JP5363121B2 - 水素透過膜、及びその製造方法 - Google Patents
水素透過膜、及びその製造方法 Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 226
- 239000001257 hydrogen Substances 0.000 title claims description 218
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 218
- 239000012528 membrane Substances 0.000 title claims description 120
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 53
- 229910010293 ceramic material Inorganic materials 0.000 claims description 44
- 239000000919 ceramic Substances 0.000 claims description 43
- 239000000758 substrate Substances 0.000 claims description 40
- 239000002923 metal particle Substances 0.000 claims description 34
- 229910052751 metal Inorganic materials 0.000 claims description 32
- 239000002184 metal Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 19
- 238000004544 sputter deposition Methods 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 15
- 150000004767 nitrides Chemical class 0.000 claims description 14
- 229910045601 alloy Inorganic materials 0.000 claims description 10
- 239000000956 alloy Substances 0.000 claims description 10
- 239000010955 niobium Substances 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims 1
- 238000000927 vapour-phase epitaxy Methods 0.000 claims 1
- 238000001947 vapour-phase growth Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 55
- 239000007789 gas Substances 0.000 description 38
- 239000002245 particle Substances 0.000 description 31
- 230000035699 permeability Effects 0.000 description 20
- 239000000463 material Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000012466 permeate Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005546 reactive sputtering Methods 0.000 description 6
- 239000003566 sealing material Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005219 brazing Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241001422033 Thestylus Species 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- GPTXWRGISTZRIO-UHFFFAOYSA-N chlorquinaldol Chemical compound ClC1=CC(Cl)=C(O)C2=NC(C)=CC=C21 GPTXWRGISTZRIO-UHFFFAOYSA-N 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
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- B01D—SEPARATION
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- B01D71/02—Inorganic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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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
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Description
3 水素透過膜ユニット
11 水素透過性金属粒子
13 セラミックス材料
23 セラミックス基板
25 封止材
27 ステンレスホルダー
31 混合ガスセル
33 混合ガス注入口
35 混合ガス吸引口
