Source: http://www.google.com/patents/US7390536?dq=6,406,777
Timestamp: 2014-08-23 19:17:41
Document Index: 331201852

Matched Legal Cases: ['Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60']

Patent US7390536 - Method for fabricating composite gas separation modules - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign in<nobr>Advanced Patent Search</nobr>PatentsThe present invention relates to a method for fabricating a composite gas separation module and to gas separation modules formed by the method. In one embodiment, the method for fabricating a composite gas separation module includes depositing a first material on a porous substrate, thereby forming a...http://www.google.com/patents/US7390536?utm_source=gb-gplus-sharePatent US7390536 - Method for fabricating composite gas separation modulesAdvanced Patent SearchPublication numberUS7390536 B2Publication typeGrantApplication numberUS 10/804,847Publication dateJun 24, 2008Filing dateMar 19, 2004Priority dateMar 21, 2003Fee statusPaidAlso published asCA2519774A1, EP1608459A1, US20040237780, WO2004085044A1Publication number10804847, 804847, US 7390536 B2, US 7390536B2, US-B2-7390536, US7390536 B2, US7390536B2InventorsYi Hua Ma, Ivan P. Mardilovich, Erik E. EngwallOriginal AssigneeWorcester Polytechnic InstituteExport CitationBiBTeX, EndNote, RefManPatent Citations (64), Non-Patent Citations (10), Referenced by (6), Classifications (50), Legal Events (2) External Links: USPTO, USPTO Assignment, EspacenetMethod for fabricating composite gas separation modulesUS 7390536 B2Abstract The present invention relates to a method for fabricating a composite gas separation module and to gas separation modules formed by the method. In one embodiment, the method for fabricating a composite gas separation module includes depositing a first material on a porous substrate, thereby forming a coated substrate. The coated substrate is abraded, thereby forming a polished substrate. A second material is then deposited on the polished substrate. The first material, the second material, or both the first material and the second material can include a gas-selective material such as a hydrogen-selective metal, e.g., palladium, or an alloy thereof. In one embodiment, the method includes the step of forming a dense gas-selective membrane over the porous substrate. The present invention also relates to a method for selectively separating hydrogen gas from a hydrogen gas-containing gaseous stream.
RELATED APPLICATION This application claims the benefit of U.S. Provisional Application No. 60/456,930, filed on Mar. 21, 2003. The entire teachings of the above application are incorporated herein by reference.
SUMMARY OF THE INVENTION The present invention relates to a method for fabricating a composite gas separation module and to gas separation modules formed by the method. The present invention also relates to a method for selectively separating hydrogen gas from a hydrogen gas-containing gaseous stream.
BRIEF DESCRIPTION OF THE DRAWINGS The FIGURE is a sectional perspective view of a composite gas separation module as one embodiment of the present invention.
The composite gas separation modules described herein each include a dense gas-selective membrane such as, for example, a dense hydrogen-selective metal membrane. In one embodiment, the composite gas separation module includes a dense hydrogen-selective metal membrane of palladium or an alloy thereof. A �dense gas-selective membrane,� as that term is used herein, refers to a component of a composite gas separation module that has one or more layers of a gas-selective material, i.e., a material that is selectively permeable to a gas, and that is not materially breached by regions or points which impair the separation of the gas by allowing the passage of an undesired gas. For instance, in one embodiment, the dense gas-selective membrane is not materially breached by regions or points which do not have the desired gas selectivity properties of the gas-selective material. An example of a dense gas-selective membrane is a dense hydrogen-selective metal membrane of palladium, or an alloy thereof, that is substantially free of open pores, holes and defects such as cracks.
The term �support,� as used herein, includes a substrate, a surface treated substrate, a coated substrate, or a coated polished substrate upon which a dense gas-selective membrane has been or will be formed. Serving as a support structure, the substrate can enhance the durability and strength of the composite gas separation module.
In one aspect, the coated substrate includes one or more unfavorable morphologies. �Unfavorable morphology,� as that term is used herein, refers to a deposit of a gas-selective material which results in the need to make a deposited gas-selective material thicker than otherwise would be needed to form a dense gas-selective membrane than if the unfavorable morphology was abraded, as described herein, or if the unfavorable morphology was not present. The presence of unfavorable morphologies can lead to an increase in the amount of gas-selective material required to achieve a dense gas-selective membrane. For example, the presence of an unfavorable morphology can result in increased thickness of the dense gas-selective membrane in the vicinity of the unfavorable morphology upon deposition of a dense gas-selective membrane component. Examples of unfavorable morphologies can include excessive crystal growth, dendrites, agglomerates, or other structures in directions generally perpendicular to the surface of the substrate. Other examples of unfavorable morphology can include a repetition of porous or powder-like morphologies from previously deposited layers of material.
