JP2007517655A - 金属パラジウム複合膜又は合金パラジウム複合膜及びその製造方法 - Google Patents
金属パラジウム複合膜又は合金パラジウム複合膜及びその製造方法 Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 239000012528 membrane Substances 0.000 title claims abstract description 86
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 17
- 239000002184 metal Substances 0.000 title claims abstract description 17
- 229910045601 alloy Inorganic materials 0.000 title abstract description 9
- 239000000956 alloy Substances 0.000 title abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 91
- 239000011148 porous material Substances 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims abstract description 46
- 239000000945 filler Substances 0.000 claims abstract description 41
- 238000007747 plating Methods 0.000 claims abstract description 10
- 239000000084 colloidal system Substances 0.000 claims description 25
- 239000002244 precipitate Substances 0.000 claims description 20
- 239000000919 ceramic Substances 0.000 claims description 18
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 238000007772 electroless plating Methods 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 238000012805 post-processing Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- -1 sols Substances 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 101150003085 Pdcl gene Proteins 0.000 claims description 3
- 239000000499 gel Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000005373 porous glass Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 3
- 238000001035 drying Methods 0.000 claims 2
- 230000003213 activating effect Effects 0.000 claims 1
- 238000002144 chemical decomposition reaction Methods 0.000 claims 1
- 238000010924 continuous production Methods 0.000 claims 1
- 230000001235 sensitizing effect Effects 0.000 claims 1
- 239000000243 solution Substances 0.000 description 38
- 239000001257 hydrogen Substances 0.000 description 34
- 229910052739 hydrogen Inorganic materials 0.000 description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 230000004048 modification Effects 0.000 description 19
- 238000012986 modification Methods 0.000 description 19
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- 239000008279 sol Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000002715 modification method Methods 0.000 description 5
- 229910001316 Ag alloy Inorganic materials 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
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- 239000003607 modifier Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
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- 229910006636 γ-AlOOH Inorganic materials 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 229910002668 Pd-Cu Inorganic materials 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
Description
・修飾技術工程中に多孔性基質管又は状況に応じて基質表面の傷を先取りすることができ、
・製造中にパラジウムが孔隙内に侵入するのを防止する。
コロイド製造:硝酸アルミニウム溶液及び炭酸ナトリウム溶液を一つのビーカーに同時に滴下し、55℃、pH=8でアルカリ炭酸アルミナコロイドを得る。当該コロイドは、蒸留水で6回洗浄する。上記炭酸ナトリウム溶液が沈降分離装置としての炭酸カリウム溶液、アンモニア溶液、水酸化ナトリウム溶液、及び/又は水酸化カリウムにより置き換えられた場合、対応するコロイド又は沈殿物が得られる。
コロイド製造:実施例1と同一である。
修飾方法は、実施例1と同一である。後処理方法は、実施例1と同一である。
コロイド製造:硝酸セリウム溶液と炭酸ナトリウム溶液を一つのビーカーに同時に滴下して55℃、PH=9でアルカリ炭酸セリウムコロイドを得る。当該コロイドは、蒸留水で5回洗浄される。上記炭酸ナトリウム溶液を沈降分離装置としての炭酸カリウム溶液、アンモニア溶液、水酸化ナトリウム溶液及び/又は水酸化カリウム溶液に置き換えた場合、対応するコロイド又は沈殿物が得られる。
コロイド製造:CO2がCa(OH)2溶液に注入されてCaCO3沈殿物を形成し、当該沈殿物を蒸留水で5回洗浄処理する。
多孔性基質表面修飾:SB粉末から得られたγ-AlOOHゾルが表面孔隙充填剤となり、基質は、アルミナ多孔性セラミック管である。多孔性基質は、まず塩酸の薄い溶液と水酸化ナトリウムの薄い溶液で洗浄処理され、次に蒸留水で洗浄され、CCl4で洗浄処理されて乾燥される。洗浄処理されたアルミナ多孔性セラミック管は、真空状態で上記Alゾル溶液中に沈み、AlOOH粒子が真空状態で孔管及びアルミナ多孔性セラミック管の表面の傷に入る。支持体表面にある余剰表面孔隙充填剤は、次に機械的洗浄により取り除かれる。
