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WO2001089665A1 - Purification de melanges gazeux - Google Patents

Purification de melanges gazeux Download PDF

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Publication number
WO2001089665A1
WO2001089665A1 PCT/NL2001/000389 NL0100389W WO0189665A1 WO 2001089665 A1 WO2001089665 A1 WO 2001089665A1 NL 0100389 W NL0100389 W NL 0100389W WO 0189665 A1 WO0189665 A1 WO 0189665A1
Authority
WO
WIPO (PCT)
Prior art keywords
membrane
gas
fuel cell
porous
liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/NL2001/000389
Other languages
English (en)
Inventor
Eleonoor Van Andel
Erik Middelman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nedstack Holding BV
Original Assignee
Nedstack Holding BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from NL1015269A external-priority patent/NL1015269C1/nl
Priority claimed from NL1015270A external-priority patent/NL1015270C1/nl
Application filed by Nedstack Holding BV filed Critical Nedstack Holding BV
Priority to AU60788/01A priority Critical patent/AU6078801A/en
Publication of WO2001089665A1 publication Critical patent/WO2001089665A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/38—Liquid-membrane separation
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide
    • 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

Definitions

  • the invention has as its purpose to provide a method and apparatus for selectively removing gasses from gas mixtures by using a membrane.
  • the method and apparatus according to the invention are specifically suitable for the selective removal of Carbon Monoxide from mixtures containing; hydrogen, water vapor and Carbon dioxide.
  • a fuel processor is an apparatus that converts fossil fuels like natural gas (LG), LPG, methanol, petrol and diesel into a gas mixture containing hydrogen.
  • This gas mixture, called reformate, produced by the fuel processor can be used to feed a fuel cell, like a PEM-fuel cell.
  • the PEM-fuel cell is an efficient electro chemical device that can convert hydrogen or hydrogen containing gas mixtures into electrical power and heat.
  • Fuel processors, PEM fuel cells and PEM fuel cell stacks are generally known.
  • Known fuel processors deliver a gas mixture that contains traces of carbon monoxide up to a level of several percent. Carbon monoxide is known to degrade the performance of PEM fuel cell, even at very low concentrations.
  • a known method is the addition of air to the reformate prior to feeding the reformate to the anode gas stream of the PEM fuel cell.
  • the oxygen oxidizes the CO to CO2 at the anode of the fuel cell.
  • This method yields acceptable results, but has severe drawbacks.
  • the oxidation of CO is not selective, and some of the oxygen reacts with hydrogen, thus reducing efficiency and can damage the fuel cell.
  • Another drawback of this method is that it requires accurate measurement of the CO concentration and accurate metering of the air.
  • NL1998001010140 Some disadvantages of the above-described method are eliminated by the CO-removal method of NL1998001010140.
  • a material and method for selective removal of CO from reformate is claimed.
  • a precious metal catalyst is applied on a porous carrier in a reactor, a small amount of oxygen or air is metered into the reformate stream at the inlet of this reactor, and this catalyst is oxidizing the CO to CO2.
  • the method still has the drawback of oxidizing part of the hydrogen, and the necessity to accurate measurement of the CO concentration and accurate metering of the air or oxygen flow.
  • the method and apparatus according to the invention provides selective removal of a gas from a gas mixture.
  • the method and apparatus are especially effective for removal of CO from a hydrogen, CO2 and water vapor containing gas stream.
  • a membrane and means to fit this membrane in are provided, with on one side the CO-containing gas, and on the other side, a oxygen containing liquid or oxygen containing gas like air.
  • the membrane according to the invention is able to selectively absorb the CO, by means of a chemical reaction or physical adsorption on the first side to form a CO containing compound (CO-X), transport this CO containing compound to the other side of the membrane, and react the CO-containing compound with oxygen to form CO2 on the second side.
  • CO-X CO containing compound
  • the membrane according to the invention preferably consists of a porous polymer containing a liquid that is able to transport the CO containing compound (X).