Depositing a first material on the porous substrate can begin the formation of a dense gas-selective membrane. However, deposition of a first material, such as a gas-selective material, can be stopped prior to achieving a dense gas-selective membrane and the product is referred to herein as a �coated substrate.� By depositing the first material (e.g., a gas-selective material) on the porous substrate, a portion, a majority, or most of the pores, holes and/or defects present in the substrate can be covered or blocked. In one embodiment, the pores, holes and/or defects of the substrate are substantially covered and/or blocked by plating the porous substrate with a hydrogen-selective metal, thereby forming a coated substrate.
In one embodiment, the dense gas-selective membrane is selectively permeable to hydrogen, e.g., the dense gas-selective membrane is a dense hydrogen-selective metal membrane and can include one or more hydrogen-selective metals or alloys thereof. �Hydrogen-selective metals� include, but are not limited to, niobium (Nb), tantalum (Ta), vanadium (V), palladium (Pd), zirconium (Zr) and hydrogen-selective alloys thereof. Palladium and alloys of palladium are preferred. For example, palladium can be alloyed with at least one of the metals selected from the group consisting of copper, silver, gold, platinum, ruthenium, rhodium, yttrium, cerium and indium.
In one embodiment, a porous metal layer intermetallic diffusion barrier includes palladium or an alloy thereof and a Group IB metal, such as copper or silver, or an alloy thereof. For example, the intermetallic diffusion barrier can include alternating porous layers of palladium and a Group IB metal or alloys thereof. Methods for fabricating composite gas separation modules that include intermetallic diffusion barriers are further discussed in U.S. Provisional Patent Application No. 60/457,061, entitled �Method of Making Intermetallic Diffusion Barrier,� by Ma, et al., filed on Mar. 21, 2003, and in U.S. patent application Ser. No. 10/804,846, entitled �Composite Gas Separation Modules Having Intermediate Porous Metal Layers,� by Ma, et al., filed on even date herewith under, each incorporated by reference herein in their entirety.
Methods for fabricating gas separation modules that include selectively surface activating a support proximate to a defect and preferentially depositing a material on the selectively surface activated portion of the support are discussed in U.S. Provisional Patent Application No. 60/456,931, entitled �Method of Producing Thin Palladium and Palladium Alloy Layers,� by Ma, et al., filed on Mar. 21, 2003, and in �Method for Curing Defects in the Fabrication of a Composite Gas Separation Module,� by Ma, et al., filed on even date herewith under, each incorporated by reference herein in their entirety.
Composite gas separation modules and methods for their fabrication suitable for use in conjunction with the present invention are described in U.S. Pat. No. 6,152,987, cited supra, and also in U.S. Provisional Patent Application No. 60/456,931, cited supra; U.S. Provisional Patent Application No. 60/457,061, cited supra; U.S. Provisional Patent Application No. 60/456,930, entitled �Method for Producing Dense Selective Layers,� by Ma, et al., filed on Mar. 21, 2003; U.S. Provisional Patent Application No. 60/467,493, entitled �High Melting Point Metal Diffusion Barriers for Composite Palladium Porous Stainless Steel Membranes,� by Ma, et al., filed on May 2, 2003; U.S. patent application Ser. No. 10/804,848, entitled �Method for Curing Defects in the Fabrication of a Composite Gas Separation Module,� by Ma, et al., cited supra; and U.S. patent application Ser. No. 10/804,846, entitled �Composite Gas Separation Modules Having Intermediate Porous Metal Layers,� by Ma, et al., cited supra, each of which is incorporated herein by reference in its entirety.
Example 1 This example describes the fabrication of a composite structure that includes palladium and a 0.1 micron grade porous 316L stainless steel (PSS) support.
Example 2 This example describes the fabrication of a composite structure that includes palladium, a porous metal layer intermetallic diffusion barrier, and a 0.1 micron grade porous HASTELLOY� C-22� support. (HASTELLOY� C-22� is a nickel-chromium-molybdenum-iron-tungsten alloy.)
