WO2003076062A2 - Steam-reforming catalytic structures - Google Patents
Steam-reforming catalytic structures Download PDFInfo
- Publication number
- WO2003076062A2 WO2003076062A2 PCT/IB2003/000899 IB0300899W WO03076062A2 WO 2003076062 A2 WO2003076062 A2 WO 2003076062A2 IB 0300899 W IB0300899 W IB 0300899W WO 03076062 A2 WO03076062 A2 WO 03076062A2
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- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- reactor
- steam
- hydrogen
- gas
- Prior art date
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- 238000000629 steam reforming Methods 0.000 title claims abstract description 30
- 230000003197 catalytic effect Effects 0.000 title claims description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 77
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 74
- 239000001257 hydrogen Substances 0.000 claims abstract description 74
- 239000012528 membrane Substances 0.000 claims abstract description 65
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000007789 gas Substances 0.000 claims abstract description 49
- 238000012546 transfer Methods 0.000 claims abstract description 23
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
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- 229910001252 Pd alloy Inorganic materials 0.000 claims abstract description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 8
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- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
- C01B2203/041—In-situ membrane purification during hydrogen production
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1005—Arrangement or shape of catalyst
- C01B2203/1035—Catalyst coated on equipment surfaces, e.g. reactor walls
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1223—Methanol
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
- H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
- H01M8/0668—Removal of carbon monoxide or carbon dioxide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
- H01M8/0687—Reactant purification by the use of membranes or filters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates broadly to steam-reforming catalytic structures and hydrogen generation, being more particularly concerned with novel unitary catalytic structures and methods for generating hydrogen by reacting steam with a gaseous or gasified fossil hydrocarbon fuel and the like at a moderately elevated temperature, and still more particularly with palladium-bearing membrane pure hydrogen generators comprising the same.
- oxygen containing fuels such as alcohols and for gasified fuels and in general
- This shift reaction (3) typically occurs simultaneously with either reaction (1) or (2) above, but is traditionally completed in a secondary steam reformer reactor at a lower temperature than the primary reactor. This is due to reactions 1 and 2 being endothermic, where reactant conversion is favored at high temperatures, while reaction 3 is exothermic with reactant conversion being favored at low temperatures.
- reaction 3 is exothermic with reactant conversion being favored at low temperatures.
- high temperature partial oxidation of the carbon bearing fuel results in a gas mixture which is predominantly CO and H 2 . This mixture can then be further reacted with steam to maximize hydrogen production according to reaction (3), again, typically in a second, low temperature reactor.
- the heat transfer gas chambers are "filled with alumina balls for promoting heat transfer", whereas the reaction gas chambers are filled with the particulate catalyst materials.
- the present invention uses a flat unitary turbulence promoting structure washcoated with catalyst which is sandwiched between the Pd-bearing membrane and a heat conducting metal plate of controlled thickness. This metallic sandwich eliminates Koga's heating chambers and simplifies heating or cooling, as the case may be, of the hydrogen generating reactions thereon within an appropriate isothermal temperature range.
- the design of the present invention is also easier to manufacture, requiring fewer specialized machining operations.
- the present invention is directed to membrane reactors comprising flat unitary catalytic structures which allow heating (without internal air oxidation) or cooling of the reaction zone, as the case may be, primarily by conduction, to keep hydrogen generation and purification going within an acceptable temperature range (herein called the "isothermal range”) at enhanced yields of hydrogen permeates.
- unitary catalytic structure means a substantially flat but open catalyst holder washcoated with an adhering steam-reforming catalyst
- dimensionally-controlled refers to selecting the structure dimensions including thickness and open area to provide convective gas flow for enhanced heat and mass transfer within the isothermal range to and/or from the catalyst, while insuring substantially unimpeded access of the hydrogen generated thereon to the selective membrane.
- the principal object of the invention is to provide a new and improved steam-reforming catalyst structure and hydrogen generator comprising the same and an improved method of such generation that shall not be subject to the above- described and other limitations and disadvantages of the prior, but, to the contrary, provide less expensive structures and improved hydrogen generation.
- a further object is to provide a novel catalytic structure utilizing, in lieu of a pellet or a monolith or the like, an inexpensive catalyzed gas porous structure including a metallic screen or a preferably non-flattened expanded metal washcoated with an appropriate oxide and a steam-reforming catalyst.
