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 PDFInfo
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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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- Prior art keywords
- hydrogen
- silica glass
- hydrogen separation
- porous
- separation material
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 248
- 239000001257 hydrogen Substances 0.000 title claims abstract description 244
- 238000000926 separation method Methods 0.000 title claims abstract description 150
- 150000002431 hydrogen Chemical class 0.000 title claims abstract description 149
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 239000000463 material Substances 0.000 title claims abstract description 107
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000008569 process Effects 0.000 title abstract description 11
- 239000000377 silicon dioxide Substances 0.000 title description 4
- 239000012528 membrane Substances 0.000 claims abstract description 53
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000000629 steam reforming Methods 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 7
- 229910052733 gallium Inorganic materials 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- -1 group 4B elements Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000002407 reforming Methods 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 50
- 239000007789 gas Substances 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000000446 fuel Substances 0.000 description 16
- 238000005229 chemical vapour deposition Methods 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 230000035939 shock Effects 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 239000002131 composite material Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 229910001252 Pd alloy Inorganic materials 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000005373 porous glass Substances 0.000 description 6
- 238000003980 solgel method Methods 0.000 description 6
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- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000012466 permeate Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
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- 239000002245 particle Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000006057 reforming reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
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- 230000000052 comparative effect Effects 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000011214 refractory ceramic Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Images
Classifications
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- 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
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- 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
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- 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
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- 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
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- 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
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
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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
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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Abstract
Description
即ち、本発明にかかる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は下記の通りである。
(2)また、本発明の水素分離材料の好適形態は、前記多孔質支持体が多孔質シリカガラスであることを特徴とする。
(3)また、本発明の水素分離材料の別の好適形態は、形状が管状であることを特徴とする。
(4)また、本発明の水素分離材料の別の好適形態は、前記多孔質シリカガラス及び/又は前記シリカガラス膜に希土類元素、4B族元素、Al及びGaから選択される少なくとも1種の元素が添加されたことを特徴とする。
(5)また、本発明の水素分離材料の別の好適形態は、前記多孔質シリカガラスを表面改質して緻密化することで、前記多孔質シリカガラスからなる多孔質支持体上に前記シリカガラス膜を形成したことを特徴とする。
(6)また、本発明の水素分離材料の別の好適形態は、前記表面改質が、CO2レーザー、プラズマアーク及び酸水素バーナーから選択される少なくとも1種を照射して前記多孔質シリカガラスの表面を緻密化する処理であることを特徴とする。
(8)また、本発明の水素分離材料の製造方法の好適形態は、前記多孔質支持体形成工程が、ダミー棒の周囲に多孔質シリカガラスを堆積させ、その後、前記ダミー棒を引き抜いて多孔質シリカガラスからなる管状の多孔質支持体を形成する工程であることを特徴とする。
(9)また、本発明の水素分離材料の製造方法の別の好適形態は、前記多孔質支持体形成工程が、ダミー棒の周囲に希土類元素、4B族元素、Al及びGaから選択される少なくとも1種の元素が添加された多孔質シリカガラスを堆積させ、その後、ダミー棒を引き抜いて多孔質シリカガラスからなる管状の多孔質支持体を形成する工程であることを特徴とする。
(10)本発明の水素分離材料の製造方法は、前記多孔質シリカガラスからなる多孔質支持体を形成する多孔質支持体形成工程と、前記多孔質シリカガラスの表面を緻密化して緻密質のシリカガラス膜を形成するシリカガラス膜形成工程とを有することを特徴とする。
(11)また、本発明の水素分離材料の製造方法の別の好適形態は、前記シリカガラス膜形成工程が、CO2レーザー、プラズマアーク及び酸水素バーナーから選択される少なくとも1種を照射して前記多孔質シリカガラスの表面を緻密化する工程であることを特徴とする。
(14)また、本発明の水素分離材料の別の好適形態は、前記多孔質支持体の厚みが0.2~5mmであることを特徴とする。
(15)また、本発明の水素分離材料の別の好適形態は、前記シリカガラス膜の厚みが 0.01~50μmであることを特徴とする。
(19)また、本発明の水素製造装置の好適形態は、前記CO除去モジュールがCOメタン化触媒を備えたことを特徴とする。
