WO2011071138A1 - シリカ系水素分離材料及びその製造方法、並びにそれを備えた水素分離モジュール及び水素製造装置 - Google Patents

シリカ系水素分離材料及びその製造方法、並びにそれを備えた水素分離モジュール及び水素製造装置 Download PDF

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WO2011071138A1
WO2011071138A1 PCT/JP2010/072201 JP2010072201W WO2011071138A1 WO 2011071138 A1 WO2011071138 A1 WO 2011071138A1 JP 2010072201 W JP2010072201 W JP 2010072201W WO 2011071138 A1 WO2011071138 A1 WO 2011071138A1
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hydrogen
silica glass
hydrogen separation
porous
separation material
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PCT/JP2010/072201
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English (en)
French (fr)
Japanese (ja)
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博匡 俵山
徹 足立
俊昭 柿井
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住友電気工業株式会社
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Priority to JP2011545256A priority Critical patent/JP5757243B2/ja
Priority to EP10836057.9A priority patent/EP2511005B1/de
Priority to CA 2783961 priority patent/CA2783961A1/en
Priority to US13/515,230 priority patent/US9126151B2/en
Priority to CN201080056142XA priority patent/CN102652036A/zh
Priority to KR1020127015087A priority patent/KR101880769B1/ko
Publication of WO2011071138A1 publication Critical patent/WO2011071138A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B01D71/027—Silicium oxide
    • 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
    • B01D53/02—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 adsorption, e.g. preparative gas chromatography
    • B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • 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
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
    • B01D67/00415—Inorganic membrane manufacture by agglomeration of particles in the dry state by additive layer techniques, e.g. selective laser sintering [SLS], selective laser melting [SLM] or 3D printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/04—Tubular membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/105—Support pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/108—Inorganic support material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/04—Glass
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
    • C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/26—Further operations combined with membrane separation processes
    • B01D2311/2626—Absorption or adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/26—Further operations combined with membrane separation processes
    • B01D2311/2696—Catalytic reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/15—Use of additives
    • B01D2323/218—Additive materials
    • B01D2323/2181—Inorganic additives
    • B01D2323/21811—Metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/04—Characteristic thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/22—Thermal or heat-resistance properties
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a hydrogen separation material for separating hydrogen with high purity from a mixed gas containing hydrogen generated by fuel reforming and the like, a method for producing the same, and a hydrogen separation module and a hydrogen production apparatus including the same.
  • the present invention relates to a hydrogen separation material in which a silica-based hydrogen permselective membrane that selectively permeates hydrogen is formed on the surface of a porous support, a method for producing the same, and a hydrogen separation module and a hydrogen production apparatus including the same.
  • hydrogen is produced by steam reforming a hydrocarbon fuel at a temperature of about 700 ° C. (CH 4 + H 2 O ⁇ CO + 3H 2 ), and then converting CO at a few hundred degrees (CO + H 2 O ⁇ CO 2 + H 2 ) is widely used from the viewpoint of price competitiveness.
  • Gas components obtained through these reactions include carbon dioxide, carbon monoxide, unreacted hydrocarbons and water in addition to hydrogen.
  • the purity of hydrogen is not increased in order to reduce costs, and a mixed gas with a hydrogen concentration of about 60% is directly used as the fuel electrode of the fuel cell.
  • the carbon monoxide that poisons the fuel electrode catalyst is oxidized to carbon dioxide (CO + 1 / 2O 2 ⁇ CO 2 ) before supply, and the concentration is removed to less than 10 ppm. Yes.
  • CO + 1 / 2O 2 ⁇ CO 2 carbon dioxide
  • concentration is removed to less than 10 ppm.
  • Examples of methods for extracting high-purity hydrogen from a mixed gas containing hydrogen include an absorption method, a cryogenic separation method, an adsorption method, and a membrane separation method.
  • the feature of the membrane separation method is high efficiency and easy miniaturization. have.
  • a membrane reactor in which a hydrogen separation membrane is inserted into a reaction vessel that performs steam reforming, hydrogen generated by the reforming reaction is continuously extracted from the reaction atmosphere, and the reforming reaction is performed even at a temperature of about 500 ° C.
  • CO shift reaction can be promoted at the same time, and high-purity hydrogen can be produced efficiently.
  • an expensive noble metal catalyst such as platinum used for CO conversion is not required in the membrane reactor, and the cost can be reduced and the equipment can be downsized.
