December 30, 1991Date of Patent: January 5, 1993Assignee: The British Petroleum Company, p.l.c.Inventors: David C. Griffiths, Brian Kneale
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Patent number: 5130115Abstract: A process is disclosed for producing hydrogen of high purity from kerosene in petroleum oil. A feed of kerosene containing up to 1,000 wt.ppm of sulfur compounds is brought into contact with a nickel-containing sorbent at below 50 kg/cm.sup.2.G and at 150.degree.-350.degree. C. The resulting kerosene feed is further treated with a reforming catalyst under standard steam reforming conditions.Type: GrantFiled: January 23, 1989Date of Patent: July 14, 1992Assignees: Nippon Oil Co., Ltd., Petroleum Energy CenterInventors: Tokuo Fujisou, Shigeyuki Hayashi, Soichi Nomura, Akira Obuchi, Hideharu Kato
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Patent number: 5130114Abstract: The present invention provides a catalyst for steam reforming of hydrocarbons which comprises ruthenium supported on a zirconia carrier; and a catalyst for steam reforming of hydrocarbons which comprises (A) at least one element selected from the group consisting of rhodium and rutheniuim as an element imparting mainly reforming activity and (B) at least one element selected from the group consisting of nickel, lanthanum, praseodymium, neodymium, samarium, thorium, uranium, chromium, magnesium, calcium, and yttrium as an element for imparting co-catalyst function which are supported on a zirconia carrier; and furthermore a catalyst for steam reforming of hydrocarbons which comprises at least one element selected from the group consisting of rhodium and ruthenium which is supported on a partially stabilized zirconia carrier.Type: GrantFiled: January 3, 1991Date of Patent: July 14, 1992Inventor: Akira Igarashi
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Patent number: 5039510Abstract: The endothermic reaction of a hydrocarbon feedstock with steam and/or carbon dioxide is carried out using a double-tube reactor. In one preferred form of the reactor the catalyst is present as a coating on the outside of the inner tube. In another form inner tubes are mounted in one tube-plate and the outer tubes in a second tube plate and the tube plates are disposed across a cylindrical shell so as to define a heat exchange zone (provided with a heat source) a reactants feed zone and a products offtake zone. The heat source is preferably a burner, to be fed with the product of the endothermic reaction, followed by a secondary reforming catalyst. The apparatus makes possible processes for making raw hydrogen-containing gases with advantageous internal heat recovery.Type: GrantFiled: May 23, 1988Date of Patent: August 13, 1991Assignee: Imperial Chemical Industries PLCInventor: Alwyn Pinto
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Patent number: 5039350Abstract: A method for the decomposition of halogenated organic compounds contained in a contaminated medium comprises adding an alkali metal carbonate or bicarbonate to the contaminated medium in an aqueous solution or in a solvent having a boiling point of at least 200.degree. C., or in the form of a solid dispersion or suspension. The medium is heated to dehydrate the medium and then is further heated at a temperature between about 250.degree. and 400.degree. C. to effect decomposition of the halogenated organic compounds. An acid is then added to the medium in an amount sufficient to neutralize the same.Type: GrantFiled: April 27, 1990Date of Patent: August 13, 1991Assignee: The United States of America as represented by the Administrator of the Environmental Protection AgencyInventors: Charles J. Rogers, Alfred Kornel, Harold L. Sparks
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Patent number: 5026536Abstract: A process is disclosed for producing hydrogen of high purity from hydrocarbons. A selected hydrocarbon feed is contacted with a nickel-containing sorbent of a specified composition at below 50 kg/cm.sup.2 G and at from 150.degree. to 500.degree. C. The hydrocarbon feed thus treated is further reformed with a catalyst of a specified composition.Type: GrantFiled: December 18, 1989Date of Patent: June 25, 1991Assignees: Nippon Oil Co., Ltd., Petroleum Energy CenterInventors: Tomonori Shioiri, Shinichi Satake, Yasuo Sekido, Tokuo Fujisou, Akira Obuchi, Hideharu Kato