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS2958391Apr 10, 1958Nov 1, 1960Universal Oil Prod CoPurification of hydrogen utilizing hydrogen-permeable membranesUS3241298Nov 26, 1962Mar 22, 1966Union Carbide CorpMethod for making a fine porosity filter elementUS3413777Jun 22, 1965Dec 3, 1968Engelhard Min & ChemHydrogen diffusion and method for producing sameUS3428476Jun 22, 1965Feb 18, 1969Engelhard Min & ChemMethod for producing hydrogen diffusion cellsUS3717525May 23, 1968Feb 20, 1973Varian Mat GmbhMethod for production of a diffusion membrane arrangementUS4496373Jun 6, 1984Jan 29, 1985Kernforschungsanlage Julich Gesellschaft Mit Beschrankter HaftungMembrane and its palladium-alloy protective coating contain a smillar metal in equilibrated concentratrion;durabilityUS4589891Sep 10, 1984May 20, 1986Kernforschungsanlage Julich Gesellschaft Mit Beschrankter HaftungHydrogen permeatin membrane, process for its manufacture and useUS4689150Feb 24, 1986Aug 25, 1987Ngk Insulators, Ltd.Separation membrane and process for manufacturing the sameUS4699637Sep 10, 1984Oct 13, 1987Kernforschungsanlage Julich Gesellschaft Mit Beschrankter HaftungHydrogen permeation membraneUS4857080Dec 2, 1987Aug 15, 1989Membrane Technology & Research, Inc.Ultrathin composite metal membranesUS5049167Dec 13, 1989Sep 17, 1991Membrane Technology & Research, Inc.Multilayer interfacial composite membraneUS5139541Jul 22, 1991Aug 18, 1992Bend Research, Inc.Hydrogen-permeable composite metal membraneUS5205841Apr 3, 1992Apr 27, 1993Tpc Technologies, Inc.Using membrane of palladium metal film and palladium-platinum black filmsUS5215729Jun 22, 1990Jun 1, 1993Buxbaum Robert EComposite metal membrane for hydrogen extractionUS5217506May 15, 1992Jun 8, 1993Bend Research, Inc.Hydrogen-permeable composite metal membrane and uses thereofUS5258339Mar 12, 1992Nov 2, 1993Worcester Polytechnic InstituteFormation of zeolite membranes from solsUS5259870Dec 7, 1992Nov 9, 1993Bend Research, Inc.Intermetallic diffusion barrier between base and coating metals; permselectivityUS5358553Jul 5, 1991Oct 25, 1994Texaco Inc.Electrodepositing group 8 noble metal on cathode; used to separate hydrogen from mixtures thereof with hydrocarbonsUS5393325Nov 8, 1993Feb 28, 1995Bend Research, Inc.Composite hydrogen separation metal membraneUS5449848Sep 23, 1991Sep 12, 1995Agency Of Industrial Science And TechnologyDehydrogenation processUS5451386May 19, 1993Sep 19, 1995The State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of OsuCatalytic decomposition of exhaust gas containing ammonia, metal-ceramic compositeUS5498278Dec 19, 1994Mar 12, 1996Bend Research, Inc.Composite hydrogen separation element and moduleUS5614001May 19, 1995Mar 25, 1997Ngk Insulators, Ltd.Hydrogen separator, hydrogen separating apparatus and method for manufacturing hydrogen separatorUS5652020Jan 29, 1996Jul 29, 1997The State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Oregon State UniversityForming palladium layer on inside surface of porous ceramic tube, promotes decomposition of ammoniaUS5672388Jul 8, 1994Sep 30, 1997Exxon Research & Engineering CompanyMembrane reparation and poer size reduction using interfacial ozone assisted chemical vapor depositionUS5738708Jun 7, 1995Apr 14, 1998The Regents Of The University Of California Office Of Technology TransferComposite metal membraneUS5782959Jun 21, 1996Jul 21, 1998Korea Advanced Institute Of Science And TechnologyProcess for preparing a composite inorganic membrane for hydrogen separationUS5782960Mar 17, 1997Jul 21, 1998Mitsubishi Jukogyo Kabushiki KaishaMembrane comprising hydrogen-permeable member, reinforcing member laminateUS5895769Jul 29, 1997Apr 20, 1999Exxon Research And Engineering CompanyIn-situ crystallized zeolite containing composition (LAI-ISC)US5904754Jun 20, 1997May 18, 1999Walter Juda AssociatesDiffusion-bonded palladium-copper alloy framed membrane for pure hydrogen generators and the like and method of preparing the sameUS6086729Apr 25, 1997Jul 11, 2000SintefMethod of manufacturing thin metal membranesUS6152987Aug 