- Another object of the invention is to provide a novel sandwich of a gas-porous metallic structure washcoated with a steam-reforming catalyst between one planar hydrogen-selective palladium alloy membrane and one planar heat-conducting metal plate in each high pressure chamber of alternating low and high pressure chambers to produce in the latter hydrogen and carbon oxides and simultaneously permeating therefrom pure hydrogen into each connected low pressure chamber, while providing the required heat transfer in situ predominantly by conduction through said plate.
- each low-pressure chamber with a metallic gas-porous membrane support sandwiched between one membrane and one plate.
- An additional object for cases where heating or cooling requirements are modest, as is the case for methanol steam-reforming and for the shift reaction in reactors of moderate capacity, is to provide novel non-metallic structures, such as a woven glass cloth, fabrics and the like with suitable catalyst and/or membrane supports.
- the invention embraces a membrane reactor/purifier for producing mixtures comprising hydrogen and carbon oxides by steam- reforming a gaseous or externally gasified fossil fuel or a derivative thereof and generating pure hydrogen therefrom by permeating through a planar hydrogen selective palladium alloy membrane at a controlled, moderately elevated isothermal temperature range, said reactor/purifier comprising a stack containing an array of pairs of high pressure and lower pressure chambers connected to each other by one said membrane, said pairs being interconnected by metallic heat conducting plates impervious to all gases including hydrogen, and each high pressure chamber being provided with a dimensionally controlled unitary structure washcoated with a steam- reforming catalyst.
- the invention describes a steam-reforming catalyst washcoated on a gas- porous preferably metallic structure sandwiched between one planar hydrogen-selective palladium alloy membrane and one planar gas (including hydrogen)-impermeable heat- conducting metal plate in each high pressure chamber of a stack array of pairs of alternating low and high pressure chambers to produce in the latter hydrogen and carbon oxides within an isothermal temperature range and simultaneously permeating therefrom pure hydrogen into each of connected low pressure product chamber connected thereto, while providing the required heat transfer to or from said catalyst in situ predominantly by conduction through said plate.
- a unitary catalytic structure of the invention combines a thin catalyst holder with a catalytic composition adhered thereon.
- the holder is a metallic screen, a woven glass cloth or a preferably non-flattened expanded metal and the composition comprises an oxide, including ceria, supporting a copper, iron and/or nickel catalyst.
- a steam- methanol mixture consisting predominantly of hydrogen and carbon oxides at the unexpectedly high catalytic efficiency of about 300,000 cc of methanol feed per hour per gram of copper catalyst.
- pure hydrogen has now been generated in a compacted reactor of enhanced utility, by reacting steam, within a controlled wide temperature range between about 200°C and 650°C, with a gaseous or gasified fossil fuel on a thin turbulence-promoting unitary structure in the high pressure chamber(s) of the reactor.
- a palladium alloy bearing-membrane reactor generating pure hydrogen has (1) its high pressure chamber(s) provided with the turbulence-promoting unitary structure of a stainless steel screen holder with its adhered ceria-containing oxide composition supporting an iron or copper catalyst, and (2) means of reacting thereon steam with methanol, syn-gas and/or carbon monoxide at a controlled temperature between about 200°C and 550°C.
- Yet another such palladium bearing-membrane pure hydrogen generating reactor in which the turbulence promoting unitary assembly bears a nickel catalyst (in lieu of an iron or copper catalyst), has means of steam-reforming thereon gaseous hydrocarbons at a controlled temperature between about 450°C and 650°C.
- a standard woven wire cloth when laid flat, has a height which is approximately twice the diameter of the wire used to form the cloth.
- the general gas flow path is in a direction perpendicular to this height, i.e. the gas is flowed along the length of the screen.
- a heat conducting plate 1 defines two chambers; a high-pressure reaction chamber la and a low pressure permeate chamber lb.
- the high-pressure chamber is filled with the unitary catalyst structure 2.
- the high and low pressure chambers are separated by a membrane 3 supported by a membrane support 4 which, if metallic, may need to be provided with means of preventing intermetallic diffusion between the support 4 and the membrane 3 as is known in the art.
- the heat conducting plate 1 is shown with heat transfer fins extending out to the two sides and the high pressure reactant flow path is directed into the page (of alternatively out of the page).
