And Another Metal Patents (Class 423/654)
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Patent number: 7771702Abstract: The invention provides active, affordable, durable, and sulfur-tolerant catalysts and related precursors and processes useful in hydrogen production. The catalysts have a wide applicability. For example, in one embodiment, the invention provides sulfur-tolerant catalysts which, when used in a catalytic fuel processor, will facilitate sufficient hydrogen generation within 30 seconds or so of automobile start-up to generate around 50 kW of fuel cell power. Catalysts of the instant invention are made by reducing a catalyst precursor comprising a support phase impregnated with one or more elemental transition metals, wherein: (a) the support phase is formed by dispersion of a monolayer on the surface of a high surface area alumina support; and (b) the monolayer comprises XOnYO2, where (1) XOn is a redox active metal oxide and n is either 1.5, 2, or 2.5 depending on the oxidation number of X, and (2) YO2 is a redox inactive metal oxide. Ni—V2O5—ZrO2/Al2O3 catalysts of the instant invention are preferred.Type: GrantFiled: February 20, 2003Date of Patent: August 10, 2010Assignees: University of Iowa Research Foundation, Honda Motor Co., Ltd.Inventors: Darrell P. Eyman, Christopher Brooks
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Method for producing functional nanocarbon and hydrogen by direct decomposition of lower hydrocarbon
Patent number: 7767182Abstract: In a reaction where a lower hydrocarbon is subjected to direct decomposition by using a catalyst to produce a functional nanocarbon and hydrogen, the lower hydrocarbon is subjected to the reaction in an coexistent gas comprising low concentration of oxidizing gas, reducing gas or a mixture thereof. The precursor of functional nanocarbon produced on the catalyst and amorphous carbon secondarily produced on the catalyst react with the coexistent gas so that being removed from the catalyst, making it possible to prevent the drop of conversion with time on stream due to the inhibition of the reaction by the precursor and by-product. In the case where the raw material of lower hydrocarbon is biogas, the coexistent gas can be easily contained in methane by lowering purification degree of methane.Type: GrantFiled: March 29, 2006Date of Patent: August 3, 2010Assignees: The Japan Steel Works, Ltd., National University Corporation Kitami Institute of Technology, Kajima CorporationInventors: Akio Tada, Satoru Nakamura, Hideaki Ito, Yoshitaka Togo, Kikuo Koseki, Hiroyuki Takasuna -
Patent number: 7722854Abstract: The present invention provides catalysts, reactors, and methods of steam reforming over a catalyst. Surprisingly superior results and properties obtained in methods and catalysts of the present invention are also described. For example, a coated catalyst was demonstrated to be highly stable under steam reforming conditions (high temperature and high pressure of steam). Methods of making steam reforming catalysts are also described.Type: GrantFiled: February 13, 2004Date of Patent: May 25, 2010Assignee: Velocy'sInventors: Junko M. Watson, Francis P. Daly, Yong Wang, Anna Lee Tonkovich, Sean P. Fitzgerald, Steven T. Perry, Laura J. Silva, Rachid Taha, Enrique Aceves de Alba, Ya-Huei Chin, Robert Rozmiarek, XiaoHong Li
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Patent number: 7700005Abstract: A method is provided for the thermo-neutral reforming of liquid hydrocarbon fuels which employs a Ni, Ce2O3, La2O3, Pt?ZrO2, Rh and Re catalyst having dual functionalities to achieve both combustion and steam reforming.Type: GrantFiled: December 26, 2006Date of Patent: April 20, 2010Assignees: Saudi Arabian Oil Company, King Fahd University of Petroleum & MineralsInventors: Tomoyuki Inui, Bashir Osama Dabbousi, Shakeel Ahmed, Fahad Ibrahim Al-Muhaish, Mohammed Abdul Bari Siddiqui
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Patent number: 7622058Abstract: A catalyst for adiabatically prereforming a feedstock wherein the catalyst comprises 1 to 20 wt. % nickel and 0.4 to 5 wt. % potassium on a calcium aluminate support. The overall catalyst porosity is greater than 40% with greater than 70% of the overall catalyst porosity contributed by pores having pore diameters of at least 500 ?, and having a median pore diameter greater than 2600 ?, and having a nitrogen BET area less than 6.5 m2/g.Type: GrantFiled: August 12, 2008Date of Patent: November 24, 2009Assignee: Air Products and Chemicals, Inc.Inventors: Diwakar Garg, Shankar Nataraj, Kevin Boyle Fogash, James Richard O'Leary, William Robert Licht, Sanjay Mehta, Eugene S. Genkin
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Patent number: 7618612Abstract: Disclosed is a method of producing hydrogen from oxygenated hydrocarbon reactants, such as methanol, glycerol, sugars (e.g. glucose and xylose), or sugar alcohols (e.g. sorbitol). The method takes place in the condensed liquid phase. The method includes the steps of reacting water and a water-soluble oxygenated hydrocarbon in the presence of a metal-containing catalyst. The catalyst contains a metal selected from the group consisting of Group VIIIB transitional metals, alloys thereof, and mixtures thereof. The disclosed method can be run at lower temperatures than those used in the conventional steam reforming of alkanes.Type: GrantFiled: May 9, 2005Date of Patent: November 17, 2009Assignee: Wisconsin Alumni Research FoundationInventors: Randy D. Cortright, James A. Dumesic