  • This liquid could be water or a solution of selected salts, these salts being preferably catalytic active.
  • An example of a catalytically active salt solution is a mixture of Palladium chloride, Ruthenium chloride, Copper (II) Chloride, Lithium Chloride.
  • the solution can contain several additives than improve performance or stability.
  • the membrane has preferably a high porosity and a small pore size, sufficiently small for immobilizing the liquid.
  • the shape of the membrane can be flat, or tube like, as for example a hollow fiber.
  • the flows on both sides of the membrane can be parallel, counter flow or cross-flow.
  • the membrane can be coated on one side, or on both sides with a material that promotes the removal of CO from the reformate, or promotes the conversion of the CO containing compound to CO2 and the original compound as it was prior to the formation of the CO containing compound.
  • the membrane surface area can be increased, and the amount of gas that can be removed will typically be linear with the surface area. If flat membranes are used the capacity can be increased by increasing the size of the membrane, or by using more membranes in parallel or in series connection. Combinations of parallel and series connected membranes is also possible.
  • the membrane can be spirally wound or hollow fiber membranes can be used.
  • the porous membrane can consist of a porous polymer film, a non-woven material like paper, or a textile web like a fabric or cloth.
  • Suitable polymers for the porous film are for example PTFE, PVDF, PE or PES.
  • Suitable fibrous materials are several organic fibers like PE, and inorganic fibers glass and graphite.
  • the method and apparatus according to the invention can be integrated in to other components of the fuel cell system. Integration is for example possible in the fuel cell stack, in the fuel processor, or in the moistening units. If the CO removing membrane is integrated in the fuel cell stack, the reformate gas stream flows along the CO removing membrane prior to the anodes of the fuel cells, while the cathode outlet gas stream of the fuel cells can be used for the CO oxidation on the other side of the membrane. The oxygen content at the cathode outlet is sufficient for oxidation of the small amounts of CO.
  • An advantage of this integration is the compactness of the system, and easy control of gas temperatures and water content.
  • the CO-removing membrane or membranes into the fuel processor were it is positioned at the outlet.
  • Advantages of this integration are compactness of the system, improved thermal efficiency, and easy control of gas temperatures and water content.
  • a potential risk of the membrane according to the invention is loss of liquid. This can be avoided or reduced by making the surface or both surfaces of the membrane hydrophobic.
  • the Hydrophobic behavior can be obtained by treating the surface with special chemicals, or for example by laminating a hydrophobic gas permeable film to one or both sides of the membrane.
  • An other potential risk of the CO removal system according to the invention is transport of metal ions from the CO removing membrane to the fuel cell trough a water film on the inside of the connections. This is avoided by using a hydrophobic connection between both units.
  • a hydrophobic connection is for example a hydrophobic tube or hydrophobic ring on the inside of a connecting tube.
  • a film of porous UHMWPE was made non porous at the edges by pressing this area at a temperature of 100 degrees Celsius.
  • the remaining porous part (400 x 400mm) of the film was impregnated with a solution containing; 0,02 M PdCI2, 1 M CuCI2 and 1 M Cu(NO3)2.
  • the film was framed, and placed between two airtight chambers, thus realizing gas separation between these chambers.
  • the chambers and membrane were placed in an oven at a temperature of 70 degrees Celcius.
  • One chamber was filled with a mixture of 45% hydrogen, 33% nitrogen, 20 % CO2 and 2% CO.
  • the other chamber was filled with air that was saturated at 70 degrees Celsius with water vapor.
  • the CO concentration was measured in both chambers. After 10 minutes the CO concentration had dropped below the CO detection limit of the sensor ( «1PPM). In the other chamber, no CO was detected.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Water Supply & Treatment (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Fuel Cell (AREA)