  • the purity of the hydrogen gas that has passed through the hydrogen separation membrane depends on the performance of the hydrogen separation membrane, but even if CO removal or high purity is required depending on the application, the load on these steps should be reduced. Is possible.
  • Non-Patent Document 1 describes a hydrogen separation membrane in which a palladium alloy membrane is supported by a zirconia porous substrate. In this hydrogen separation membrane, hydrogen is dissolved as atoms in the palladium alloy, and is separated by a method of diffusing with the concentration gradient and allowing only pure hydrogen to permeate, so that high purity hydrogen can be obtained in principle.
  • Non-Patent Document 2 describes a hydrogen separation membrane in which a silica glass membrane is supported by an alumina porous substrate. This hydrogen separation membrane utilizes the fact that the silica glass membrane has pores with a size (0.3 nm) that allows only hydrogen molecules to pass through, and separates hydrogen by a molecular sieving function that selectively permeates hydrogen molecules. Is.
  • Non-Patent Document 1 due to long-term use, the mechanical strength decreases due to hydrogen embrittlement of the palladium alloy membrane and impurities such as sulfur and iron contained in the raw material gas. There is a disadvantage that the palladium alloy film is broken by alloying. Furthermore, palladium, which is a raw material, is not suitable for mass production because it is expensive and has a poor stable supply capability. Zirconia porous support is a material that has high thermal shock resistance among typical ceramics and has a small difference in thermal expansion coefficient from the palladium alloy film. There is a drawback of peeling from the porous support.
  • a hydrogen separation material comprising a membrane and its support
  • the membrane is a silica glass membrane
  • the linear thermal expansion coefficient of the support is By defining the above, it is possible to obtain a hydrogen separation material that is resistant to thermal shock and excellent in hydrogen separation characteristics, and in the production method, a porous support is formed that forms a porous support made of porous silica glass. It has been found that a desired hydrogen separation material can be produced by including a step and a silica glass film forming step of forming a silica glass film on the surface of the porous silica glass, and the present invention has been completed. That is, a hydrogen separation material and a method for producing the same according to the present invention, a hydrogen separation module and a hydrogen production apparatus including the same are as follows.
  • the hydrogen separation material of the present invention is characterized in that a silica glass membrane is formed on a porous support having a linear thermal expansion coefficient of 2 ⁇ 10 ⁇ 6 / K or less.
  • the suitable form of the hydrogen separation material of this invention is characterized by the said porous support body being porous silica glass.
  • Another preferred embodiment of the hydrogen separation material of the present invention is characterized in that the shape is tubular.
  • another preferred embodiment of the hydrogen separation material of the present invention is that the porous silica glass and / or the silica glass film has at least one element selected from rare earth elements, group 4B elements, Al and Ga. Is added.
  • the silica is formed on the porous support made of the porous silica glass by surface-modifying and densifying the porous silica glass. A glass film is formed.
  • the surface modification is performed by irradiating at least one selected from a CO 2 laser, a plasma arc and an oxyhydrogen burner, and the porous silica glass. It is the process which densifies the surface of this.
  • the method for producing a hydrogen separation material of the present invention includes a porous support forming step for forming a porous support made of porous silica glass, and a silica for forming a silica glass film on the surface of the porous silica glass. And a glass film forming step.
  • the porous support forming step deposits porous silica glass around the dummy rod, and then pulls out the dummy rod to make it porous. Characterized in that it is a step of forming a tubular porous support made of porous silica glass.
  • the porous support forming step is at least selected from a rare earth element, a group 4B element, Al and Ga around a dummy rod. This is characterized in that a porous silica glass to which one kind of element is added is deposited, and then a dummy rod is pulled out to form a tubular porous support made of porous silica glass.
  • the method for producing a hydrogen separation material of the present invention comprises a porous support forming step of forming a porous support made of the porous silica glass, and a dense surface by densifying the surface of the porous silica glass.
  • the silica glass film forming step irradiates at least one selected from a CO 2 laser, a plasma arc, and an oxyhydrogen burner. It is a step of densifying the surface of the porous silica glass.
  • Another hydrogen separation material of the present invention is obtained by any one of the above-described methods for producing a hydrogen separation material of the present invention.
  • Another preferred embodiment of the hydrogen separation material of the present invention is characterized in that the porosity of the porous support is 20 to 70%.