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Patent number: 7591992Abstract: The present invention relates to a process for producing a hydrogen-containing gas. The process comprises introducing a regeneration gas into a hydrogen reaction vessel containing solid packing material thereby at least partially regenerating the solid packing material and forming an effluent gas from the regeneration gas. At least a portion of the effluent gas is introduced into another hydrogen reaction vessel containing solid packing material. The effluent gas may be used, for example, to purge the other hydrogen reaction vessel and/or regenerate the solid packing material in the other hydrogen reaction vessel. Solid packing materials may include at least one of a complex metal oxide, a steam hydrocarbon reforming catalyst, an oxygen ion conducting ceramic, a hydrocarbon partial oxidation catalyst, and a hydrocarbon cracking catalyst.Type: GrantFiled: January 25, 2006Date of Patent: September 22, 2009Assignee: Air Products and Chemicals, Inc.Inventors: Xiang-Dong Peng, Shankar Nataraj
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Patent number: 7578986Abstract: Materials that are useful for absorption enhanced reforming (AER) of a fuel, including absorbent materials such as Group 1 and Group 2 metal oxides that are adapted to absorb CO2 and catalyst materials such as reforming catalysts and water-gas shift catalysts, and methods for using the materials. The materials can be fabricated by spray processing. The use of the materials in AER can produce a H2 product gas having a high H2 content and a low level of carbon oxides.Type: GrantFiled: August 31, 2007Date of Patent: August 25, 2009Assignee: Cabot CorporationInventors: Mark J. Hampden-Smith, Paolina Atanassova, Jian-Ping Shen, Paul Napolitano, James Brewster
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Patent number: 7572432Abstract: Disclosed herein is a method comprising combusting a feed stream to form combustion products; and reforming the combustion products to produce a gaseous composition comprising hydrogen. Disclosed herein too is a method for producing hydrogen comprising introducing a feed stream comprising natural gas and air or oxygen into a cyclical compression chamber; compressing the feed stream in the cyclical compression chamber; combusting the feed stream in the cyclical compression chamber to produce combustion products; discharging the combustion products from the cyclical compression chamber into a reforming section; and reforming the combustion products with steam in the reforming section to produce a gaseous composition comprising hydrogen.Type: GrantFiled: April 13, 2004Date of Patent: August 11, 2009Assignee: General Electric CompanyInventors: Sauri Gudlavalleti, Michael Bowman, Chellappa Balan, Shailesh Singh Bhaisora, Andrei Colibaba-Evulet, Narayan Ramesh
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Patent number: 7572304Abstract: An apparatus and method for the preferential oxidation of carbon monoxide in a hydrogen-rich fluid. The apparatus utilizes one or more reactors that are dimensioned to optimize the exothermic oxidation reaction and the transfer of heat to and from the catalyst bed. A reactor of the apparatus has an elongated cylindrical catalyst bed and heat transfer means adjacent the catalyst bed. The heat transfer means is suitable for pre-heating the catalyst bed during start-up operations and for removing the heat from the catalyst bed during the oxidation reaction. One or more reactors of different dimensions may be utilized depending upon the pressure of the hydrogen-rich fluid to be directed into the apparatus and the pressure requirements for the carbon monoxide-depleted fluid exiting the apparatus. For instance, in low pressure operations where it may be desirable to minimize the pressure drop across the apparatus, two or more reactors having relatively smaller dimensions can be utilized.Type: GrantFiled: September 28, 2004Date of Patent: August 11, 2009Assignee: Texaco Inc.Inventors: W. Spencer Wheat, Daniel G. Casey, Curtis L. Krause, Marshall D. Wier, David W. Harrison, Sr.
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Publication number: 20090196822Abstract: Complex metal oxide-containing pellets and their use for producing hydrogen. The complex metal oxide-containing pellets are suitable for use in a fixed bed reactor due to sufficient crush strength. The complex metal oxide-containing pellets comprise one or more complex metal oxides and at least one of in-situ formed calcium titanate and calcium aluminate. calcium titanate and calcium aluminate are formed by reaction of suitable precursors in a mixture with one or more complex metal carbonates. The complex metal oxide-containing pellets optionally comprise at least one precious metal.Type: ApplicationFiled: January 13, 2009Publication date: August 6, 2009Applicant: AIR PRODUCTS AND CHEMICALS, INC.Inventors: Diwakar Garg, Robert Quinn, Frederick Carl Wilhelm, Gokhan Alptekin, Margarita Dubovik, Matthew Schaefer
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Patent number: 7556872Abstract: The present invention provides an adsorbent for removing sulfur compounds, which adsorbent can effectively remove a variety of sulfur compounds contained in a hydrocarbon fuel to a low concentration even at room temperature; a process for effectively producing hydrogen that can be used in a fuel cell; and a fuel cell system employing hydrogen produced through the process. The adsorbent for removing a sulfur compound contained in a hydrocarbon fuel contains cerium oxide. The process for producing hydrogen that can be used in a fuel cell includes desulfurizing a hydrocarbon fuel through removal of a sulfur compound contained in the a hydrocarbon fuel by use of the aforementioned adsorbent and, subsequently, bringing the thus-desulfurized fuel into contact with a partial-oxidation reforming catalyst, an authothermal reforming catalyst, or a steam reforming catalyst. The fuel cell system employs hydrogen produced through the process.Type: GrantFiled: August 26, 2003Date of Patent: July 7, 2009Assignee: Idemitsu Kosan Co., Ltd.Inventors: Kozo Takatsu, Gakuji Takegoshi