- a plurality of these elements is assembled to form a stack as shown in Figure 1 by repeating such chamber pairs.
- the flow of reactants in parallel to the stack can be accomplished by appropriate flow distribution means, i.e. a header or manifold arrangement. Other flow arrangements are also possible, i.e. series or series/parallel.
- the high-pressure cavity la wherein the catalyzed wire cloth 2 is housed should be of a height dimension equal to or preferably slightly higher than the height of the catalyzed screen in order to prevent rupturing of the membrane during assembly operations. It has been found that a cavity dimension about 5-10% higher than the height of the screen can be used while still obtaining the benefits of the tortuous flow path on gas mixing.
- the catalyzed screen 2 is fabricated in such a way as to allow adequate communication between the three surfaces of interest. It is an object of this invention to provide a combined catalyst structure and channel geometry such that a gas stream when passing along the channel "simultaneously" contacts all three surfaces 1, 2 and 3 providing efficiency in mass transfer to the catalyst surface 2 and the hydrogen membrane surface 3, and in heat transfer with the heat conducting surface 1 and the catalyst surface 2. It is therefore critical that the flow velocity be sufficient to achieve this mixing given the other dimensions of the device. Thus the combination of low flow rates with large height; open cavities must be avoided because it is the mixing of the gas that serves to achieve the objects of this invention.
- Atypical reaction channel in this invention will therefore have length in the direction of the flow equal to or greater than it's width perpendicular to the flow path, which is at least in the range from 10-100 times the height of the channel, and hence screen. It has been determined that good reactor performance is achievable if the Reynolds number, herein defined according to the inlet gas properties at the reactor temperature and using the standard definition of an equivalent pipe diameter for the rectangular cross section channel (here 4 times the rectangular cross sectional area divided by its perimeter), is greater than about 1.0 and less than about 1000 and preferably in the range from about 10 to about 100.
- the catalyst washcoat must be provided in such a fashion as to prevent undesirable "blocking" of the spaces between the wires. It is therefore desirable to provide washcoats which block less than 50%, and preferably less than 25% and more preferably less than 5% of the screen openings. It is appreciated that in the extreme case of full blockage, the screen is thus transformed into a catalyst "slab" which effectively blocks gas phase communication between the heat transfer surface and the hydrogen membrane surface. In this instance, although contact with the catalyst 2 may still be substantial overall, a substantial portion of the gas phase will infrequently contact the hydrogen membrane 3 whereas the other substantial portion will infrequently contact the heat transfer surface 1. These instances of "channeling" are partially representative of what this invention seeks to overcome in a practical fashion.
- this reactor device should efficiently utilize each of it's elements, these being the heat transfer wall, the catalyst structure, and the hydrogen permeable membrane.
- the hydrogen membrane 3 must be provided with sufficient hydrogen to achieve optimal performance.
- the amount of active catalyst surface in proportion to the membrane surface be sufficient.
- High activity catalysts are naturally preferred.
- overloading the catalyst can lead to high reaction at the inlet, which, in the case of exothermic reactions, can lead to localized overheating and possible damage.
- the plate itself should have a high thermal conductivity.
- the plate is also required to provide structural rigidity surface on the edge and is therefore must maintain it's rigidity at temperature.
- the overall module design will often be elongated in the direction of the reactant flow. The flow will be directed along the long axis and the heat transfer will primarily be directed from the sides, in the direction perpendicular to the main flow direction. In these instances, to achieve high heat transfer rates into the design it is desirable that the heat transfer plates extend outwards from the stack into the heat source zone so as to enhance convective heat transfer to the stack by the use of so-called heat transfer enhancing fins.
- external heat sources may provide heat by conduction, convection, radiation, or combinations of these.
- convection of heat from a second, externally generated gas stream is the preferred means of providing heat to the endothermic reactor.
- the temperature of the externally generated hot gas stream can be controlled to a pre-specified value prior to contacting the membrane reactor.
- the said externally generated high temperature gas stream may be achieved by combustion of a fuel with air, or by combusting the unpermeated, retentate gas stream with air.
- thermal efficiency is best preserved by directing the retentate stream immediately to the burner zone so as to maintain its sensible heat.
- feed preheating and vaporization can be achieved by appropriate contacting of the feed materials with the flue gas exhaust from the high temperature reactor zone.
