KR100531130B1 - Preparation of composite palladium membranes using etching process of metal chlorides - Google Patents
Preparation of composite palladium membranes using etching process of metal chlorides Download PDFInfo
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- KR100531130B1 KR100531130B1 KR10-2003-0068298A KR20030068298A KR100531130B1 KR 100531130 B1 KR100531130 B1 KR 100531130B1 KR 20030068298 A KR20030068298 A KR 20030068298A KR 100531130 B1 KR100531130 B1 KR 100531130B1
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- Prior art keywords
- palladium
- composite membrane
- hydrogen gas
- palladium composite
- gas separation
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 217
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 109
- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 239000012528 membrane Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000005530 etching Methods 0.000 title claims abstract description 30
- 229910001510 metal chloride Inorganic materials 0.000 title claims abstract description 22
- 230000008569 process Effects 0.000 title abstract description 8
- 238000002360 preparation method Methods 0.000 title description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000926 separation method Methods 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 4
- 239000000956 alloy Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 239000010409 thin film Substances 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910003902 SiCl 4 Inorganic materials 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910007926 ZrCl Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 33
- 238000010438 heat treatment Methods 0.000 abstract description 13
- 230000007547 defect Effects 0.000 abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 10
- 239000002923 metal particle Substances 0.000 abstract description 9
- 239000010408 film Substances 0.000 description 23
- 229910001873 dinitrogen Inorganic materials 0.000 description 13
- 238000007772 electroless plating Methods 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000000151 deposition Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 101150003085 Pdcl gene Proteins 0.000 description 4
- 230000004913 activation Effects 0.000 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 description 3
- 229910001252 Pd alloy Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 238000005371 permeation separation Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
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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
- 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
- C01B3/505—Membranes containing palladium
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0083—Thermal after-treatment
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
- B01D71/022—Metals
-
- 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
Abstract
본 발명은 수소기체 분리용 팔라듐 복합막의 제조방법에 관한 것으로써, 보다 상세하게는 다공성 지지체에 팔라듐 또는 팔라듐을 포함하는 합금이 코팅된 팔라듐 복합막을 제조한 후 상기 팔라듐 복합막을 4가 금속염화물 용액으로 에칭한 후 열처리하는 후처리 공정을 수행함으로써 기존의 다양한 방법으로 제조된 팔라듐 복합막에서 발생할 수 있는 핀홀 등의 공통적인 결함으로 지적되던 지지체 표면에 코팅된 금속입자들간의 간극을 메워서 팔라듐 복합막의 치밀성이 높아짐에 따라 수소기체에 대한 선택성이 높아지게 되고 질소의 흐름이 최소화된 수소기체 분리용 팔라듐 복합막의 제조방법에 관한 것이다.The present invention relates to a method for producing a hydrogen gas separation palladium composite membrane, and more particularly, to prepare a palladium composite membrane coated with an alloy containing palladium or palladium on a porous support, the palladium composite membrane to a tetravalent metal chloride solution By performing a post-treatment process after etching and heat treatment, the gap between the metal particles coated on the surface of the support, which has been pointed out as a common defect such as pinholes, which may occur in conventional palladium composite films, is filled. The present invention relates to a method for preparing a hydrogen gas separation palladium composite membrane in which the selectivity to hydrogen gas is increased and the flow of nitrogen is minimized as the density increases.
Description
본 발명은 수소기체 분리용 팔라듐 복합막의 제조방법에 관한 것으로써, 보다 상세하게는 다공성 지지체에 팔라듐 또는 팔라듐을 포함하는 합금이 코팅된 팔라듐 복합막을 제조한 후 상기 팔라듐 복합막을 4가 금속염화물 용액으로 에칭한 후 열처리하는 후처리 공정을 수행함으로써 기존의 다양한 방법으로 제조된 팔라듐 복합막에서 발생할 수 있는 핀홀 등의 공통적인 결함으로 지적되던 지지체 표면에 코팅된 금속입자들간의 간극을 메워서 팔라듐 복합막의 치밀성이 높아짐에 따라 수소기체에 대한 선택성이 높아지게 되고 질소의 흐름이 최소화된 수소기체 분리용 팔라듐 복합막의 제조방법에 관한 것이다.The present invention relates to a method for producing a hydrogen gas separation palladium composite membrane, and more particularly, to prepare a palladium composite membrane coated with an alloy containing palladium or palladium on a porous support, the palladium composite membrane to a tetravalent metal chloride solution By performing a post-treatment process after etching and heat treatment, the gap between the metal particles coated on the surface of the support, which has been pointed out as a common defect such as pinholes, which may occur in conventional palladium composite films, is filled. The present invention relates to a method for preparing a hydrogen gas separation palladium composite membrane in which the selectivity to hydrogen gas is increased and the flow of nitrogen is minimized as the density increases.