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Patent number: 7553475Abstract: A method and apparatus for use in producing high-pressure hydrogen from natural gas, methanol, ethanol, or other fossil fuel-derived and renewable hydrocarbon resources. The process can produce hydrogen at pressure ranging from 2000 to 12,000 pounds per square inch (psi) using a hydrogen feedstock (16, 18) high pressure water (12, 18), and an appropriate catalyst. Following making and heating in preheater (14), the catalyst reacts with the hydrogen feedstock (16, 18) and high pressure water (12, 18) in a catalytic reformer (20) maintained under desired temperature and pressure conditions. Reformate products exit reformer (200) and flow into condenser (22), in which water and a portion of the carbon dioxide product are condensed.Type: GrantFiled: April 15, 2004Date of Patent: June 30, 2009Assignee: Energy & Environmental Research Center FoundationInventors: Ronald C. Timpe, Ted R. Aulich
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Patent number: 7550635Abstract: Process for the preparation hydrogen and a mixture of hydrogen and carbon monoxide containing gas from a carbonaceous feedstock by performing the following steps: (a) preparing a mixture of hydrogen and carbon monoxide having a temperature of above 700° C. (51); (b) catalytic steam reforming a carbonaceous feedstock in a Convective Steam Reformer zone (44), wherein the required heat for the steam reforming reaction is provided by convective heat exchange between the steam reformer reactor zone and the effluent of step (a) to obtain as separate products a steam reforming product having a hydrogen to CO molar ratio of greater than 2 and a cooled effluent of step (a), and (c) separating hydrogen from the steam reforming product.Type: GrantFiled: April 13, 2004Date of Patent: June 23, 2009Assignee: Shell Oil CompanyInventor: Thian Hoey Tio
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Patent number: 7547332Abstract: Process and apparatus for the preparation of synthesis gas by catalytic steam and/or CO2 reforming of a hydrocarbon feedstock comprising the following steps: (a) heating the reaction mixture of hydrocarbon and steam and/or CO2 in a heated steam reforming unit integrated with the flue gas containing waste heat section from the fired tubular reformer in which reforming of the reaction mixture takes place by contact with a solid reforming catalyst (b) feeding the partially steam reformed mixture to the fired tubular reformer and further reforming the mixture to the desired composition and temperature, wherein the heated steam reforming unit comprises a piping system containing reaction sections with solid reforming catalyst comprising catalyst pellets and/or catalysed structured elements, the piping system being part of the process gas piping system integrated with the flue gas-containing waste heat section.Type: GrantFiled: February 23, 2006Date of Patent: June 16, 2009Assignee: Haldor Topsoe A/SInventors: Peter Scier Christensen, Thomas Rostrup Nielsen, Niels Erikstrup, Kim Assberg-Petersen, Jens-Henrik Bak Hansen, Ib Dybkjer
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Patent number: 7544346Abstract: A multi-step process of converting hydrocarbon fuel to a substantially pure hydrogen gas feed includes a plurality of modules stacked end-to-end along a common axis. Each module includes a shell having an interior space defining a passageway for the flow of gas from a first end of the shell to a second end of the shell opposite the first end, and a processing core being contained within the interior space for effecting a chemical, thermal, or physical change to a gas stream passing axially through the module. The multi-step process includes: providing a fuel processor having a plurality of modules stacked end-to-end along a common axis; and feeding the hydrocarbon fuel successively through each of the modules in an axial direction through the tubular reactor to produce the hydrogen rich gas.Type: GrantFiled: July 19, 2006Date of Patent: June 9, 2009Assignee: Texaco Inc.Inventors: Curtis L. Krause, James K. Wolfenbarger, Paul F. Martin
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Patent number: 7510648Abstract: The invention provides an optimum method for utilizing a desulfurizing agent for liquid hydrocarbons which can efficiently remove sulfur content from kerosene without performing addition of hydrogen to a low sulfur concentration and which has a prolonged lifetime. The invention provides a desulfurization method which includes removing sulfur content from kerosene by use of a metallic desulfurizing agent without performing addition of hydrogen, characterized in that the method employs desulfurization conditions satisfying the following formula (1): 1.06×Pope0.44<Tope/T50<1.78×Pope0.22??(1) (wherein Tope is operation temperature (° C.); Pope is operation pressure (MPa); and T50 is a temperature per 50 percent recovered as determined by “test method for distillation at atmospheric pressure” stipulated in JIS K2254 “Petroleum products—Determination of distillation characteristics as revised in 1998”).Type: GrantFiled: July 22, 2003Date of Patent: March 31, 2009Assignee: Idemitsu Kosan Co., Ltd.Inventors: Tadashi Kisen, Hiroto Matsumoto, Hisashi Katsuno, Kazuhito Saito
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Patent number: 7504048Abstract: A steam/hydrocarbon reformer employing a conventional radiantly heated first reformer section and a flue-gas heated second reformer section is disclosed. The second reformer section comprises catalyst-containing tubes for partially reforming a hydrocarbon stream. The catalyst-containing tubes in the second reformer section are disposed in a conduit for conveying flue gas from the first reformer section, thereby receiving heat from the flue gases. The flue gases flow either cocurrent or countercurrent to the process gas in the catalyst-containing tubes in the second reformer section. The partially reformed hydrocarbon stream from the second reformer section is fed to the catalyst-containing tubes in the first reformer section thereby producing a hydrogen-rich synthesis gas.Type: GrantFiled: June 14, 2005Date of Patent: March 17, 2009Assignee: Air Products and Chemicals, Inc.Inventor: William Robert Licht