- a CO-containing stream may be generated in an external, high temperature process herein referred to as the primary reformer.
- primary reformers include high temperature steam reforming, coal gasification, and the like.
- the syn-gas generated in the primary reformer will be at a higher temperature than the membrane reactor, and thus the stream is preferably cooled prior to being fed to the shift reactor.
- Such cooling can be achieved by direct injection of any additional reactant liquid water into the hot gas stream, the vaporization and heating of the water providing an excellent cooling means.
- additional reactant water is not required (as is often the case in primary steam reforming)
- the cooling of the syn-gas can be accomplished by indirect pre-heating and/or vaporization of one or more of the primary reformer feed streams.
- Example 1 Methanol steam reforming:
- the invention may be described as preferably embodying a membrane reactor consisting of a palladium copper membrane 25 microns thick supported between two screens, one as a membrane support residing in the low pressure permeate chamber, and the other, a screen coated with catalyst, in the high pressure, reaction chamber.
- the catalyst was a co-precipitated mixture of copper, cerium, and lanthanum oxides in the proportions of 10% copper, 5% lanthanum, and the balance cerium oxide produced by urea co-precipitation and calcined in air at 450°C for 12 hours.
- the area was 38 square centimeters in a rectangle of 2:1 aspect ratio, and the catalyst weight was 150 mg applied as a thin coating to an oxidized standard 40 mesh aluminum screen 0.020" thick (prior to coating) having the same length and width as the high pressure chamber of the reactor.
- the screen was housed in the high-pressure chamber which itself was 0.030" in height.
- the high-pressure chamber is bound on one side and on the edges by a solid, heat- conducting wall, and on the other side by the palladium/copper membrane.
- the feed to the reactor was premixed methanol and water in a molar ratio of 1.5 moles of water to 1.0 moles of methanol.
- the feed was first pumped under pressure into a hot vaporizer unit and the fully vaporized mixture was then fed directly into the membrane reactor.
- the total feed rate was 0.25 ml/min of liquid, corresponding to a molar feed rate of 0.004 moles/minute of methanol.
- the reactor was held at a temperature of 420°C and the pressure held at 150 psig in the high-pressure chamber. Hydrogen was permeated at atmospheric pressure.
- the activity of G66A was determined to be 0.06 moles methanol/gm (CuO)-hr, nearly 200 times lower than the above described experiment. Correcting for the temperature differences between the two experiments (assuming an activation energy of 20 kcal/mol) reveals an expected rate on G66A of 1.2 moles methanol/gm (CuO)-hr, still a factor of 10 lower than the above described reactor. In fact, G66A is not operable at 420°C for long periods due to activity loss.
- Example 2 The same membrane reactor geometry as in Example 1.
- the catalyst was WC301B, a proprietary noble metal based water gas shift catalyst supplied by S ⁇ d-Chemie, Inc. of Louisville, Kentucky.
- the reactor was operated isothermally at 450°C and at a pressure of 100 psig.
- the membrane was a 10 micron thick Pd/Cu 60/40wt%. Values are reported to 2 significant figures. Permeate pressure is ambient.
- the equilibrium constant for the WGS reaction at 450°C is around 11.9.
- the value of 37.8 represents a temperature of approximately 325°C.
- the membrane reactor benefit is about 125°C.
- Example 3 Same reactor configuration as in Example 3; membrane is 18 microns thick, the catalyst is designated FCR-HC 14, WC-723B also supplied by S ⁇ d-Chemie, Inc. of Louisville, Kentucky. Reaction conditions were 200 psig, 550°C isothermal operation permeate pressure is ambient.