  • Another preferred embodiment of the hydrogen separation material of the present invention is characterized in that the porous support has a thickness of 0.2 to 5 mm.
  • Another preferred embodiment of the hydrogen separation material of the present invention is characterized in that the silica glass membrane has a thickness of 0.01 to 50 ⁇ m.
  • the hydrogen separation module of the present invention is characterized by including any of the hydrogen separation materials of the present invention described above and a steam reforming catalyst.
  • the hydrogen production apparatus of the present invention is characterized by including the hydrogen separation module of the present invention described above.
  • Another hydrogen production apparatus of the present invention includes the above-described hydrogen separation module and CO removal module of the present invention.
  • a preferred embodiment of the hydrogen production apparatus of the present invention is characterized in that the CO removal module includes a CO methanation catalyst.
  • the suitable form of the hydrogen production apparatus of this invention was equipped with the hydrogen separation module of this invention mentioned above, and the hydrogen purification module which applied the pressure swing adsorption (PSA) method.
  • PSA pressure swing adsorption
  • a hydrogen separation material that is resistant to thermal shock, has good adhesion between a membrane and a support, and has excellent hydrogen separation characteristics, a method for producing the same, and a hydrogen separation equipped with the same A module and a hydrogen production apparatus can be provided.
  • FIG. 1 is a partial cross-sectional view showing an example of the hydrogen separation material of the present invention.
  • the hydrogen separation material 10 is formed by forming a silica glass membrane 12 on a porous support 11 having a linear thermal expansion coefficient of 2 ⁇ 10 ⁇ 6 / K or less.
  • the silica glass film 12 is used as a hydrogen permeable film in this way, thereby suppressing hydrogen embrittlement and film deterioration due to reaction with raw material impurities.
  • the thickness of the silica glass film 12 is not particularly limited, but is preferably 0.01 to 50 ⁇ m, more preferably 0.02 to 10 ⁇ m, and further preferably 0.03 to 5 ⁇ m. preferable. If it is less than 0.01 ⁇ m, the hydrogen purity of the permeate gas becomes too low, and if it exceeds 50 ⁇ m, the hydrogen permeation rate becomes too low, and it may be difficult to obtain practically sufficient hydrogen separation performance.
  • the porous support 11 can be used to support the thin film without interfering with hydrogen permeation through the silica glass film 12.
  • the porosity of the porous support 11 is not particularly limited, but is preferably 20 to 70% from the balance of mechanical strength and gas permeability.
  • the “porosity” can be calculated as the ratio of the air volume per unit volume.
  • the linear thermal expansion coefficient of the porous support 11 is 2 ⁇ 10 ⁇ 6 / K or less as described above. When it exceeds 2 ⁇ 10 ⁇ 6 / K, the generated thermal stress increases, and the desired thermal shock resistance cannot be obtained.
  • the material of the porous support 11 is not particularly limited as long as it has a prescribed linear thermal expansion coefficient, but is preferably a material whose linear thermal expansion coefficient approximates that of the silica glass film 12 from the viewpoint of thermal shock resistance.
  • the thickness of the porous support 11 is not particularly limited, but is preferably 0.2 to 5 mm, more preferably 0.5 to 3 mm, from the balance of mechanical strength and gas permeability. preferable.
  • the shape of the hydrogen separation material 10 of the present invention is not particularly limited, and may be any shape such as a planar shape. However, in order to increase the contact area with the hydrogen-containing mixed gas from the viewpoint of reaction efficiency. It is preferable that it is tubular.
  • FIG. 2 shows an example of a tubular hydrogen separation material 20.
  • the hydrogen separation material 20 has a substantially cylindrical shape, and has a central hole 23 having a substantially circular cross section extending in the longitudinal direction at the center thereof.
  • the hydrogen separation material 20 has a porous support 21 and a silica glass membrane 22 in this order as tube walls on the outer periphery of the center hole 23.
  • the outer diameter T is 2 mm to 50 mm
  • the inner diameter (diameter of the center hole 23) P is 1.6 mm to 48 mm
  • the length L is about 200 mm to 400 mm. It is desirable that one end 23a of the center hole 23 is closed. Further, in order to increase the surface area of the tube, the outer diameter T and the inner diameter P may be periodically changed in the longitudinal direction, and the thickness can be partially changed in order to reinforce the mechanical strength.
  • the porous support 11 is preferably selected from those whose linear thermal expansion coefficient approximates that of the silica glass film 12.