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Patent number: 4985230Abstract: A catalytic chemical process is carried out non-adiabatically using as a catalyst a body with two sets of channels throughout the body. One set of channels leads the process fluid towards one of two parallel walls of the catalyst chamber, the other set towards the outer wall, In slits between walls and catalyst heat is exchanged between process fluid and at least one of these walls upon reflecting the process fluid leaving channels of one set and entering channels of the other. The body may be made of alternatingly corrugated and plane sheets using in turn two different orientations for the corrugated sheets. It is preferred that the sheets are arranged orthogonal to the heat transmitting wall(s) and parallel to the overall direction of flow. The method is preferred for endothermic processes, especially steam reforming of hydrocarbon(s).Type: GrantFiled: August 26, 1988Date of Patent: January 15, 1991Assignee: Haldor Topsoe A/SInventors: Niels T. Baden, Ernst J. Jensen, Jorgen G. Larsen
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Patent number: 4985231Abstract: A mixture (34) of a hydrocarbon feedstock with steam and/or carbon dioxide is preheated and adiabatically steam reformed giving a partially reformed gas (26) which is then, optionally after reheating, further steam reformed inannular catalyst regions (32) of a double tube reformer (14). The outer tubes (28) of the double tube reformer are heated by a hot gas stream (12), e.g. in a fired furnace or by the hot gas stream produced by subjecting the reformed gas withdrawn from the inner tubes (30) of the double tube reformer to secondary reforming. The preheating (18), and the reheating (20), if any, is effected by indirect heat exchange with a hot gas after the latter has heated the outer tubes of the double tube reformer and/or with the reformed gas.Type: GrantFiled: December 7, 1988Date of Patent: January 15, 1991Assignee: Imperial Chemical Industries PLCInventor: Warwick J. Lywood
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Patent number: 4863712Abstract: A catalyst, or a precursor thereto, comprises, as the active material or as a support therefor, a ceramic foam having a network of irregular passages extending therethrough, said passages having an average minimum dimension in the range 20 to 300 .mu.m, said foam having a total porosity in the range 40 to 85% and an apparent density of at least 0.7 g. cm-3. The foam may be made by forming a negative replica of an open cell plastics foam by impregnation of the latter with a dispersion of the ceramic material, followed by drying and calcining the impregnated foam to remove the plastics material and to cause the ceramic material to sinter.For a steam reforming catalyst the ceramic may be alpha alumina and the active material nickel and/or cobalt.Type: GrantFiled: December 30, 1988Date of Patent: September 5, 1989Assignee: Imperial Chemical Industries PLCInventors: Martyn V. Twigg, William M. Sengelow
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Patent number: 4849155Abstract: Process for decontaminating exhaust gas from a fusion reactor fuel cycle of exhaust gas components containing at least one heavy hydrogen isotope selected from tritium and deuterium in compound form, in which the at least one heavy hydrogen isotope is liberated from its compound, separated out from the exhaust gas and fed back into the fuel cycle, the compound form being at least one compound which is ammonia or a hydrocarbon, comprising:(a) converting the at least one heavy hydrogen-containing compound into its elements in the exhaust gas by cracking the at least one heavy hydrogen containing compound with a cracking medium to liberate the hydrogen isotope,(b) passing the liberated hydrogen isotope through a membrane to separate out the liberated hydrogen isotope from the flow of the remaining exhaust gas, and(c) discharging the remaining decontaminated exhaust gas into the surrounding air.Type: GrantFiled: February 27, 1987Date of Patent: July 18, 1989Assignee: Kernstorschungzentrum Karlsruhe GmbHInventors: Ralf-Dieter Penzhorn, Manfred Glugla, Peter Schuster
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Patent number: 4707351Abstract: Reforming a hydrocarbon, or hydrocarbon derivative, feedstock with steam and/or carbon dioxide using saddle shaped units made of a low silica calcium aluminate cement composition as the catalyst support. The support preferably has a surface area of at least 0.5 m.sup.2 g.sup.-1 and a pore volume of at least 0.1 cm.sup.3 g.sup.-1.Type: GrantFiled: January 14, 1986Date of Patent: November 17, 1987Assignee: Imperial Chemical Industries PLCInventors: Leslie W. Lord, Kevin Kendall, David T. Williams, John H. Bateson