(20)また、本発明の水素製造装置の好適形態は、上述した本発明の水素分離モジュールと圧力スウィング吸着(PSA)法を適用した水素高純度化モジュールとを備えたことを特徴とする。
図1は、本発明の水素分離材料の一例を示す部分断面図である。水素分離材料10は、線熱膨張係数が2×10-6/K以下の多孔質支持体11の上に、シリカガラス膜12を形成してなる。
本発明においては、このようにシリカガラス膜12を水素透過膜として使用するが、それにより、水素脆性や原料不純物との反応による膜の劣化を抑制した。シリカガラス膜12の厚みは、特に限定されるものではないが、0.01~50μmであることが好ましく、0.02~10μmであることがより好ましく、0.03~5μmであることが更に好ましい。0.01μm未満では、透過ガスの水素純度が低くなりすぎ、また、50μmを超えると水素透過速度が小さくなりすぎ、実用上十分な水素分離性能が得られにくくなる場合がある。
また、多孔質支持体11の線熱膨張係数は、上述のように、2×10-6/K以下である。2×10-6/Kを超えると、発生する熱応力が大きくなり、所望の耐熱衝撃性が得られない。多孔質支持体11の材料については、規定の線熱膨張係数を有するものであれば特に限定はされないが、耐熱衝撃性の観点からシリカガラス膜12と線熱膨張係数が近似するものが好ましい。
該多孔質支持体11の厚みは、特に限定されるものではないが、機械的強度とガス透過性のバランスから0.2~5mmであることが好ましく、0.5~3mmであることがより好ましい。
図2に、管状の水素分離材料20の一例を示す。水素分離材料20は略円柱形状であり、その中心には長手方向に延びる略円形断面の中心孔23を有する。水素分離材料20は、中心孔23の外周上に管壁として多孔質支持体21およびシリカガラス膜22をこの順に有してなる。その外径Tは2mm~50mm、内径(中心孔23の径)Pは1.6mm~48mm、長さLは200mm~400mm程度である。中心孔23の一方の端部23aは塞がれていることが望ましい。また、管の表面積を大きくするため、外径Tおよび内径Pを長手方向に周期的に変化させても良く、機械的強度を補強するため厚みを部分的に変化させることもできる。
例えば、本発明の水素分離材料10を炭化水素燃料の水蒸気改質に用いる場合、500℃以上の水蒸気に必然的に接触するため、このように他成分を導入することにより耐水蒸気性能を向上させることが好ましい。
上記したように、ゾルゲル法やCVD法でもシリカガラス膜12を製造できるが、表面改質による形成法によれば、多孔質支持体11を構成する多孔質シリカガラスとシリカガラス膜12を別々に製造して積層する製造方法より、膜と支持体との接合強度を上げることができ、またシリカガラス膜12の厚さや孔の大きさを緻密化の程度によって、簡単に制御することができる。シリカガラス膜12の緻密化の程度は、分離する気体の分子サイズで設定される。水素透過の観点から、シリカガラス膜12の孔径が0.3nm程度となるように緻密化されることが望ましい。
本発明の水素分離材料の製造方法は、(1)多孔質シリカガラスからなる多孔質支持体を形成する多孔質支持体形成工程、(2)前記多孔質シリカガラスの表面にシリカガラス膜を形成するシリカガラス膜形成工程、を含む。以下、本発明の水素分離材料の製造方法について、図面を参照しつつ説明する。
多孔質シリカガラスを製造する方法は、特に限定はされないが、例えば、スス付け法(CVD法)、射出成形法を挙げることができる。
また、前記で説明した管状の水素分離材料20であって、その多孔質支持体21が多孔質シリカガラスである場合の製造方法の好適例として、ダミー棒の周囲に多孔質シリカガラスを堆積した後(堆積工程)、該ダミー棒を引き抜いて(引抜工程)行う方法を挙げることができる。図3を用いて、当該方法の一実施形態を以下に説明する。
多孔質シリカガラスからなる多孔質支持体が形成された後、ゾルゲル法やCVD法、多孔質シリカガラスを表面改質する方法などにより、該多孔質支持体の表面にシリカガラス膜が形成される。図3(c)は、該実施形態に係るシリカガラス膜形成工程を説明する図である。ここでは、多孔質シリカガラスの表面を、表面処理装置により表面改質して、シリカガラス膜を形成する方法について説明する。
上記多孔質支持体工程で得られた多孔質シリカガラス25は、表面処理装置36によって、その表面を緻密質なシリカガラス膜22に緻密化することで表面改質される。表面処理装置36としては、例えば高温のエネルギー線を照射できるものであればよく、CO2レーザー、プラズマアーク、酸水素バーナーなどを単独で、又は複数組合せて用いるができる。こうして多孔質シリカガラス25を表面改質することで、多孔質支持体21とシリカガラス膜22とが形成される。
シリカガラス膜22の表面改質の程度は、シリカガラス膜22が水素透過膜として機能する範囲であれば特に限定されるものではないが、水素分子分離性の観点から、その厚みは0.01~50μmであることが好ましく、0.02~10μmであることがより好ましく、0.03~5μmであることが更に好ましい。また、シリカガラス膜22は水素分子のみを透過するように直径0.3nm程度の孔を有していることが好ましい。
本発明の水素分離モジュールは、本発明の水素分離材料と、水蒸気改質触媒を含む。以下、本発明の水素分離モジュールの一実施形態について、図4を参照して説明する。図4は、水素分離材料20を適用した水素分離モジュールを説明する図である。