37 混合ガス圧力センサー
41 透過ガスセル
43 透過ガスサンプリング口
45 透過ガス吸引口
47 透過ガス圧力センサー
本発明において、水素透過性金属粒子11は、パラジウム(Pd)、ニオブ(Nb)、バナジウム(V)、タンタル(Ta)又はこれらの合金の少なくとも1種からなる粒子である。これらの水素透過性金属粒子は、金属元素粒子としてセラミックス材料中に分散させても良く、合金粒子として分散させても良い。水素透過性金属の合金は、従来から水素透過膜の製造材料に用いられている合金である。水素透過性金属の合金としては、例えば、上記水素透過性金属とカルシウム、鉄、銅、バナジウム、ニッケル、チタン、クロム、ジルコニウム、銀等の金属との合金を挙げることができる。
水素透過膜1のマトリックスを構成するセラミックス材料3は、IVa、Va、VIa属金属元素の窒化物、又は酸化物が好ましい。セラミックス材料3の具体例としては、TiN0.3−2.5、ZrN0.3−2.5、HfN0.3−2.5、VN0.3−2.5、NbN0.3−2.5、TaN0.8−2、CrN0.5−3、MoN0.5−3、WN0.5−3等の窒化物や、TiO0.5−3、ZrO1−3、HfO1−3、VO0.5−3、NbO0.5−3、TaO1−3、CrO0.5−5、MoO1−4、WO1−4等の酸化物が挙げられる。
本発明の水素透過膜1は、その厚みが5〜1000nmで、10〜500nmが好ましい。この厚みが5nm未満の場合、水素透過膜の強度が不足する。一方、厚みが1000nmを超える場合、水素透過能が不十分となり、更に水素透過性金属の使用量の節約に起因するコスト低減効果も減少する。尚、水素透過性金属としてPdを用いる場合、Pdは水素ガスと他のガスとの分離能に優れるので、透過膜の厚みを特に薄くすることができる。
多孔性セラミックス基板23の表裏間は、基板内部に存在する細孔を通して、ガスが透過できる。本発明において使用する多孔性セラミックス基板は、通常市販されている多孔性セラミックスを用いることができる。多孔性セラミックス基板に存在する細孔は、孔径1〜200nmであることが好ましく、5〜100nmがより好ましい。この孔径が1nm未満であると、水素の透過能が不十分となる。一方、200nmを超えると、水素ガスとその他のガス(例えば窒素ガス)との分離性能が不十分になることがある。尚、多孔性セラミックス基板の表裏間は、連続した細孔が形成されていることが好ましい。
本発明の水素透過膜は、多孔性セラミックス基板23の少なくとも片面に、セラミックス材料と、前記セラミックス材料の内部に分散する水素透過性金属又はその合金粒子と、からなる薄膜を成膜することにより得られる。成膜は、セラミックス材料と水素透過性金属とを、同時に気相成長させる方法、又はスパッタリング法によることが好ましい。
3元高周波マグネトロンスパッタリング装置を用い、多孔性セラミックス基板上に水素透過膜を形成した。形成した水素透過膜はTaN−Pd系である。
Ta及びPdターゲットを同時にスパッタする反応スパッタにより、ガラス基板上にTaN0.8−2からなるマトリックス中にPd粒子を分散する、膜厚100nmの水素透過膜を成膜した。気圧9.31×10−1Pa、基板温度は200℃に設定した。スパッタリング装置内に導入したアルゴンガスと窒素ガスの容積比は40:60、ターゲットの出力はTa:Pd=160W:35Wとした。成膜した水素透過膜におけるPd粒子の含有量は45質量%であった。
HfO2及びPdターゲットを同時にスパッタする反応スパッタにより、ガラス基板上にHfO1−3からなるマトリックスにPd粒子を分散する、膜厚100nmの水素透過膜を成膜した。スパッタリング装置内は真空(1Pa以下)、ターゲットの出力はHfO2:Pd=220W:40Wとした。成膜した水素透過膜におけるPd粒子の含有量は35質量%であった。
Al及びPdターゲットを同時スパッタする反応スパッタにより、ガラス基板上に、AlN0.5−1.5からなるマトリックスにPd粒子を分散する水素透過膜を成膜した。スパッタリング装置内の気圧9.31×10−1Pa、基板温度は200℃に設定した。スパッタリング装置内に導入したアルゴンガスと窒素ガスの容積比は70:30、ターゲットの出力はAl:Pd=150W:30Wとした。成膜した水素透過膜におけるPd粒子の含有量は30質量%であった。
水素透過膜の耐水性を調べるため、実施例2、3、比較例1で製造した水素透過膜を試料として用い、下記の沸騰水浸漬試験を行った。
Claims (7)
- 周期表の第4族、第5族、又は第6族に属する金属元素の窒化物又は酸化物からなるセラミックス材料と、前記セラミックス材料中に分散させてなるパラジウム(Pd)、ニオブ(Nb)、バナジウム(V)、タンタル(Ta)及びこれらの合金から選ばれる少なくとも1種の水素透過性金属粒子とを有する、気相成長させる方法、又はスパッタリング法によって成膜された水素透過膜であって、該水素透過膜中の水素透過性金属粒子の割合が20〜70質量%であり、該水素透過膜の厚みが5〜1000nmであることを特徴とする水素透過膜。
- 水素透過性金属が、Pd又はその合金である請求項1に記載の水素透過膜。
- 水素透過性金属粒子の形状が、不定形状又はアスペクト比1〜10の棒状である請求項1に記載の水素透過膜。
- 多孔性セラミックス基板の少なくとも片面上に請求項1に記載の水素透過膜を成膜した水素透過膜ユニット。
- 多孔性セラミックス基板が孔径1〜200nmの細孔を有する請求項4に記載の水素透過膜ユニット。
- 多孔性セラミックス基板の少なくとも片面上に気相成長法又はスパッタリング法により請求項1に記載の水素透過膜を成膜する水素透過膜の製造方法。
- 多孔性セラミックス基板が孔径1〜200nmの細孔を有する請求項6に記載の水素透過膜の製造方法。
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