  • the material of the porous support 11 is preferably porous silica glass.
  • the silica glass film 12 and the porous silica glass constituting the porous support 11 are used.
  • a rare earth element, a 4B group element, Al, Ga, or a combination of two or more of these elements can be added to either one or both. This is because by adjusting the components of the porous silica glass and the silica glass film 12 constituting the porous support 11, desired mechanical properties, water vapor resistance, and the like can be obtained.
  • the hydrogen separation material 10 of the present invention when used for steam reforming of hydrocarbon fuel, it necessarily comes into contact with steam at 500 ° C. or higher, so that the steam resistance performance is improved by introducing other components in this way. It is preferable.
  • the porous silica glass which comprises the porous support body 11 can be manufactured by manufacturing methods, such as a sooting method (CVD method) and an injection molding method.
  • the method for forming the silica glass film 12 is not particularly limited, but means other than the sol-gel method and the CVD method can be used for forming the surface by modifying the surface of the porous silica glass constituting the porous support 11. .
  • “Surface modification” means that a portion that becomes a surface membrane, for example, the vicinity of the surface of the porous silica glass that constitutes the porous support 11 is somewhat densified in order to produce a hydrogen permeable membrane portion.
  • One of the methods is heating.
  • the silica glass film 12 can be manufactured by a sol-gel method or a CVD method.
  • the porous silica glass and the silica glass film 12 constituting the porous support 11 are separately formed.
  • the degree of densification of the silica glass film 12 is set by the molecular size of the gas to be separated. From the viewpoint of hydrogen permeation, it is desirable that the silica glass film 12 be densified so that the pore diameter is about 0.3 nm.
  • the method for producing a hydrogen separation material of the present invention includes (1) a porous support forming step for forming a porous support made of porous silica glass, and (2) forming a silica glass film on the surface of the porous silica glass. A silica glass film forming step.
  • porous support body formation process Although the method to manufacture porous silica glass is not specifically limited, For example, a sooting method (CVD method) and the injection molding method can be mentioned. In addition, as a preferable example of the manufacturing method in the case where the tubular hydrogen separation material 20 described above has a porous support 21 made of porous silica glass, porous silica glass is deposited around a dummy rod. A method of pulling out the dummy rod (drawing step) later (deposition step) can be mentioned. An embodiment of the method will be described below with reference to FIG.
  • FIG. 3A is a diagram illustrating a deposition process according to the embodiment
  • FIG. 3B is a diagram illustrating a drawing process according to the embodiment.
  • the dummy bar 30 is arranged vertically with the tip portion facing down. Moreover, it is good also as a form arrange
  • alumina, glass, refractory ceramics, carbon or the like can be used as a material of the dummy bar 30, alumina, glass, refractory ceramics, carbon or the like can be used. After the dummy bar 30 is fixed, it is rotated about the central axis. Then, glass particles are deposited on the outer periphery of the dummy bar 30 by a burner 35 disposed on the side of the dummy bar 30 by an external CVD method (OVD method). Depending on the desired mechanical properties and water vapor resistance, rare earth elements, group 4B elements, Al, Ga, or a combination of two or more of these elements can be added to the glass fine particles. That is, according to
  • the burner 35 When depositing the glass particles, the burner 35 is traversed in the axial direction of the dummy bar 30 or the dummy bar 30 is traversed in the axial direction.
  • the feed material and the supply amount can be varied for each number of traverses.
  • the glass fine particles deposited on the outer periphery of the dummy bar 30 have a predetermined bulk density and composition distribution in the radial direction. Further, by depositing glass particles on the tip of the dummy rod 30, a tubular porous silica glass 25 having a closed tip is produced.
  • silica glass fine particles may be heat-sintered and densified so that the porosity is in the range of 20 to 70% after silica glass fine particles are deposited.
  • the porosity may be controlled by adjusting the temperature.
  • the temperature for heating and sintering after deposition is not particularly limited, but is preferably 1000 ° C. to 1400 ° C. If it is less than 1000 ° C., sintering may not proceed sufficiently, and if it exceeds 1400 ° C., the porosity may be too small.
  • the temperature is not particularly limited, but is preferably set to 1400 ° C. to 1700 ° C., for example.
  • the deposition temperature is more preferably 1500 ° C. to 1600 ° C.
  • the drawing process after the deposition process will be described with reference to FIG.
  • the dummy rod 30 is pulled out from the porous silica glass 25.