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Publication number: 20090014315Abstract: An apparatus for producing hydrogen by microwave includes a microwave heater, a reaction tube comprising a catalyst bed, a cap, an output unit and a microwave control box. A method of producing hydrogen using microwaves has steps of feeding gas and liquid, vaporizing the liquid to from a mixed gas and heating the mixed gas. A liquid and a gas are selected at predetermined ratios to form the mixed gas that reacts on the catalyst bed to from hydrogen. Microwaves allow the apparatus to be ready for production quicker and reduce space required by the apparatus. Heating the liquid and gas using microwaves is fast so has a good energy efficiency.Type: ApplicationFiled: July 13, 2007Publication date: January 15, 2009Inventor: Wei-Hsin Chen
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Patent number: 7449167Abstract: A process for adiabatically prereforming a feedstock, includes: providing an adiabatic reactor; providing a catalyst containing 1-20 wt. % nickel and 0.4-5 wt. % potassium, wherein the catalyst has an overall catalyst porosity of 25-50% with 20-80% of the overall catalyst porosity contributed by pores having pore diameters of at least 500 ?; providing the feedstock containing natural gas and steam, wherein the natural gas contains an initial concentration of higher hydrocarbons, and a ratio of steam to natural gas in the feedstock is from 1.5:1 to 5:1; preheating the feedstock to a temperature of 300-700° C. to provide a heated feedstock; providing the heated feedstock to the reactor; and producing a product containing hydrogen, carbon monoxide, carbon dioxide, unreacted methane, and steam, wherein said product contains a reduced concentration of higher hydrocarbons less than the initial concentration of higher hydrocarbons, to prereform the feedstock.Type: GrantFiled: July 8, 2004Date of Patent: November 11, 2008Assignee: Air Products and Chemicals, Inc.Inventors: Diwakar Garg, Shankar Nataraj, Kevin Boyle Fogash, James Richard O'Leary, William Robert Licht, Sanjay Mehta, Eugene S. Genkin
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Patent number: 7445647Abstract: A method for making fuel cells is disclosed and includes placing catalyst strips on an anode side and a cathode side of a proton exchange membrane disposed between carbon bases. The method includes metalizing at least two collectors, and drilling a plurality of paths through the body portions to form a first and second metalized collectors, which are placed on opposite sides of the proton exchange membrane to form a membrane electrode assembly. The metalized collectors are connected to form an electrical circuit for operating the fuel cell. A flexible fuel plenum and a flexible oxidant plenum are disposed on opposite sides of the membrane electrode assembly, and a fuel manifold and an oxidant manifold of a sealable two-part housing engage the membrane electrode assembly to provide oxidant to the flexible oxidant plenum and fuel to the flexible fuel plenum forming an operational singe unit fuel cell.Type: GrantFiled: May 19, 2006Date of Patent: November 4, 2008Assignee: Hydra Fuel Cell CorporationInventors: Edward Lee Davis, Benjamin Franklin Schafer
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Patent number: 7442290Abstract: Mesoporous aluminum oxides with high surface areas have been synthesized using inexpensive, small organic templating agents instead of surfactants. Optionally, some of the aluminum can be framework-substituted by one or more other elements. The material has high thermal stability and possesses a three-dimensionally randomly connected mesopore network with continuously tunable pore sizes. This material can be used as catalysts for dehydration, hydrotreating, hydrogenation, catalytic reforming, steam reforming, amination, Fischer-Tropsch synthesis and Diels-Alder synthesis, etc.Type: GrantFiled: March 21, 2007Date of Patent: October 28, 2008Assignee: Lummus Technology Inc.Inventors: Zhiping Shan, Jacobus Cornelius Jansen, Chuen Y. Yeh, Philip J. Angevine, Thomas Maschmeyer
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Patent number: 7438889Abstract: A process for producing hydrogen comprising reacting at least one hydrocarbon and steam in the presence of a complex metal oxide and a steam-hydrocarbon reforming catalyst in a production step under reaction conditions sufficient to form hydrogen and a spent complex metal oxide, wherein the complex metal oxide is represented by the formula (A?xCax?Mgx?)x(B?yMny?Fey?)yOn where A? represents at least one element selected from the group consisting of Sr, Ba, a Group 1 element, and an element of the Lanthanide series according to the IUPAC Periodic Table of the Elements; B? represents at least one element selected from the group consisting of Cu, Ni, Co, Cr, and V; 0?x?1, 0?x??1, 0?x??1 wherein x+x?+x?=x; 0?y?1, 0?y??1, 0?y??1 wherein y+y?+y?=y; 1?x?10; 1?y?10; and n represents a value such that the complex metal oxide is rendered electrically neutral.Type: GrantFiled: June 24, 2005Date of Patent: October 21, 2008Assignee: University of South CarolinaInventors: Guido Peter Pez, Baolong Zhang, Hans-Conrad zur Loye
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Patent number: 7429373Abstract: Process for producing hydrogen comprising reacting at least one hydrocarbon and steam in the presence of a complex metal oxide and a steam-hydrocarbon reforming catalyst in a production step under reaction conditions sufficient to form hydrogen gas and a spent complex metal oxide, wherein the complex metal oxide is represented by the formula AxByOn wherein A represents at least one metallic element having an oxidation state ranging from +1 to +3, inclusive, wherein the metallic element is capable of forming a metal carbonate; x is a number from 1 to 10, inclusive; B represents at least one metallic element having an oxidation state ranging from +1 to +7, inclusive; y is a number from 1 to 10, inclusive; and n represents a value such that the complex metal oxide is rendered electrically neutral.Type: GrantFiled: June 24, 2005Date of Patent: September 30, 2008Assignee: Air Products and Chemicals, Inc.Inventors: Guido Peter Pez, Robert Quinn, Shankar Nataraj