コロイド製造:手順は、実施例3の手順と同一である。
多孔性基質表面修飾:多孔性γ-Al2O3が蒸留水中で懸濁し、基質はアルミナ多孔性セラミック管である。アルミナ多孔性セラミック管は、真空状態で上記懸濁液中に沈み、多孔性γ-Al2O3粒子が真空状態で孔管及びアルミナ多孔性セラミック管の表面の傷に入る。当該粒子は基質を修飾する。γ-Al2O3の代わりにCeO2、TiO2及びZrO2で表面修飾しても同様である。
多孔性基質表面修飾:基質は多孔性ステンレス鋼管である。表面修飾方法は、実施例7で示したものと同一である。
Claims (15)
- 多孔性基質支持体とパラジウム膜又はパラジウム合金膜とからなり、パラジウム金属が実質的に多孔性基質支持体の外側表面に存在し、基質の孔管内にはほとんど又は全く存在しないことを特徴とする二層金属パラジウム複合膜又はパラジウム合金複合膜。
- 多孔性基質支持体とパラジウム膜又はパラジウム合金膜とからなり、以下の連続的工程を特徴とする二層金属パラジウム複合膜又はパラジウム合金複合膜の製造方法において、
1)多孔性基質支持体を洗浄処理/洗浄及び乾燥する工程と、
2)孔隙充填剤で多孔性基質支持体を処理することにより当該支持体の孔隙と状況に応じて基質表面の傷を修飾する工程と、
3)状況に応じて、余剰の孔隙充填剤が基質支持体表面に存在する場合、基質支持体を洗浄することによりこの余剰の表面孔隙充填剤を取り除く工程と、
4)修飾された基質支持体をパラジウム溶液で感作して活性化する工程と、
5)得られた支持体をパラジウム溶液でメッキして二層複合膜を形成する工程と、
6)乾燥工程と、
7)状況に応じて、得られた複合膜を後処理して多孔性基質の孔管内にある孔隙充填剤を加熱又は物質的/化学的分解のいずれかにより取り除き又は減量する工程の連続工程からなる製造方法。 - 工程2を真空状態で実施し、好適には孔隙充填剤溶液中に多孔性基質を沈めて実施することにより、孔隙と状況に応じて基質の傷を充填剤で先取りして連続的な製造工程中に孔隙に侵入するパラジウムが存在しないよう確保することを特徴とする請求項2に記載の方法。
- 工程4において多孔性基質支持体がそれぞれSnCl2溶液で感作され、且つPdCl2溶液で活性化されることを特徴とする請求項2又は3のいずれかに記載の方法。
- 工程5において、多孔性基質を無電解メッキ溶液に沈めることを特徴とする請求項2乃至4のいずれかに記載の方法。
- 無電解メッキ溶液が[Pd(NH3)2]Cl2、EDTA・2Na、NH2-NH2・H2O、NH3・H2Oの典型的組成を具備することを特徴とする請求項5に記載の方法。
- 後処理工程7が必須であることを特徴とする請求項2乃至6のいずれかに記載の方法。
- 複合膜を乾燥し、次に少なくとも300℃で焼成することを特徴とする請求項7に記載の方法。
- 使用する孔隙充填剤が0.2ミクロン未満の粒径、好適には0.1ミクロン未満であり、より好ましくは0.05ミクロン未満であることを特徴とする請求項2乃至8のいずれかに記載の方法。
- 表面孔隙充填剤がゲル、ゾル、コロイド又は沈殿物の中から選択されることを特徴とする請求項2乃至9のいずれかに記載の方法。
- 孔隙充填剤がAlゾル、Siゾル、Tiゾル、Zrゾル及び/又はCeゾルの中から選択されることを特徴とする請求項10に記載の方法。
- 孔隙充填剤が水酸化コロイド、アルカリ炭酸塩コロイド及び/又は炭酸塩コロイドの中から選択されることを特徴とする請求項10に記載の方法。
- 孔隙充填剤が水酸化沈殿物、アルカリ炭酸塩沈殿物及び/又は炭酸塩沈殿物の中から選択されることを特徴とする請求項10に記載の方法。
- 請求項2乃至13のいずれかにより得られる二層金属パラジウム複合膜又はパラジウム合金複合膜。
- 多孔性基質支持体は、多孔性ステンレス鋼、多孔性ニッケル、多孔性ガラス、又は多孔性セラミックスという多孔性材料のうちの一つから選択されることを特徴とする請求項1又は14のいずれかに記載の複合膜又は、請求項2乃至13のいずれかに記載の製造方法。
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CNB2004100210256A CN1327942C (zh) | 2004-01-09 | 2004-01-09 | 一种复合金属钯膜或合金钯膜及其制备方法 |
PCT/GB2005/000041 WO2005065806A1 (en) | 2004-01-09 | 2005-01-07 | A metal palladium composite membrane or alloy palladium composite membrane and their preparation methods |
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Cited By (2)
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JP5891512B2 (ja) * | 2010-03-29 | 2016-03-23 | 国立研究開発法人産業技術総合研究所 | 多孔性フィルター、その製造方法、多孔性フィルターを支持体とする水素分離膜、欠陥の封止方法、及び水素分離方法 |
JP2016041420A (ja) * | 2014-08-13 | 2016-03-31 | ヨウル チョン ケミカル カンパニー, リミテッド | ポリベンズイミダゾール系高分子膜を支持体とするパラジウムメッキ分離膜及びその成膜方法 |
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JP5891512B2 (ja) * | 2010-03-29 | 2016-03-23 | 国立研究開発法人産業技術総合研究所 | 多孔性フィルター、その製造方法、多孔性フィルターを支持体とする水素分離膜、欠陥の封止方法、及び水素分離方法 |
JP2016041420A (ja) * | 2014-08-13 | 2016-03-31 | ヨウル チョン ケミカル カンパニー, リミテッド | ポリベンズイミダゾール系高分子膜を支持体とするパラジウムメッキ分離膜及びその成膜方法 |
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WO2005065806A1 (en) | 2005-07-21 |
ZA200605552B (en) | 2008-04-30 |
CN1640530A (zh) | 2005-07-20 |
CA2552485A1 (en) | 2005-07-21 |
KR20060121927A (ko) | 2006-11-29 |
SG149057A1 (en) | 2009-01-29 |
AU2005203910A1 (en) | 2005-07-21 |
EP1701779A1 (en) | 2006-09-20 |
BRPI0506744A (pt) | 2007-05-15 |
EA200601293A1 (ru) | 2007-04-27 |
MXPA06007876A (es) | 2007-03-01 |
DE602005022670D1 (de) | 2010-09-16 |
EP1701779B1 (en) | 2010-08-04 |
ATE476249T1 (de) | 2010-08-15 |
US20090130477A1 (en) | 2009-05-21 |
US8052775B2 (en) | 2011-11-08 |
EA011051B1 (ru) | 2008-12-30 |
TNSN06215A1 (en) | 2007-12-03 |
PL1701779T3 (pl) | 2011-05-31 |
UA92314C2 (ru) | 2010-10-25 |
AU2005203910B2 (en) | 2010-05-27 |
JP4528785B2 (ja) | 2010-08-18 |
ES2350356T3 (es) | 2011-01-21 |
CN1327942C (zh) | 2007-07-25 |
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