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Patent number: 4560547Abstract: A process for production of hydrogen from oil shale fines by direct introduction of the oil shale fines into a fluidized bed at temperatures about 1200.degree. to about 2000.degree. F. to obtain rapid heating of the oil shale. The bed is fluidized by upward passage of steam and oxygen, the steam introduced in the weight ratio of about 0.1 to about 10 on the basis of the organic carbon content of the oil shale and the oxygen introduced in less than the stoichiometric quantity for complete combustion of the organic carbonaceous kerogen content of the oil shale. Embodiments are disclosed for heat recovery from the spent shale and heat recovery from the spent shale and product gas wherein the complete process and heat recovery is carried out in a single reaction vessel.Type: GrantFiled: June 28, 1982Date of Patent: December 24, 1985Assignee: Institute of Gas TechnologyInventors: Frank C. Schora, John C. Janka, Harlan L. Feldkirchner
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Patent number: 4530918Abstract: The invention relates to a nickel containing catalyst composition of high thermal stability and which has outstanding resistance to carbon deposition, and is particularly but not exclusively for use in the steam reforming of hydrocarbons. The object of the invention is to provide an improved catalyst, which object is met by a catalyst derived from a precursor of approximate chemical compositionNi.sub.6 Al.sub.x La.sub.y (CO.sub.3).sub.(x+y)/2 (OH).sub.12+2(x+y) nH.sub.2 Owhere x is not less than 1 and not greater than 4; y is not less than 0.05 and not greater than 1.5 and n is approximately 4.Type: GrantFiled: October 26, 1983Date of Patent: July 23, 1985Assignee: Dyson Refractories LimitedInventors: Rodney M. Sambrook, Julian R. H. Ross
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Patent number: 4522940Abstract: An improved catalyst for the high temperature steam reforming of hydrocarbons is provided. The method of preparing the catalyst includes the steps of: (1) impregnating a ceramic matrix with a solution containing soluble salts of the catalytic components and a delayed precipitating agent; (2) removing the matrix from the solution; (3) draining the matrix; (4) heating the matrix to a temperature suitable for the controlled hydrolysis of the precipitation agent, thus increasing the pH of the absorbed solution and bringing about deposition of the insoluble hydroxides within the pores; (5) calcining the precipitate within the pores to a mixture of the oxides; and (6) reducing the oxides.Type: GrantFiled: July 16, 1981Date of Patent: June 11, 1985Assignee: Dyson Refractories LimitedInventors: Rodney M. Sambrook, Julian R. H. Ross
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Patent number: 4503029Abstract: High activity, sulfur tolerant steam reforming catalysts are described comprising rhodium or nickel supported on lanthanum stabilized alumina or magnesium promoted lanthanum stabilized alumina. The catalysts have improved activity over conventionally used catalysts in the presence of sulfur containing hydrocarbon fuel (such as No. 2 fuel oil) in a steam reforming environment. The material has particular utility in autothermal, tubular, cyclic and adiabatic steam reforming processes.Type: GrantFiled: March 1, 1984Date of Patent: March 5, 1985Assignee: United Technologies CorporationInventor: Herbert J. Setzer
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Patent number: 4491573Abstract: Desulfurized hydrocarbons are reacted with water vapor on catalysts at temperatures of 700.degree. to 1200.degree. C. to form a high-hydrogen product gas, which is separated in a pressure-swing adsorber into purified hydrogen and a separated gas, which contains substantially carbon oxides and methane. The purified hydrogen is supplied to a hydrogenating plant, which is operated at temperatures in the range of 250.degree. to 500.degree. C. and pressures of 200 to 400 bars. High-hydrogen gas from the hydrogenating plant flows in a pipeline through a heater and is then recycled to the hydrogenating plant. The heater consists of a fuelfired reheater, in which the separated gas is used as a fuel. The pipeline in which the high-hydrogen gas is recycled between the hydrogenating plant and the heater consists of an alloy steel, in which the carbon is combined in carbides with at least one of the alloying constituents chromium, molybdenum, tungsten or vanadium.Type: GrantFiled: March 19, 1984Date of Patent: January 1, 1985Assignee: Metallgesellschaft AktiengesellschaftInventors: Hans-Martin Stonner, Friedemann Marschner