  • the central hole 23 formed by drawing does not penetrate, the lower end side (tip end side) 23a is closed, and only the upper end side is opened (see FIG. 2).
  • FIG.3 (c) is a figure explaining the silica glass film formation process which concerns on this embodiment.
  • a method for forming a silica glass film by modifying the surface of the porous silica glass with a surface treatment apparatus will be described.
  • the surface of the porous silica glass 25 obtained in the porous support process is modified by densifying the surface of the porous silica glass 25 into a dense silica glass film 22 by the surface treatment device 36.
  • the porous support 21 and the silica glass film 22 are formed by surface modification of the porous silica glass 25.
  • the degree of surface modification of the silica glass membrane 22 is not particularly limited as long as the silica glass membrane 22 functions as a hydrogen permeable membrane, but from the viewpoint of hydrogen molecule separability, the thickness is 0.01. It is preferably from ⁇ 50 ⁇ m, more preferably from 0.02 to 10 ⁇ m, and even more preferably from 0.03 to 5 ⁇ m.
  • membrane 22 has a hole about 0.3 nm in diameter so that only a hydrogen molecule may permeate
  • a drawing step is performed in which only the dummy rod 30 is drawn from the porous silica glass 25 deposited around the dummy rod 30 before the silica glass film forming step.
  • the silica glass film forming step may be performed in a state where the porous silica glass 25 is deposited.
  • the tubular hydrogen separation material 20 can be formed by pulling out only the dummy rod 30.
  • the hydrogen separation module of the present invention includes the hydrogen separation material of the present invention and a steam reforming catalyst.
  • FIG. 4 is a diagram illustrating a hydrogen separation module to which the hydrogen separation material 20 is applied.
  • a hydrogen separation module 40 shown in FIG. 4 includes a hydrogen separation material 20 and a steam reforming catalyst 41 in a reaction vessel 42.
  • the reaction vessel 42 has an introduction port 43 for introducing the raw material gas 50 into the reaction vessel 42, an exhaust port 44 for discharging the exhaust gas 51 from the reaction vessel 42, and an installation for installing the hydrogen separation material 20 in the reaction vessel 42. And a mouth 45.
  • the steam reforming catalyst 41 is packed around the hydrogen separation material 20 in the reaction vessel 42.
  • the raw material gas 50 is obtained by burning fuel such as city gas, propane gas, kerosene, petroleum, biomethanol, natural gas, methane hydrate and the like.
  • the source gas 50 is heated at about 500 ° C. and reformed by the steam reforming catalyst 41 (for example, a Ru-based catalyst) to generate hydrogen gas.
  • the generated hydrogen gas is selectively extracted by the tubular hydrogen separation material 20, permeated to the central hole 23 inside the tube, and taken out of the reactor 42. For this reason, hydrogen production is promoted in a chemical equilibrium, the reaction temperature can be lowered, and a CO shift reaction occurs at the same time, so that a CO shift catalyst is theoretically unnecessary.
  • the hydrogen production apparatus of the present invention includes the hydrogen separation module of the present invention.
  • the hydrogen separated and produced by the hydrogen separation module of the present invention is considered to have a high purity of 99% or more.
  • a CO selective oxidation catalyst may be used instead of the CO methanation catalyst. In this case, oxygen or air must be supplied between the hydrogen separation module and the CO removal module, and the reaction between hydrogen and oxygen.
  • FIG. 5 is a diagram illustrating a hydrogen production apparatus including a hydrogen separation module 40 and a CO removal module having a CO methanation catalyst.
  • a hydrogen production apparatus 60 shown in FIG. 5 includes a hydrogen separation module 40 and a CO removal module 65.
  • the CO removal module 65 includes a reaction vessel 61 in which a CO removal reaction is performed, and a CO methanation catalyst (for example, a Ru-based catalyst) 62 therein.
  • the hydrogen production apparatus 60 includes a heating element 53 for causing a steam reforming reaction of the raw material gas 50 in the vicinity of the hydrogen separation module 40 and a heating element 63 for causing a CO removal reaction in the vicinity of the CO removal module 65.
  • the CO removal module 65 is connected to the hydrogen separation module 40 through a connection pipe 54 using a connection joint 48.
  • the hydrogen gas generated by the hydrogen separation module 40 is introduced into the CO removal module 65 through the connecting pipe 54 and used for the CO removal reaction. In this way, the highly purified hydrogen gas is taken out from the discharge port 64.