Abstract

L'épuration des gaz et l'élimination sélective de gaz spécifiques de mélanges gazeux sont très importants dans de nombreux processus. Le procédé et l'appareil de l'invention permettent d'éliminer sélectivement des gaz spécifiques comme le monoxyde de carbone de mélanges gazeux contenant de l'hydrogène. Ce procédé consiste à mettre le mélange gazeux contenant l'hydrogène et le CO en contact avec un côté d'une membrane, alors que de l'autre côté de la membrane un gaz contenant de l'oxygène est fourni. Le CO se fixe sur la membrane ou sur certaines espèces chimiques de la membrane sur un côté, puis se déplace de l'autre côté de la membrane où il se transforme avec l'oxygène en CO2.
PCT/NL2001/000389 2000-05-23 2001-05-21 Purification de melanges gazeux Ceased WO2001089665A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU60788/01A AU6078801A (en) 2000-05-23 2001-05-21 Purification of gas mixtures

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
NL1015269 2000-05-23
NL1015270 2000-05-23
NL1015269A NL1015269C1 (nl) 2000-05-23 2000-05-23 Methode voor de continue selectieve verwijdering van gassen uit gasmengsels.
NL1015270A NL1015270C1 (nl) 2000-05-23 2000-05-23 Membraanscheidingsmethode voor de continue selectieve verwijdering van gassen uit gasmengsels.

Publications (1)

Publication Number Publication Date
WO2001089665A1 true WO2001089665A1 (fr) 2001-11-29

Family

ID=26643178

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL2001/000389 Ceased WO2001089665A1 (fr) 2000-05-23 2001-05-21 Purification de melanges gazeux

Country Status (2)

Country Link
AU (1) AU6078801A (fr)
WO (1) WO2001089665A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005519012A (ja) * 2002-02-27 2005-06-30 ボルボ テクノロジー コーポレイション 燃料電池用水素燃料発生システム

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4147754A (en) * 1975-07-28 1979-04-03 General Electric Company System for selective removal of hydrogen sulfide from a mixture of gases
US4474858A (en) * 1981-07-10 1984-10-02 Ube Industries, Ltd. Aromatic polyimide gas-separating membrane
EP0349204A2 (fr) * 1988-06-28 1990-01-03 Bend Research, Inc. Utilisation et régénération de réactifs en utilisant des réactions couplées et des barrières permsélectives
EP0434562A1 (fr) * 1989-12-20 1991-06-26 MEDAL 1.p. Procédé et dispositif pour éliminer le monoxyde de carbone des mélanges de gaz contenant de l'hydrogène
EP0435724A2 (fr) * 1989-12-27 1991-07-03 Petroleum Energy Center Amélioration du procédé de génération de courant avec des piles à combustible
EP0989093A2 (fr) * 1998-09-21 2000-03-29 Air Products And Chemicals, Inc. Production de gaz de synthèse avec des membranes mixtes conductrices avec conversion integrée en produits liquides

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4147754A (en) * 1975-07-28 1979-04-03 General Electric Company System for selective removal of hydrogen sulfide from a mixture of gases
US4474858A (en) * 1981-07-10 1984-10-02 Ube Industries, Ltd. Aromatic polyimide gas-separating membrane
EP0349204A2 (fr) * 1988-06-28 1990-01-03 Bend Research, Inc. Utilisation et régénération de réactifs en utilisant des réactions couplées et des barrières permsélectives
EP0434562A1 (fr) * 1989-12-20 1991-06-26 MEDAL 1.p. Procédé et dispositif pour éliminer le monoxyde de carbone des mélanges de gaz contenant de l'hydrogène
EP0435724A2 (fr) * 1989-12-27 1991-07-03 Petroleum Energy Center Amélioration du procédé de génération de courant avec des piles à combustible
EP0989093A2 (fr) * 1998-09-21 2000-03-29 Air Products And Chemicals, Inc. Production de gaz de synthèse avec des membranes mixtes conductrices avec conversion integrée en produits liquides

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005519012A (ja) * 2002-02-27 2005-06-30 ボルボ テクノロジー コーポレイション 燃料電池用水素燃料発生システム
EP1808410A3 (fr) * 2002-02-27 2007-08-01 Volvo Technology Corporation Systeme de generation de combustible a hydrogene pour une pile a combustible
JP2009179555A (ja) * 2002-02-27 2009-08-13 Volvo Technology Corp 燃料電池用水素燃料発生システム

Also Published As

Publication number Publication date
AU6078801A (en) 2001-12-03

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