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Patent number: 4469815Abstract: A nickel containing catalyst composition of high thermal stability and outstanding resistence to carbon deposition is provided for use in the steam reforming of hydrocarbons. The catalyst is derived from a precursor having lanthanum ions incorporated into a layer structure by means of coprecipitation from a solution containing soluble salts of the catalytically active components. The precursor is of approximate chemical composition Ni.sub.6 Al.sub.x La.sub.y (CO.sub.3).sub.x+y /2(OH).sub.12+2(x+y) nH.sub.2 O. A range of atomic ratios for the component is disclosed. Additional embodiments of the precursor are disclosed wherein anions other than carbonate are present and various proportions of the nickel content are replaced by magnesium.Type: GrantFiled: July 16, 1981Date of Patent: September 4, 1984Assignee: Dyson Refractories LimitedInventors: Rodney M. Sambrook, Julian R. H. Ross
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Patent number: 4331451Abstract: A process for catalytic gasification of heavy oil of a specific gravity of higher than 0.7 with steam or steam/oxygen-containing gas characterized in that the heavy oil is contacted with chromium oxide catalyst or a catalyst comprising a mixture of chromium oxide and one or more of alkaline earth metal oxides, aluminum oxide, zirconium oxide, nickel oxide and cobalt oxide.More particularly, the present invention relates to a process for catalytic gasification of heavy oil of a specific gravity of higher than 0.7 characterized in that the heavy oil is contacted with a gasification catalyst comprising calcium aluminate, an alkali aluminate or tungsten-containing nickel and then the heavy oil is further contacted with said chromium oxide catalyst or chromium oxide-containing catalyst.Type: GrantFiled: February 4, 1980Date of Patent: May 25, 1982Assignees: Mitsui Toatsu Chemicals, Inc., Toyo Engineering CorporationInventors: Kazuyoshi Isogaya, Eiiti Sugiyama, Kenji Yoshida, Katsutoshi Kikuchi
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Patent number: 4285837Abstract: A catalyst for steam reforming of hydrocarbons comprises porous aluminum oxide and nickel oxide, characterized in that the porous aluminum oxide in which the pore volume given by the pores of the pore diameter ranging from 60 to 120 A is not less than 0.35 ml./g. and the pore volume given by the pores of the pore diameter of more than 120 A is not less than 0.1 ml./g. and the purity determined upon ignition dryness is not less than 98% by weight is impregnated with nickel in an amount ranging from 10 to 30% by weight, as converted to nickel oxide basis, based on the total amount by weight of the catalyst.Type: GrantFiled: April 9, 1980Date of Patent: August 25, 1981Assignees: Fujimi Kenmazai Kogyo Co., Ltd., Toyo Engineering CorporationInventors: Nobuhiro Sato, Yoshinobu Yamaguchi, Hitoshi Kodama, Isamu Koshdyama, Nanahiko Kitano, Shigeharu Tsutsumi
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Patent number: 4216123Abstract: Steam reforming catalyst having good sinter and polymer resistance and which include a Group VIII metal such as nickel and alumina, have in their calcined but unreduced precursor form pore size distributions defined in the following relationships:(i) at least 55% of the pore volume of pores having a pore radius between 12 and 120 Angstrom Units is in the range 12-30 Angstrom Units, and(ii) the ratio of the pore volume contained in pores of 10-50 A to the pore volume contained in pores of 50-300 A is at least 5:1.These catalysts are prepared by coprecipitation at temperatures of not greater than 60.degree. C. wherein a solution of an alkali precipitating agent is added to a solution of the catalytic components.Type: GrantFiled: July 11, 1978Date of Patent: August 5, 1980Assignee: British Gas CorporationInventors: Reginald G. S. Banks, Alan Williams
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Patent number: 4207211Abstract: A catalyst is provided for the steam reforming of normally liquid hydrocarbons to produce carbon monoxide and hydrogen, which does not promote the deposition of carbonaceous materials upon the catalytic surfaces. The catalyst consists of nickel promoted with the oxides of iron and manganese within a specific manganese to iron ratio, said metal and metal oxides being supported upon a refractory support. The support is preferably aluminum oxide in its alpha phase having a surface area of less than 15 m.sup.2 /gm. The metallic constituents are impregnated onto said refractory low surface area support as salts and are calcined at sufficiently high temperature to convert the salts to the oxide but at a sufficiently low temperature that they do not chemically react with the support.Type: GrantFiled: May 19, 1978Date of Patent: June 10, 1980Assignee: United Catalysts Inc.Inventors: Karl J. Russ, Donald R. Broughton