  • FIG. 6 is a diagram for explaining a hydrogen production apparatus including a hydrogen separation module 40 and a hydrogen purification module to which a pressure swing adsorption (PSA) method is applied.
  • a hydrogen production apparatus 70 shown in FIG. 6 includes a plurality of hydrogen separation modules 40 and a hydrogen purification module (PSA unit) 75 to which the PSA method is applied.
  • PSA unit hydrogen purification module
  • a hydrogen discharge portion (not shown) in the hydrogen separation material 20 is connected to the PSA unit 75 via a connection pipe 71.
  • a panel-like heating element (shown by a dotted line) 72 is installed in the vicinity of the plurality of hydrogen separation modules 40 to cause a steam reforming reaction.
  • the generated hydrogen gas is introduced into the PSA unit 75 through the connecting pipe 71, and then gas components other than hydrogen are removed to produce high purity hydrogen gas.
  • Example 1 Porous glass having the composition shown in Table 1 (mol%) is deposited on a carbon-coated one-end-sealed alumina tube using an external CVD method, and a dummy rod is pulled out to obtain an outer diameter of 10 mm, a thickness of 1 mm, and a length. An end-sealed porous glass having a thickness of 300 mm was produced. A silica glass film having a thickness of 50 nm was formed on the surface of the porous glass using a sol-gel method. When these composite structures were heated to 500 ° C. in an electric furnace and quickly dropped into water at 30 ° C., no breakage of the composite structure or crack formation of the silica glass film was observed.
  • Example 4 Porous silica glass was deposited on a carbon-coated one-end-sealed alumina tube using an external CVD method. Next, the surface of the porous silica glass was irradiated with a CO 2 laser to form a dense silica glass film having a thickness of 1 micron. A dummy rod was pulled out from this composite structure to produce a tubular hydrogen separation material having an outer diameter of 16 mm, a thickness of 1.5 mm, a length of 300 mm, a porosity of 40%, and a linear thermal expansion coefficient of 0.7 ⁇ 10 ⁇ 6 / K. .
  • the hydrogen concentration of the atmospheric gas permeated to the inside of the hydrogen separation material was 99% or more, and 550 ° C.
  • the hydrogen permeation coefficient was 4 ⁇ 10 ⁇ 7 mol ⁇ m ⁇ 2 ⁇ s ⁇ 1 ⁇ Pa ⁇ 1 .
  • Example 5 Porous silica glass was deposited on a carbon-coated one-end-sealed alumina tube using an external CVD method. Next, the surface of this porous body was irradiated with a plasma arc to form a silica glass dense film having a thickness of 20 microns. A dummy bar was pulled out from this composite structure to produce a tubular hydrogen separation material having an outer diameter of 10 mm, a thickness of 1 mm, a length of 300 mm, a porosity of 68%, and a linear thermal expansion coefficient of 0.7 ⁇ 10 ⁇ 6 / K.
  • the hydrogen concentration of the atmospheric gas permeated to the inside of the hydrogen separation material was 99% or more, and 550 ° C.
  • the hydrogen permeation coefficient was 0.3 ⁇ 10 ⁇ 7 mol ⁇ m ⁇ 2 ⁇ s ⁇ 1 ⁇ Pa ⁇ 1 .
  • Example 6 Porous silica glass was deposited on a carbon-coated one-end-sealed alumina tube using an external CVD method. Next, the surface of the porous body was irradiated with an oxyhydrogen burner flame to form a silica glass dense film having a thickness of 40 microns. A dummy bar was pulled out from this composite structure to produce a tubular hydrogen separation material having an outer diameter of 16 mm, a thickness of 4 mm, a length of 300 mm, a porosity of 22%, and a linear thermal expansion coefficient of 0.7 ⁇ 10 ⁇ 6 / K.
  • the hydrogen concentration of the atmospheric gas permeated to the inside of the hydrogen separation material was 99% or more, and 550 ° C.
  • the hydrogen permeation coefficient was 0.05 ⁇ 10 ⁇ 7 mol ⁇ m ⁇ 2 ⁇ s ⁇ 1 ⁇ Pa ⁇ 1 .