図4に示す水素分離モジュール40は、水素分離材料20と水蒸気改質触媒41を反応容器42内に備える。反応容器42は、原料ガス50を反応容器42内に導入する導入口43と、反応容器42から排ガス51を排出する排出口44と、水素分離材料20を反応容器42内に設置するための設置口45とを備える。水蒸気改質触媒41は、反応容器42内の水素分離材料20の周囲に詰められる。
原料ガス50は、都市ガス、プロパンガス、灯油、石油、バイオメタノール、天然ガス、メタンハイドレート等の燃料を燃焼することにより得られる。原料ガス50は、反応器42内に導入された後に500℃程度で加熱され、水蒸気改質触媒41(例えばRu系触媒)により改質されて水素ガスを生成する。改質反応中、生成した水素ガスは管状の水素分離材料20によって選択的に引抜かれて管の内部の中心孔23まで透過され、反応器42の外へ取り出される。そのため、化学平衡的に水素生成が促進され、反応の低温化を実現することができ、同時にCO変成反応も起こるため、CO変成触媒は理論的に不要となる。
本発明の水素製造装置は、本発明の水素分離モジュールを備える。本発明の水素分離モジュールにより分離生成された水素は99%以上の高純度であると考えられるが、混入するCO量をより低減するため(好ましくは10ppm以下)、例えば家庭用定置型燃料電池に用いる水素製造装置の場合は、COメタン化触媒等を有するCO除去モジュールを更に備えることが好ましい。なお、COメタン化触媒の代わりにCO選択酸化触媒を用いてもよいが、この場合、水素分離モジュールとCO除去モジュールの間で酸素または空気を供給する必要があること、水素と酸素の反応による水生成や窒素などの混入により水素濃度が低下することなどの欠点がある。自動車用燃料電池に用いる水素の製造装置の場合は、更にCO濃度が低く(1ppm未満)高純度の水素(99.99%以上)が求められるため、圧力スウィング吸着(PSA)法を適用した水素高純度化モジュールを更に備えることが好ましい。
図5は、水素分離モジュール40と、COメタン化触媒を有するCO除去モジュールとを備えた水素製造装置を説明する図である。
図5に示す水素製造装置60は、水素分離モジュール40と、CO除去モジュール65とを備える。CO除去モジュール65は、CO除去反応が行なわれる反応容器61と、その内部にCOメタン化触媒(例えばRu系触媒)62とから構成される。また、水素製造装置60は、水素分離モジュール40の近傍に原料ガス50の水蒸気改質反応を起こすための発熱体53を、CO除去モジュール65の近傍にCO除去反応を起こすための発熱体63を更に備える。CO除去モジュール65は連結管54を介して連結継手48を用いて水素分離モジュール40に連結されている。水素分離モジュール40により生成された水素ガスは連結管54を通じてCO除去モジュール65に導入され、CO除去反応に供されることとなる。こうしてより高純度化された水素ガスは排出口64から取り出される。
図6に示す水素製造装置70は、複数個の水素分離モジュール40と、PSA法を適用した水素高純度化モジュール(PSAユニット)75とを備える。各々の水素分離モジュール40は、その水素分離材料20における水素排出部分(不図示)が連結管71を介してPSAユニット75に連結されている。複数の水素分離モジュール40の近傍にはパネル状の発熱体(点線で示す)72が設置されており、水蒸気改質反応を生起する。生成した水素ガスは連結管71を通じてPSAユニット75に導入された後、水素以外のガス成分が除去されることで高純度の水素ガスが製造される。
外径10mm、厚み1mm、長さ300mmの一端封じ多孔質アルミナまたは多孔質ジルコニア管の支持体表面にゾルゲル法を用いて、厚み50nmのシリカガラス膜を形成した。これらの複合構造体を、耐熱衝撃性の確認のため、電気炉にて500℃に加熱し、30℃の水中にすばやく落下(水中落下試験)させたところ、複合構造体は破断した。
カーボンコートした一端封じアルミナ管に、外付けCVD法を用いて表1に記載の組成(mol%)の多孔質ガラスを堆積し、ダミー棒を引抜くことで、外径10mm、厚み1mm、長さ300mmの一端封じ多孔質ガラスを作製した。この多孔質ガラスの表面にゾルゲル法を用いて、厚み50nmのシリカガラス膜を形成した。この複合構造体を電気炉にて500℃に加熱し、30℃の水中にすばやく落下させたところ、複合構造体が破断することはなかったが、電子顕微鏡観察によりシリカガラス膜にクラックが形成されていることを確認した。
カーボンコートした一端封じアルミナ管に、外付けCVD法を用いて表1に記載の組成(mol%)の多孔質ガラスを堆積し、ダミー棒を引抜くことで、外径10mm、厚み1mm、長さ300mmの一端封じ多孔質ガラスを作製した。この多孔質ガラスの表面にゾルゲル法を用いて、厚み50nmのシリカガラス膜を形成した。これらの複合構造体を電気炉にて500℃に加熱し、30℃の水中にすばやく落下させたところ、複合構造体の破断やシリカガラス膜のクラック形成は観察されなかった。