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Patent number: 7427388Abstract: A process for prereforming natural gas containing higher hydrocarbons and methane, includes providing a reactor having a nickel catalyst; providing steam, hydrogen, and natural gas containing higher hydrocarbons and methane to the reactor; adding an oxidant to the feedstock, wherein the oxidant provides oxygen in an amount less than the amount required to partially oxidize all higher hydrocarbons to a mixture of carbon monoxide and hydrogen; reacting the oxidant with higher hydrocarbons; and forming a gaseous mixture containing methane, carbon monoxide, carbon dioxide, steam and hydrogen substantially free of higher hydrocarbons and oxygen. The gaseous mixture can be reformed. An apparatus for performing the process includes a reactor; a feedstock source containing steam, hydrogen, and natural gas comprising higher hydrocarbons and methane; an oxidant source; valves and pipes connecting the natural gas source, the oxidant source and the reactor; and a nickel-containing catalyst within the reactor.Type: GrantFiled: March 19, 2004Date of Patent: September 23, 2008Assignee: Air Products and Chemicals, Inc.Inventors: Diwakar Garg, Shankar Nataraj, John Nelson Armor, John Michael Repasky
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Patent number: 7344789Abstract: The invention provides a controlled hypergolic approach to using concentrated hydrogen peroxide in combination with certain hydrocarbons such as ethanol, methanol, methane as well as more common fuels such as gasoline, diesel, DME, JP5, JP8 and the like to generate a gas mixture primarily composed of hydrogen and carbon dioxide. Because air is not used as the oxygen source, this novel process does not allow the formation of nitrous oxide (NOx) compounds, thereby avoiding the primary source of nitrogen contamination as well. The process is executed in a constraining system on a micro scale such that the resulting hydrogen supply is self-pressurizing. This enables the incorporation of an “on-demand” hydrogen fuel source for a variable output fuel cell power plant such as those proposed for use in automobiles, marine vessels and stationary power sources. In another embodiment of the present invention hydrogen peroxide is catalytically, or thermally reacted to provide H2O vapor and O2.Type: GrantFiled: July 1, 2004Date of Patent: March 18, 2008Assignee: CBH2 Technologies, Inc.Inventors: Jeffrey L. Barber, Jeremiah J. Cronin
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Patent number: 7309480Abstract: A catalyst that can be used for the production of hydrogen from hydrocarbon fuels in steam reforming processes contains an active metal of, e.g., at least one of Ir, Pt and Pd, on a catalyst support of, e.g., at least one of monoclinic zirconia and an alkaline-earth metal hexaaluminate. The catalyst exhibits improved activity, stability in both air and reducing atmospheres, and sulfur tolerance.Type: GrantFiled: April 16, 2004Date of Patent: December 18, 2007Assignees: H2Gen Innovations, Inc., Süd-Chemie, Inc.Inventors: Franklin D. Lomax, Jr., John Lettow, Aaron L. Wagner, Jon P. Wagner, Duane Myers
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Patent number: 7297169Abstract: The present invention is an apparatus arranged to maximize heat utilization for a hydrocarbon steam reforming process to produce synthesis gas. The apparatus comprises a refractory lined vessel with partition walls that divide the inside of the vessel into (1) a combustion chamber(s) containing one or more burners, and (2) convection chambers used as a means to remove combustion products from the combustion chamber through one or more openings at the opposite end of the burner end. The combustion chamber contains one or more reformer tubes in which a mixed-feed of hydrocarbon and steam flow co-current with combustion products and receive direct radiant heat from the combustion flame through the tube wall. The convection chambers contain a tube-in-tube device filled with catalyst in the annuli.Type: GrantFiled: December 24, 2003Date of Patent: November 20, 2007Assignee: Air Products and Chemicals, Inc.Inventors: Hoanh Nang Pham, David Hon Sing Ying, Shoou-I Wang, Scott David Madara, Joel Charles MacMurray
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Patent number: 7267811Abstract: Materials that are useful for absorption enhanced reforming (AER) of a fuel, including absorbent materials and catalyst materials, and methods for using such materials for the conversion of carbon-based fuels to a H2-rich product gas. The materials can be fabricated by spray processing. The use of the materials in AER can produce a H2 product gas having a high H2 content and a low level of carbon oxides. The method for converting carbon-based fuels to a H2-rich product gas includes forming an intermediate gas product from the carbon-based fuel using a catalyst and contacting the intermediate gas product with an absorbent to absorb CO2. The absorbent can be regenerated while retaining a high absorption capacity.Type: GrantFiled: November 26, 2003Date of Patent: September 11, 2007Assignee: Cabot CorporationInventors: Mark J. Hampden-Smith, Paolina Atanassova, Jian-Ping Shen, Paul Napolitano, James Brewster
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Patent number: 7268097Abstract: 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: GrantFiled: April 2, 2001Date of Patent: September 11, 2007Assignee: Idemitsu Kosan Co., Ltd.Inventors: Hisashi Katsuno, Satoshi Matsuda, Kazuhito Saito, Masahiro Yoshinaka