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- Combustion & Propulsion (AREA)
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Abstract
Description
Claims
Priority Applications (5)
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CA002477852A CA2477852A1 (en) | 2002-03-12 | 2003-03-12 | Steam-reforming catalytic structures |
MXPA04008857A MXPA04008857A (en) | 2002-03-12 | 2003-03-12 | Steam-reforming catalytic structures. |
AU2003212554A AU2003212554A1 (en) | 2002-03-12 | 2003-03-12 | Steam-reforming catalytic structures |
EP03708375A EP1519784A2 (en) | 2002-03-12 | 2003-03-12 | Steam-reforming catalytic structures |
JP2003574324A JP2005519830A (en) | 2002-03-12 | 2003-03-12 | Steam reforming catalytic structure |
Applications Claiming Priority (2)
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US36367202P | 2002-03-12 | 2002-03-12 | |
US60/363,672 | 2002-03-12 |
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WO2003076062A2 true WO2003076062A2 (en) | 2003-09-18 |
WO2003076062A3 WO2003076062A3 (en) | 2003-11-27 |
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PCT/IB2003/000899 WO2003076062A2 (en) | 2002-03-12 | 2003-03-12 | Steam-reforming catalytic structures |
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US (1) | US7182917B2 (en) |
EP (1) | EP1519784A2 (en) |
JP (1) | JP2005519830A (en) |
CN (1) | CN1638859A (en) |
AU (1) | AU2003212554A1 (en) |
CA (1) | CA2477852A1 (en) |
MX (1) | MXPA04008857A (en) |
WO (1) | WO2003076062A2 (en) |
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- 2003-03-12 WO PCT/IB2003/000899 patent/WO2003076062A2/en active Application Filing
- 2003-03-12 JP JP2003574324A patent/JP2005519830A/en active Pending
- 2003-03-12 MX MXPA04008857A patent/MXPA04008857A/en active IP Right Grant
- 2003-03-12 CN CNA038057077A patent/CN1638859A/en active Pending
- 2003-03-12 EP EP03708375A patent/EP1519784A2/en not_active Withdrawn
- 2003-03-12 CA CA002477852A patent/CA2477852A1/en not_active Abandoned
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US7850749B2 (en) | 2004-04-02 | 2010-12-14 | Nissan Motor Co., Ltd. | Fuel reformer suppressing uneven temperature distribution in reforming element |
WO2005095267A1 (en) * | 2004-04-02 | 2005-10-13 | Nissan Motor Co., Ltd. | Fuel reformer |
US7896933B2 (en) | 2005-04-15 | 2011-03-01 | Hitachi, Ltd. | Hydrogen supplying apparatus and method of manufacturing hydrogen supplying apparatus |
DE102006017046B4 (en) * | 2005-04-15 | 2009-07-30 | Hitachi, Ltd. | Hydrogen supply device and method for its production |
WO2007043247A1 (en) * | 2005-09-30 | 2007-04-19 | Nissan Motor Co., Ltd. | Fuel reformer |
EP2026901A4 (en) * | 2006-04-07 | 2010-06-30 | Chart Ind Inc | Supercritical process, reactor and system for hydrogen production |
EP2026901A2 (en) * | 2006-04-07 | 2009-02-25 | Chart Industries, Inc. | Supercritical process, reactor and system for hydrogen production |
US8597383B2 (en) | 2011-04-11 | 2013-12-03 | Saudi Arabian Oil Company | Metal supported silica based catalytic membrane reactor assembly |
US9745191B2 (en) | 2011-04-11 | 2017-08-29 | Saudi Arabian Oil Company | Auto thermal reforming (ATR) catalytic structures |
US10071909B2 (en) | 2011-04-11 | 2018-09-11 | Saudi Arabian Oil Company | Auto thermal reforming (ATR) catalytic structures |
US10093542B2 (en) | 2011-04-11 | 2018-10-09 | Saudi Arabian Oil Company | Auto thermal reforming (ATR) catalytic structures |
US10252911B2 (en) | 2011-04-11 | 2019-04-09 | Saudi Arabian Oil Company | Auto thermal reforming (ATR) catalytic systems |
US10252910B2 (en) | 2011-04-11 | 2019-04-09 | Saudi Arabian Oil Company | Auto thermal reforming (ATR) catalytic structures |
Also Published As
Publication number | Publication date |
---|---|
US7182917B2 (en) | 2007-02-27 |
CA2477852A1 (en) | 2003-09-18 |
JP2005519830A (en) | 2005-07-07 |
AU2003212554A8 (en) | 2003-09-22 |
US20030172589A1 (en) | 2003-09-18 |
CN1638859A (en) | 2005-07-13 |
AU2003212554A1 (en) | 2003-09-22 |
EP1519784A2 (en) | 2005-04-06 |
WO2003076062A3 (en) | 2003-11-27 |
MXPA04008857A (en) | 2005-09-08 |
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