24, 1998Nov 28, 2000Worcester Polytechnic InstituteMethod for selectively separating hydrogen from hydrogen-producing reactantsUS6152995Mar 22, 1999Nov 28, 2000Idatech LlcEtching to control thicknessUS6183542Nov 9, 1998Feb 6, 2001Peter R. BossardMethod and apparatus for purifying hydrogenUS6267801Sep 8, 1999Jul 31, 2001W. C. Heraeus Gmbh & Co. KgPalladium, platinum, or alloy thereofUS6309546Jan 6, 1998Oct 30, 2001Ellipsis CorporationMicro and ultrafilters with controlled pore sizes and pore size distribution and methods for makingUS6372363Apr 24, 2000Apr 16, 2002Walter Juda Associates, Inc.Making palladium-copper alloy billet by freezing the alloy melt; forming a thin foil by mechanically pressure-rolling the heated billet; heating foil in inert gas below melting point of alloyUS6379524Dec 24, 1998Apr 30, 2002Korea Research Institute Of Chemical TechnologyMethod for preparing composite membrane for separation of hydrogen gasUS6419728Nov 27, 2000Jul 16, 2002Idatech, LlcHydrogen-permeable metal membrane and method for producing the sameUS6475268Dec 22, 2000Nov 5, 2002Ford Global Technologies, Inc.Supported membrane for hydrogen separationUS6547858Jul 19, 2000Apr 15, 2003Idatech, LlcHydrogen-permeable metal membrane and hydrogen purification assemblies containing the sameUS6596057Jul 15, 2002Jul 22, 2003Idatech, LlcHydrogen-selective metal membranes, membrane modules, purification assemblies and methods of forming the sameUS6730145Dec 31, 2002May 4, 2004L'air Liquide Societe AnonymeTreating gas separation membrane with aqueous reagent dispersionUS6916454Mar 30, 2001Jul 12, 2005Siemens Westinghouse Power CorporationMetal gas separation membraneUS6964697Jul 3, 2002Nov 15, 2005Fraunhofer-Gesellschaft zur F�rderung der angewandten Forschung e.V.Metal solution-diffusion membrane and method for producing the sameUS7018446Sep 24, 2003Mar 28, 2006Siemens Westinghouse Power CorporationMetal gas separation membraneUS20020083829Dec 19, 2001Jul 4, 2002Edlund David J.Hydrogen purification membranes, components and fuel processing systems containing the sameUS20030183080Mar 5, 2003Oct 2, 2003Mundschau Michael V.Hydrogen transport membranesUS20030190486Apr 3, 2003Oct 9, 2003Fernando RoaProcess for Preparing Palladium Alloy Composite Membranes for Use in Hydrogen Separation, Palladium Alloy Composite Membranes and Products Incorporating or Made from the MembranesUS20030213365Apr 7, 2003Nov 20, 2003W.C. Heraeus Gmbh & Co. KgComposite membrane and production method thereforUS20040037962Feb 12, 2002Feb 26, 2004Takashi UemuraForming an antipeeling protective palladium thin film, by diffusing a reductant from the other side of porous support, metallization, hydrogenation, reduction, electroless depositionUS20040244589Feb 2, 2004Dec 9, 2004Bossard Peter R.Composite structure for high efficiency hydrogen separation and its associated methods of manufacture and useUS20050072304Feb 14, 2002Apr 7, 2005Claude EtievantComposite structures of membranes that are selectively permeable to hydrogen and combustible gas processors using sameUS20060188737May 3, 2006Aug 24, 2006Colorado School Of MinesProcess for Preparing Palladium Alloy Composite Membranes for Use in Hydrogen Separation, Palladium Alloy Composite Membranes and Products Incorporating or Made from the MembranesEP1180392A1Jul 21, 2001Feb 20, 2002OMG AG &amp; Co. KGSupported metal membrane, method for the production and the use thereofEP1208904A1Nov 22, 2001May 29, 2002Sumitomo Electric Industries, Ltd.Substance separation structure and method of preparing the sameEP1277512A1Feb 12, 2002Jan 22, 2003Sumitomo Electric Industries, Ltd.Hydrogen-permeable structure and method for manufacture thereof or repair thereofJPH0585702A Title not availableJPH1028850A Title not availableJPH05123548A Title not availableWO1999033545A1Dec 24, 1998Jul 8, 1999Korea Res Inst Chem TechMethod for preparing composite membrane for separation of hydrogen gasWO2002066144A2Feb 14, 2002Aug 29, 2002Cie D Etude Des Tech De L HydrComposite structures of membranes that are selectively