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Patent number: 7264788Abstract: Materials that are useful for absorption enhanced reforming (AER) of a fuel, including absorbent materials and catalyst materials and methods for using the materials. The materials can be fabricated by spray processing. The use of the materials in AER can produce a H2 product gas having a high H2 content and a low level of carbon oxides.Type: GrantFiled: November 24, 2004Date of Patent: September 4, 2007Assignee: Cabot CorporationInventors: Mark J. Hampden-Smith, Paolina Atanassova, Jian-Ping Shen, James Brewster, Paul Napolitano
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Patent number: 7250151Abstract: Integrated Combustion Reactors (ICRS) and methods of making ICRs are described in which combustion chambers (or channels) are in direct thermal contact to reaction chambers for an endothermic reaction. Particular reactor designs are also described. Processes of conducting reactions in integrated combustion reactors are described and results presented. Some of these processes are characterized by unexpected and superior results, and/or results that can not be achieved with any prior art devices.Type: GrantFiled: August 15, 2002Date of Patent: July 31, 2007Assignee: VelocysInventors: Anna Lee Tonkovich, Sean P. Fitzgerald, Paul W. Neagle, Dongming Qiu, Matthew B. Schmidt, Steven T. Perry, David J. Hesse, Robert J. Luzenski, G. Bradley Chadwell, Ying Peng, James A. Mathias, Richard Q. Long, Wm. Allen Rogers, Ravi Arora, Wayne W. Simmons, Barry L. Yang, Yong Wang, Thomas Forte, Robert Jetter
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Patent number: 7226574Abstract: A process is disclosed for converting a hydrocarbon reactant to a product comprising CO and H2. The process comprises: (A) flowing a reactant composition comprising the hydrocarbon reactant and oxygen or a source of oxygen through a microchannel reactor in contact with a catalyst under reaction conditions to form the product, the microchannel reactor comprising at least one process microchannel with the catalyst positioned within the process microchannel, the hydrocarbon reactant comprising methane, the contact time for the reactant composition within the process microchannel being up to about 500 milliseconds, the temperature of the reactant composition and product within the process microchannel being up to about 1150° C., the conversion of the hydrocarbon reactant to carbon oxide being at least about 50%. The product formed in step (A) may be converted to a product comprising CO2 and H2O in a microchannel reactor.Type: GrantFiled: May 30, 2003Date of Patent: June 5, 2007Assignee: Velocys, Inc.Inventors: Richard Q. Long, Anna Lee Tonkovich, Eric Daymo, Barry L. Yang, Yong Wang, Francis P. Daly
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Patent number: 7217303Abstract: The present invention provides an improvement in the process of producing hydrogen from hydrocarbon-containing streams. A cyclic reforming process, referred to as pressure swing reforming, provides an efficient means for producing a hydrogen containing synthesis gas for fuel cell applications. Pressure swing reforming may be integrated with shift reactions, preferential oxidation, and membrane separation, achieving thermal and material efficiencies relative to conventional hydrogen production. In one embodiment, at least some synthesis gas which is first produced in the pressure swing reforming process is combusted with air to provide the heat for the regeneration step of the pressure swing reforming process.Type: GrantFiled: January 13, 2004Date of Patent: May 15, 2007Assignee: ExxonMobil Research and Engineering CompanyInventors: Frank Hershkowitz, Paul J. Berlowitz, Randall D. Partridge
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Patent number: 7160344Abstract: The present invention relates to a catalytic process for the continuous production of carbon monoxide-free hydrogen from methane or methane-rich hydrocarbons using a solid catalyst comprising at least one group VIII metal in two parallel catalytic reactors.Type: GrantFiled: December 18, 2002Date of Patent: January 9, 2007Assignee: Council of Scientific and Industrial ResearchInventors: Vasant Ramchandra Choudhary, Amarjeet Munshiram Rajput
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Patent number: 7070752Abstract: Supported perovskite-type oxides are described. The perovskite-type oxides have the general formula of AxA?x?ByB?y?O3??, wherein A is an ion of a metal of Group IIIa or IIIb of the periodic table of elements or mixtures thereof; A? is an ion of a metal of Groups Ia or IIa of the periodic table or mixtures thereof; B and B? are ions of a d-block transition metal of the periodic table or mixtures thereof; x, x?, y and y? vary from 0 to 1; 0.95<x+x?<1.05; 0.95<y+y?<1.05; ? is the deviation from ideal oxygen stoichiometry. This invention also provides for the selection of support materials and the shapes of supported perovskite-type oxides as well as the methods for making them.Type: GrantFiled: January 19, 2005Date of Patent: July 4, 2006Assignee: The BOC Group, Inc.Inventors: Yongxian Zeng, Rudolph J. Wolf, Frank R. Fitch, Martin Bülow, Satish S. Tamhankar, Divyanshu R. Acharya
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Patent number: 7067453Abstract: The subject invention is a catalyst consisting of an oxide or mixed oxide support and bimetallic catalytically active compounds. The supporting oxide can be a single oxide, such as Al2O3; it also can be a mixture of oxides, such as Y2O3 stabilized ZrO2 (YSZ), Al2O3 with CeO2, Al2O3 with YSZ and others. The bimetallic compounds, acting as active components, are selected from platinum, and ruthenium, prepared in an appropriate ratio. The catalyst is used in the steam reforming of hydrocarbons to produce hydrogen for applications such as polymer electrolyte membrane fuel cells.Type: GrantFiled: July 15, 2002Date of Patent: June 27, 2006Assignee: InnovaTek, Inc.Inventors: Qimin Ming, Todd Healey, Patricia Marie Irving