  • Example 7 to 10 Four types of porous silica glass added with 1000 ppm of Y, Al, Ti, and Ga were deposited on a carbon-coated one-end-sealed alumina tube using an external CVD method. Next, the surface of this porous body was irradiated with a CO 2 laser to form a silica glass dense film having a thickness of 3 microns. A dummy rod was pulled out from this composite structure to produce a tubular hydrogen separation material having an outer diameter of 16 mm, a thickness of 1.5 mm, a length of 300 mm, a porosity of 40%, and a linear thermal expansion coefficient of 0.7 ⁇ 10 ⁇ 6 / K. .
  • H 2 O / CH 4 3 source gas was supplied to the reaction vessel of the hydrogen separation module equipped with the tubular hydrogen separation material of Example 9 and a commercially available Ru-based reforming catalyst, Steam reforming was performed at a temperature of 550 ° C. and a pressure of 0.5 MPaG.
  • the hydrogen concentration of the gas permeated inside the tubular hydrogen separation material was 99% or more, the carbon monoxide concentration was about 500 ppm, and the hydrogen production rate was 0.02 Nm 3 / h.
  • the carbon monoxide concentration after passing this gas through a CO removal module equipped with a commercially available Ru-based CO methanation catalyst was 10 ppm or less.
  • Table 2 shows the characteristics and the like of Examples 4 to 12 above.
  • the porous support by making the porous support the same material with a thermal expansion coefficient of 2 ⁇ 10 ⁇ 6 / K or less and a thermal expansion coefficient approximate to that of the silica glass film, it becomes more resistant to thermal shock.
  • An excellent hydrogen separation material can be obtained.
  • a hydrogen separation material having high bonding strength between the membrane and the support can be obtained, and the thickness and pores of the silica glass membrane can be obtained. Can be easily controlled by the degree of modification (densification).

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PCT/JP2010/072201 2009-12-11 2010-12-10 シリカ系水素分離材料及びその製造方法、並びにそれを備えた水素分離モジュール及び水素製造装置 WO2011071138A1 (ja)

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EP10836057.9A EP2511005B1 (de) 2009-12-11 2010-12-10 Verfahren zur herstellung von kieselsäurehaltigem wasserstofftrennmaterial
CA 2783961 CA2783961A1 (en) 2009-12-11 2010-12-10 Silica-based hydrogen separation material and manufacturing method therefor, as well as hydrogen separation module and hydrogen production apparatus having the same
US13/515,230 US9126151B2 (en) 2009-12-11 2010-12-10 Silica-based hydrogen separation material and manufacturing method therefor, as well as hydrogen separation module and hydrogen production apparatus having the same
CN201080056142XA CN102652036A (zh) 2009-12-11 2010-12-10 石英类氢分离材料及其制造方法、包括该氢分离材料的氢分离模块及氢制造装置
KR1020127015087A KR101880769B1 (ko) 2009-12-11 2010-12-10 실리카계 수소 분리 재료 및 그 제조 방법과 그것을 포함한 수소 분리 모듈 및 수소 제조 장치

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JP2013056788A (ja) * 2011-09-07 2013-03-28 Sumitomo Electric Ind Ltd 多孔質ガラス管の製造方法
JP2013234082A (ja) * 2012-05-07 2013-11-21 Sumitomo Electric Ind Ltd ガラス管およびその製造方法、ガラス管を用いた流体分離材料
JP2015024363A (ja) * 2013-07-25 2015-02-05 住友電気工業株式会社 流体分離材料及びその製造方法
JP2018111629A (ja) * 2017-01-11 2018-07-19 日本電気硝子株式会社 ガラス部材及びその製造方法
CN117863707A (zh) * 2024-03-11 2024-04-12 杭州邦齐州科技有限公司 一种预键合玻璃分离治具及其分离方法
JP7561416B2 (ja) 2020-09-25 2024-10-04 学校法人 工学院大学 水素製造装置、水素分離膜及び水素分離膜の製造方法

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JP2013056788A (ja) * 2011-09-07 2013-03-28 Sumitomo Electric Ind Ltd 多孔質ガラス管の製造方法
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CN117863707A (zh) * 2024-03-11 2024-04-12 杭州邦齐州科技有限公司 一种预键合玻璃分离治具及其分离方法
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JP5757243B2 (ja) 2015-07-29
US9126151B2 (en) 2015-09-08
CA2783961A1 (en) 2011-06-16
CN102652036A (zh) 2012-08-29
EP2511005B1 (de) 2020-02-19
US20130022509A1 (en) 2013-01-24
KR101880769B1 (ko) 2018-07-20

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