カーボンコートした一端封じアルミナ管に、外付けCVD法を用いて多孔質シリカガラスを堆積させた。次にCO2レーザーをこの多孔質シリカガラスの表面に照射し、厚さ1ミクロンのシリカガラス緻密膜を形成させた。この複合構造体からダミー棒を引き抜き、外径16mm、厚み1.5mm、長さ300mm、気孔率40%、線熱膨張係数0.7×10-6/Kの管状の水素分離材料を作製した。この水素分離材料の外側に0.2MPaGの50%H2‐50%N2ガスを供給したところ、水素分離材料の内側に透過した大気圧のガスの水素濃度は99%以上であり、550℃の水素透過係数は4×10-7mol・m-2・s-1・Pa-1であった。また、この水素分離材料の外側を0.2MPaG、600℃の水蒸気に120時間暴露した後、その表面を電子顕微鏡で観察したところ、ごく小面積の変質層が認められたものの、クラックなどの欠陥は観察されなかった。
カーボンコートした一端封じアルミナ管に、外付けCVD法を用いて多孔質シリカガラスを堆積させた。次にプラズマアークをこの多孔体の表面に照射し、厚さ20ミクロンのシリカガラス緻密膜を形成させた。この複合構造体からダミー棒を引き抜き、外径10mm、厚み1mm、長さ300mm、気孔率68%、線熱膨張係数0.7×10-6/Kの管状の水素分離材料を作製した。この水素分離材料の外側に0.2MPaGの50%H2-50%N2ガスを供給したところ、水素分離材料の内側に透過した大気圧のガスの水素濃度は99%以上であり、550℃の水素透過係数は0.3×10-7mol・m-2・s-1・Pa-1であった。
カーボンコートした一端封じアルミナ管に、外付けCVD法を用いて多孔質シリカガラスを堆積させた。次に酸水素バーナー火炎をこの多孔体の表面に照射し、厚さ40ミクロンのシリカガラス緻密膜を形成させた。この複合構造体からダミー棒を引き抜き、外径16mm、厚み4mm、長さ300mm、気孔率22%、線熱膨張係数0.7×10-6/Kの管状の水素分離材料を作製した。この水素分離材料の外側に0.2MPaGの50%H2‐50%N2ガスを供給したところ、水素分離材料の内側に透過した大気圧のガスの水素濃度は99%以上であり、550℃の水素透過係数は0.05×10-7mol・m-2・s-1・Pa-1であった。
カーボンコートした一端封じアルミナ管に、外付けCVD法を用いてそれぞれ1000ppmのY、Al、Ti、Gaを添加した4種類の多孔質シリカガラスを堆積させた。次にCO2レーザーをこの多孔体の表面に照射し、厚さ3ミクロンのシリカガラス緻密膜を形成させた。この複合構造体からダミー棒を引き抜き、外径16mm、厚み1.5mm、長さ300mm、気孔率40%、線熱膨張係数0.7×10-6/Kの管状の水素分離材料を作製した。この水素分離材料の外側に0.2MPaGの50%H2‐50%N2ガスを供給したところ、水素分離材料の内側に透過した大気圧のガスの水素濃度はいずれも99%以上であり、550℃の水素透過係数は1×10-7mol・m-2・s-1・Pa-1であった。また、この管状の水素分離材料の外側を0.2MPaG、600℃の水蒸気に120時間暴露した後、その表面を電子顕微鏡で観察したが、変質層やクラックなどの欠陥は観察されなかった。
図5に示したように、実施例9の管状の水素分離材料と市販のRu系改質触媒を備えた水素分離モジュールの反応容器にH2O/CH4=3の原料ガスを供給し、温度550℃、圧力0.5MPaGで水蒸気改質を行った。管状の水素分離材料の内側に透過したガスの水素濃度は99%以上、一酸化炭素濃度はおよそ500ppmであり、水素製造速度は0.02Nm3/hであった。また、このガスを市販のRu系COメタン化触媒を備えたCO除去モジュールを通過させた後の一酸化炭素濃度は10ppm以下であった。
実施例9の管状の水素分離材料と市販のRu系改質触媒を備えた水素分離モジュール52台を図6に示したように連結した。全モジュールの反応容器にH2O/CH4=3の原料ガスを供給し、温度550℃、圧力0.5MPaGで水蒸気改質を行った。水素分離材料の内側に透過したガスの水素濃度は99%以上、一酸化炭素濃度はおよそ500ppmであり、水素製造速度は1Nm3/hであった。また、このガスを市販のPSA型水素精製器を用いて精製した後の水素濃度は99.99%以上であり、一酸化炭素濃度は1ppm以下であった。
なお、本出願は、2009年12月11日付で出願された日本特許出願(特願2009-282210)に基づいており、その全体が引用により援用される。また、ここに引用されるすべての参照は全体として取り込まれる。
Claims (20)
- 線熱膨張係数が2×10-6/K以下の多孔質支持体上に、シリカガラス膜を形成した水素分離材料。
- 前記多孔質支持体が多孔質シリカガラスである請求項1に記載の水素分離材料。
- 形状が管状である請求項2に記載の水素分離材料。
- 前記多孔質シリカガラス及び/又は前記シリカガラス膜に希土類元素、4B族元素、Al及びGaから選択される少なくとも1種の元素が添加された請求項2又は3に記載の水素分離材料。
- 前記多孔質シリカガラスからなる多孔質支持体を表面改質して緻密化することで、前記多孔質シリカガラスからなる多孔質支持体上に前記シリカガラス膜を形成した請求項2~4の何れか一項に記載の水素分離材料。
- 前記表面改質が、CO2レーザー、プラズマアーク及び酸水素バーナーから選択される少なくとも1種を照射して前記多孔質シリカガラスの表面を緻密化する処理である請求項2~5の何れか一項に記載の水素分離材料。
- 多孔質シリカガラスからなる多孔質支持体を形成する多孔質支持体形成工程と、前記多孔質シリカガラスの表面にシリカガラス膜を形成するシリカガラス膜形成工程と、を有する水素分離材料の製造方法。