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Patent number: 7060118Abstract: Process for the preparation of hydrogen and carbon monoxide rich gas by steam reforming of hydrocarbon feedstock in presence of a steam reforming catalyst supported as thin film on the wall of a reactor, comprising steps of (a) optionally passing a process gas of hydrocarbon feedstock through a first reactor with a thin film of steam reforming catalyst supported on walls of the reactor in heat conducting relationship with a hot gas stream; (b) passing effluent from the first reactor to a subsequent tubular reactor being provided with a thin film of steam reforming catalyst and/or steam reforming catalyst pellets and being heated by burning of fuel, thereby obtaining a partially steam reformed gas effluent and a hot gas stream of flue gas; (c) passing the effluent from the second reactor to an autothermal reformer; and (d) withdrawing from the autothermal reformer a hot gas stream of product gas rich in hydrogen and carbon monoxide.Type: GrantFiled: July 21, 1998Date of Patent: June 13, 2006Assignee: Haldor Topse A/SInventors: Ib Dybkjaer, Peter Seier Christensen, Viggo Lucassen Hansen, J. R. Rostrup-Nielsen
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Patent number: 7037485Abstract: A steam methane reforming method in which a feed stream is treated in a reactor containing a catalyst that is capable of promoting both hydrogenation and partial oxidation reactions. The reactor is either operated in a catalytic hydrogenation mode to convert olefins into saturated hydrocarbons and/or to chemically reduce sulfur species to hydrogen sulfide or a catalytic oxidative mode utilizing oxygen and steam to prereform the feed and thus, increase the hydrogen content of a synthesis gas produced by a steam methane reformer. The method is applicable to the treatment of feed streams containing at least 15% by volume of hydrocarbons with two or more carbon atoms and/or 3% by volume of olefins, such as a refinery off-gas. In such case, the catalytic oxidative mode is conducted with a steam to carbon ratio of less than 0.5, an oxygen to carbon ratio of less than 0.25 and a reaction temperature of between about 500° C. and about 860° C.Type: GrantFiled: June 14, 2005Date of Patent: May 2, 2006Assignee: Praxair Technology, Inc.Inventors: Raymond Francis Drnevich, Vasilis Papavassiliou
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Patent number: 7025903Abstract: A process for removing contaminants from a reformer comprises removal of particulate matter under operating, or stand-by conditions, or at the start of a shutdown procedure, by introducing a gas mixture to the reformer system having an oxidant-to-fuel ratio concentration leaner than a normal oxidant-to-fuel ratio concentration and at a gas flow rate less than a peak flow rate. The process produces elevated temperatures at the reformer inlet and elevated levels of carbon dioxide and water that combine to remove the contaminants. Another embodiment includes removal of particulate matter during a shutdown procedure by cycling the flow of fuel and air on and off; monitoring an exit temperature of a catalyst substrate and alternatively, cycling the oxidant flow on and off when the exit temperature is less than or greater than a threshold temperature such that the exit temperature of the catalyst substrate is maintained below the temperature at which aging of the catalyst and/or a washcoat material may occur.Type: GrantFiled: November 29, 2001Date of Patent: April 11, 2006Assignee: Delphi Technologies, Inc.Inventors: Malcolm James Grieve, Juergen T. Kammerer, Amanda M. Weiss, David Robert Schumann
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Patent number: 7011807Abstract: Supported reactive catalysts having a controlled coordination structure and methods for their production are disclosed. The supported catalysts of the present invention are useful for the preparation of hydrogen peroxide with high selectivity in addition to other chemical conversion reactions. The supported catalyst comprises catalyst particles having top or outer layer of atoms in which at least a portion of the atoms exhibit a controlled coordination number of 2. The catalyst and methods may be used for the concurrent in situ and ex situ conversion of organic compounds. In addition, a process is provided for catalytically producing hydrogen peroxide from hydrogen and oxygen feeds by contacting them with the catalysts of the invention and a suitable organic liquid solvent having a Solvent Selection Parameter (SSP) between 0.14×10?4 and 5.0×10?4.Type: GrantFiled: July 14, 2003Date of Patent: March 14, 2006Assignee: Headwaters Nanokinetix, Inc.Inventors: Bing Zhou, Michael Rueter, Sukesh Parasher
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Patent number: 6984371Abstract: A process for catalytic reforming of a hydrocarbon feed stream containing H2O, CO2, CH4 and CO at levels such that the H2O/CH4 is less than 0.8 and the CO2/CH4 is greater than 0.5 and the feed stream further contains quantities of sulfur compounds up to about 20 ppm. The catalyst used in this process contains from about 0.5 percent to about 25 percent by weight of a calcium compound additive, from about 2 percent to about 30 percent by weight nickel, and from about 25 percent to about 98 percent by weight of an aluminum compound carrier, wherein substantially all of the calcium is combined with the alumina. The reforming process can be utilized to produce syngas, especially low hydrogen to carbon monoxide ratio syngas for applications such as iron ore reduction.Type: GrantFiled: October 20, 2004Date of Patent: January 10, 2006Assignee: Sud-Chemie Inc.Inventors: Shizhong Zhao, Jon P. Wagner