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Patent number: 4142962Abstract: This invention relates to a method for making supported nickel catalysts which are characterized as having the nickel in a highly dispersed state, the catalysts and use thereof in hydrogenation, reforming and hydrocarbon synthesis reactions, for example, Fischer-Tropsch reactions. Catalysts prepared by the method of the instant invention, wherein nonaqueous solutions are used in preparing the catalyst, are characterized as having a degree of dispersion of at least 10% greater than similar catalysts prepared by the prior art aqueous impregnation techniques and in some instances show an improved degree of dispersion of more than 50% over the catalysts prepared by the prior art methods.Type: GrantFiled: February 13, 1978Date of Patent: March 6, 1979Assignee: Exxon Research & Engineering Co.Inventors: David J. C. Yates, Lawrence L. Murrell
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Patent number: 4110256Abstract: A catalyst for reforming fuel into a reformed gas rich in hydrogen comprises a catalyst carrier consisting of .gamma.-Al.sub.2 O.sub.3 and a catalyst metal mixture of the Cu--Ni--Cr type supported on the carrier, the metal mixture having the following composition: Cu = 36-62% by weight, Ni = 8-32% by weight, and Cr = 18-41% by weight, provided that Cu + Ni + Cr = 100% by weight. This catalyst is effective in reforming a fuel, especially methyl alcohol, into hydrogen over a wide temperature range from a low temperature to a high temperature. It is further improved by impregnating the carrier with at least one metal oxide selected from BaO, La.sub.2 O.sub.3, SiO.sub.2, CeO.sub.2, and SrO or by admixing the catalyst metal mixture with at least one of the oxides.Type: GrantFiled: June 10, 1977Date of Patent: August 29, 1978Assignee: Nippon Soken, Inc.Inventors: Yukihisa Takeuchi, Masao Wakayama
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Patent number: 4105591Abstract: A catalyst suitable for the high pressure gasification of heavy hydrocarbons to produce methane-containing gases is a calcined coprecipitated-alumina containing from 50- 65% Ni on a calcined unreduced basis. The catalyst contains (1) from 0 to not more than 0.43% K and from 0 to not more than 0.1% Na, (2) the combined weights of Na+ K does not exceed 0.011 gm atoms/100 gm of catalyst, (3) the ratio of Na:K falls within the area defined by ABCDEO in FIG. 1 of the drawings and (3) at combined Na+ K weights of from 0 to 0.05% the water loss is not more than 11.2%.The catalysts are prepared with the aid of a filtering aid selected from (NH.sub.4).sub.2 CO.sub.3, Na.sub.2 CO.sub.3, K.sub.2 CO.sub.3, Na NO.sub.3 or K NO.sub.3 to obtain low levels of alkali in the precursor. The catalyst may be employed for steam reforming reactions to produce methane-containing gases.Type: GrantFiled: July 12, 1976Date of Patent: August 8, 1978Assignee: British Gas CorporationInventors: Reginald G. S. Banks, Alan Williams
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Patent number: 4101449Abstract: A catalyst comprising 10 to 30 wt.% of nickel as nickel oxide, 20 to 60 wt.% of calcium as calcium oxide, 10 to 70 wt.% of aluminum as aluminum oxide and containing less than 1 wt.% of silicon dioxide. The catalyst is prepared by using: as the starting material for the nickel component, fine particles of nickel oxide obtained by heating a nickel compound which is decomposed to nickel oxide by heating at a temperature in the range of 400.degree. to 800.degree. C in the presence of oxygen; as the starting material for the calcium component, calcium oxide per se or a calcium compound which is decomposed to calcium oxide by heating and; as the starting material for the aluminum component, alumina cement of a high purity. The catalyst is prepared by mixing and kneading the starting materials with water, molding the same, then keeping the catalyst composition under a highly humid atmosphere at a temperature in the range of 5.degree. to 35.degree.Type: GrantFiled: May 9, 1977Date of Patent: July 18, 1978Assignees: Fujimi Kenmazai Kogyo Co., Ltd., Toyo Engineering CorporationInventors: Mikio Noda, Yoshinobu Yamaguchi, Ken-ichiro Uwano, Nobuhiro Sato, Tadayoshi Tomita, Koji Otsuka