permeable to hydrogen and combustible gas processors using sameWO2003011433A1Jul 3, 2002Feb 13, 2003Fraunhofer Ges ForschungMetal solution-diffusion membrane and method for producing the sameWO2005075060A1May 14, 2004Aug 18, 2005Bossard Peter RComposite structure for high efficiency hydrogen separation and its associated methods of manufacture and useNon-Patent CitationsReference1Gryaznov, V. M., "Metal Containing Membranes for the Production of Ultrapure Hydrogen and the Recovery of Hydrogen Isotopes," Separation and Purification Methods (now Separation and Purification Reviews), 29(2):171-187 (2000).2Gryaznov, V. M., et al., "Preparation and catalysis over Palladium Composite Membranes," Applied Catalysis A: General, 96:15-23 (1993).3Ma, Y. H., et al., "Characterization of Intermetallic Diffusion Barrier and Alloy Formation for Pd/Cu and Pd/Ag Porous Stainless Steel Composite Membranes," I & EC Research, 43:2936-2945 (2004).4Ma, Y. H., et al., "Thin Composite Palladium and Palladium/Alloy Membranes for Hydrogen Separation," Ann. N.Y. Acad. Sci., 984:346 (2003).5Mardilovich, I. P., et al., "Dependence of Hydrogen Flux on The Pore Size and Plating Surface Topology of Asymmetric Pd-Porous Stainless Steel Membranes," Desalination, 144:85-89 (2002).6Nam, S.-E., et al., "Hydrogen Separation by Pd Alloy Composite Membranes," J. Membrane Sci., 192:177-185 (2001).7Ozaki, T., et al., "Preparation of Palladium-coated V and V-15 Ni Membranes for Hydrogen Purification by Electroless Plating Technique," Int. J. Hydrogen Energy, 28:297 (2003).8Roa, F., "Preparation and Characterization of Pd-Cu Composite Membranes for Hydrogen Separation," Chem. Eng. J., 93:11 (2003).9Roa, F., et al., "The Influence of Alloy Composition on The H<SUB>2 </SUB>Flux of Composite Pd-Cu Membranes," Desalination, 147:411-416 (2002).10Shu, J., et al., "Structurally Stable Pd-Ag Alloy Membranes: Introduction of a Diffusion Barrier," Thin Solid Films, 286:72-79 (1996).Referenced byCiting PatentFiling datePublication dateApplicantTitleUS7985708 *Jul 7, 2006Jul 26, 2011Compactgtl Plccatalyst support is made by coating a metal substrate with a solution containing a precursor for a ceramic and an amphiphilic compound, and treating the coating such that it forms a micelle structure. The coating is then treated to form a mesoporous ceramic coating on the metal substrateUS8366805Apr 4, 2008Feb 5, 2013Worcester Polytechnic InstituteComposite structures with porous anodic oxide layers and methods of fabricationUS8652239May 3, 2011Feb 18, 2014Worcester Polytechnic InstituteHigh permeance sulfur tolerant Pd/Cu alloy membranesWO2013074654A1Nov 14, 2012May 23, 2013Shell Oil CompanyA method of preparing or reconditioning a leak stable gas separation membrane systemWO2013096183A1Dec 17, 2012Jun 27, 2013Shell Oil CompanyA method of making a hydrogen separation composite membraneWO2013096186A1Dec 17, 2012Jun 27, 2013Shell Oil CompanyMethod of making a composite metal gas separation membrane* Cited by examinerClassifications U.S. Classification427/402, 427/595, 427/446, 427/404, 427/255.28, 427/355, 427/421.1, 427/270, 427/419.1, 427/455, 427/383.1International ClassificationC01B3/50, B01D69/12, B01D69/10, B01D71/02, B05D3/12, B01D53/22, B01D67/00, B01D53/00Cooperative ClassificationB01D67/0072, B01D53/228, B01D71/028, B01D2313/22, B01D71/022, B01D67/0069, B01D63/06, B01D69/10, B01D67/0086, B01D53/22, C01B3/505, B01D63/061, B01D69/141, C01B2203/0475, B01D69/12, B01D2325/04, B01D2313/42, C01B2203/0405European ClassificationB01D67/00M22, B01D67/00M24, B01D63/06B, B01D53/22, B01D63/06, B01D53/22M, B01D69/14B, B01D69/10, B01D69/12, B01D71/02M, C01B3/50B2B, B01D71/02Z, B01D67/00R12Legal EventsDateCodeEventDescriptionNov 16, 2011FPAYFee paymentYear of fee payment: 4Aug 3, 2004ASAssignmentOwner name: WORESTER POLYTECHNIC INSTITUTE, MASSACHUSETTSFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MA, YI HUA;MARDILOVICH, IVAN P.;ENGWALL, ERIK E.;REEL/FRAME:015043/0596Effective date: 20040416RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google