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Patent number: 6972119Abstract: A hydrogen producing apparatus comprising: a reforming section having a reforming catalyst which causes a reaction between a carbon-containing organic compound as a feedstock and water; a feedstock supply section for supplying the feedstock to the reforming section; a water supply section for supplying water to the reforming section; a heating section for heating the reforming catalyst; a shifting section having a shift catalyst which causes a shift reaction between carbon monoxide and water contained in a reformed gas supplied from the reforming section; and a purifying section having a purifying catalyst which causes oxidation or methanation of carbon monoxide contained in a gas supplied from the shifting section, wherein the shift catalyst comprises a platinum group metal and a metal oxide.Type: GrantFiled: December 27, 2000Date of Patent: December 6, 2005Assignee: Matsushita Electric Industrial Co., Ltd.Inventors: Kiyoshi Taguchi, Takeshi Tomizawa, Kunihiro Ukai, Toshiyuki Shono, Koichiro Kitagawa, Tetsuya Ueda, Seiji Fujihara, Yutaka Yoshida
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Patent number: 6967063Abstract: A method for reforming a sulfur-containing carbonaceous fuel in which the sulfur-containing carbonaceous fuel is mixed with H2O and an oxidant, forming a fuel/H2O/oxidant mixture. The fuel H2O/oxidant mixture is brought into contact with a catalyst composition comprising a dehydrogenation portion, an oxidation portion and a hydrodesulfurization portion, resulting in formation of a hydrogen-containing gas stream.Type: GrantFiled: May 18, 2001Date of Patent: November 22, 2005Assignee: The University of ChicagoInventors: Michael Krumpelt, John P. Kopasz, Shabbir Ahmed, Richard Li-chih Kao, Sarabjit Singh Randhava
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Patent number: 6953488Abstract: There is provided a process for preparation of synthesis gas from feedstocks containing methane and/or higher hydrocarbons having from about 2 to about 12 carbon atoms by an initial catalytic treatment of feedstock to provide a methane-containing gaseous mixture substantially free of compounds having 2 or more carbon atoms, and reforming the gaseous mixture at elevated temperatures using nickel-containing catalytic materials that are unusually active under mild conditions of conversion and resistant to deactivation. The process consists fundamentally in converting the higher hydrocarbon compounds to form the methane-containing gaseous mixture in an initial conversion zone containing a catalyst while controlling temperatures within the initial conversion zone to temperatures in a range downward from about 500° C. to about 300° C., and reforming the methane-containing gaseous mixture in a subsequent zone to form synthesis gas.Type: GrantFiled: March 13, 2003Date of Patent: October 11, 2005Assignee: BP Corporation North America Inc.Inventors: Alakananda Bhattacharyya, Wen-Dong Chang
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Patent number: 6797253Abstract: 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: GrantFiled: November 26, 2001Date of Patent: September 28, 2004Assignee: General Electric Co.Inventor: Richard K. Lyon
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Patent number: 6793698Abstract: This invention relates to a compact apparatus for generating hydrogen. More particularly, this invention relates to a compact hydrogen generating apparatus suitable for use in conjunction with a fuel cell. The compact hydrogen generating apparatus comprises a fuel processor reactor having an integrated pre-reforming zone embedded within a secondary reforming zone.Type: GrantFiled: March 9, 2001Date of Patent: September 21, 2004Assignee: UOP LLCInventors: Robert J. Sanger, Kurt M. Vanden Bussche, Daniel R. Sioui
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Publication number: 20040142817Abstract: 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;-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: January 5, 2004Publication date: July 22, 2004Applicants: KOREA RESEARCH INSTITUTE OF CHEMICAL TECHNOLOGY, KOREA GAS CORPORATION, KYUNGDONG CITYGAS CO., LTD.Inventors: 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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Patent number: 6746624Abstract: Process for the preparation of hydrogen and carbon monoxide rich gas by catalytic steam reforming of a hydrocarbon feedstock comprising steps of: (a) optionally passing a process gas of hydrocarbon feedstock through a first reactor with a steam reforming catalyst heated by a hot gas stream; (b) passing the effluent from the first reactor to a subsequent tubular reactor containing a steam reforming catalyst and being heated by burning of fuel, thereby obtaining a hot gas stream of steam reformed product gas and a hot gas stream of flue gas; and wherein a reforming catalyst is placed on a metallic support having substantially the same shape as a wall of the reactor and being arranged in heat conduction relationship with the reactor wall.Type: GrantFiled: March 29, 2001Date of Patent: June 8, 2004Assignee: Haldor Topsøe A/SInventors: Peter Seier Christensen, Viggo Lucassen Hansen, J. R. Rostrup-Nielsen
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Publication number: 20040077496Abstract: A calcium promoted, aluminum compound supported nickel reforming catalyst for use in a hydrocarbon feed stream containing steam, CO2, CH4 and CO at levels such that the H2O/CH4 is less than 0.8 and the CO2/CH4 is greater than 0.5 and the feed stream further containing quantities of sulfur compounds up to about 20 ppm. The catalyst contains from about 0.5 percent to about 25 percent by weight of a calcium compound additive, from about 2 percent to about 30 percent by weight nickel, and from about 25 percent to about 98 percent by weight of an aluminum compound carrier, wherein substantially all of the calcium is combined with the alumina. The catalyst can be used in reforming reactions to produce syngas and has advantages in producing low hydrogen to carbon monoxide ratio syngas for applications such as iron ore reduction.Type: ApplicationFiled: July 26, 2002Publication date: April 22, 2004Inventors: Shizhong Zhao, Jon P. Wagner