- 前記多孔質支持体形成工程は、ダミー棒の周囲に多孔質シリカガラスを堆積させ、その後、前記ダミー棒を引き抜いて多孔質シリカガラスからなる管状の多孔質支持体を形成する工程である請求項7に記載の水素分離材料の製造方法。
- 前記多孔質支持体形成工程は、ダミー棒の周囲に希土類元素、4B族元素、Al及びGaから選択される少なくとも1種の元素が添加された多孔質シリカガラスを堆積させ、その後、前記ダミー棒を引き抜いて多孔質シリカガラスからなる管状の多孔質支持体を形成する工程である請求項8に記載の水素分離材料の製造方法。
- 前記多孔質シリカガラスからなる多孔質支持体を形成する多孔質支持体形成工程と、前記多孔質シリカガラスの表面を緻密化して緻密質のシリカガラス膜を形成するシリカガラス膜形成工程と、を有する請求項7~9の何れか一項に記載の水素分離材料の製造方法。
- 前記シリカガラス膜形成工程が、CO2レーザー、プラズマアーク及び酸水素バーナーから選択される少なくとも1種を照射して前記多孔質シリカガラスの表面を緻密化する工程である請求項10に記載の水素分離材料の製造方法。
- 請求項7~11の何れか一項に記載の方法により得られる水素分離材料。
- 前記多孔質支持体の気孔率が20~70%である請求項1~6及び12の何れか一項に記載の水素分離材料。
- 前記多孔質支持体の厚みが0.2~5mmである請求項1~6、12及び13の何れか一項に記載の水素分離材料。
- 前記シリカガラス膜の厚みが0.01~50μmである請求項1~6及び12~14の何れか一項に記載の水素分離材料。
- 請求項1~6及び12~15の何れか一項に記載の水素分離材料と、水蒸気改質触媒と、を備えた水素分離モジュール。
- 請求項16記載の水素分離モジュールを備えた水素製造装置。
- 請求項16記載の水素分離モジュールとCO除去モジュールとを備えた水素製造装置。
- 前記CO除去モジュールがCOメタン化触媒を備えた請求項18に記載の水素製造装置。
- 請求項16記載の水素分離モジュールと圧力スウィング吸着(PSA)法を適用した水素高純度化モジュールとを備えた水素製造装置。
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JP2013022553A (ja) * | 2011-07-25 | 2013-02-04 | Sumitomo Electric Ind Ltd | 流体分離材料及びその製造方法 |
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 |
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US10222519B2 (en) * | 2016-03-10 | 2019-03-05 | Coorstek Kk | Composite silica glass made light diffusion member |
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- 2010-12-10 CA CA 2783961 patent/CA2783961A1/en not_active Abandoned
- 2010-12-10 CN CN201080056142XA patent/CN102652036A/zh active Pending
- 2010-12-10 WO PCT/JP2010/072201 patent/WO2011071138A1/ja active Application Filing
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013022553A (ja) * | 2011-07-25 | 2013-02-04 | Sumitomo Electric Ind Ltd | 流体分離材料及びその製造方法 |
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 |
CN117863707B (zh) * | 2024-03-11 | 2024-05-10 | 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 |
Also Published As
Publication number | Publication date |
---|---|
US9126151B2 (en) | 2015-09-08 |
EP2511005A4 (en) | 2016-11-16 |
CA2783961A1 (en) | 2011-06-16 |
CN102652036A (zh) | 2012-08-29 |
KR101880769B1 (ko) | 2018-07-20 |
JP5757243B2 (ja) | 2015-07-29 |
KR20120114261A (ko) | 2012-10-16 |
EP2511005B1 (en) | 2020-02-19 |
EP2511005A1 (en) | 2012-10-17 |
JPWO2011071138A1 (ja) | 2013-04-22 |
US20130022509A1 (en) | 2013-01-24 |
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