일반적으로 팔라듐 금속막은 수소에 대한 투과 선택성이 우수하여 수소기체분리용 막으로 널리 알려져 있으며, 고순도의 수소 분리·정제 장치나 촉매 막반응기로 사용되고 있다. 그러나, 팔라듐은 귀금속으로서 가격이 비싸기 때문에 지지체 위에 박막으로 코팅하는 팔라듐 복합막의 형태로 제조하여 사용되고 있다. 즉, 상기한 팔라듐 복합막은 지지체 위에 팔라듐을 코팅하여 제조하는데, 이때 팔라듐 금속막의 두께를 30 ㎛ 이하로 아주 얇게 코팅함으로써 팔라듐 사용량을 대폭 줄일 수 있게 되고, 또한 선택투과층의 두께 감소에 따른 기체의 투과속도를 향상시킬 수 있는 잇점이 있다. Generally, palladium metal membranes are widely known as hydrogen gas separation membranes because of their excellent permeation selectivity to hydrogen, and are used as high-purity hydrogen separation / purification devices or catalytic membrane reactors. However, since palladium is expensive as a precious metal, it is manufactured and used in the form of a palladium composite membrane coated with a thin film on a support. That is, the palladium composite membrane is prepared by coating palladium on a support, wherein the thickness of the palladium metal film is very thin to 30 μm or less, thereby significantly reducing the amount of palladium used, and also reducing the thickness of the selective permeable layer. There is an advantage that can improve the transmission rate.
이와 같은 팔라듐 복합막의 제조방법으로는 무전해도금법(electroless plating), 화학증착법(chemical vapor deposition), 전기도금법(electrodepostion), 스퍼터링(sputtering), 고온 열분해법(spray pyrolysis) 및 용액 침적법(wet impregnation depostion) 등이 있으며, 박막에 요구되는 특성, 재질, 지지체의 성질에 따라 알맞은 방법을 선택하여 사용하고 있다. Such palladium composite membranes can be prepared by electroless plating, chemical vapor deposition, electrodepostion, sputtering, spray pyrolysis and wet impregnation. depostion), and appropriate methods are used depending on the properties, materials, and support properties required for thin films.
이때, 화학증착법은 코팅하고자 하는 금속을 진공 중에서 기상으로 가열 증발시켜 화학반응을 통하여 금속 또는 비금속 제품의 표면에 박막화하는 방법인데, 플라스틱이나 유리와 같은 부도체 위에도 아주 얇은 두께로 도금이 가능하나, 사용되는 화합물의 순도가 매우 높아야 하며, 까다로운 공정 및 조건이 요구되는 문제점을 갖고 있다. 전기 도금법은 지지체가 도체 물질인 경우에만 적용 가능하고 도금용액 중의 불순물은 금속과 함께 도금되어 박막의 형성과 특성에 영향을 미칠 수 있다. 스퍼터링법은 고에너지의 이온이 금속 타겟(target)를 때려 나온 금속 원자가 지지체에 증착되어 박막으로 이루어지는 방법으로써, 금속막의 생성이 빠르게 일어나며 두께의 조절이 용이하다는 장점은 있지만, 핀홀이 없는 막을 제조하기가 매우 어려운 문제점을 갖고 있다. 열 분해법은 금속 용융염이 고온의 기체 속으로 분사되어 열 분해되면서 금속산화물의 분말이 형성 및 박막화되는 방법이며, 용액 침적법은 지지체 표면에서 유기금속 전구체가 수소와 반응하여 형성된 금속 입자들이 지지체 표면에 침적되어 팔라듐계 복합막을 제조하는 것이다.At this time, the chemical vapor deposition is a method of thinning the metal to be coated on the surface of the metal or non-metallic product through a chemical reaction by heating and evaporating the metal to be vaporized in a vapor phase. The purity of the compound to be very high and has a problem that demanding processes and conditions are required. The electroplating method is applicable only when the support is a conductor material, and impurities in the plating solution may be plated together with the metal to affect the formation and properties of the thin film. Sputtering is a method of forming a thin film by depositing a metal atom in which high energy ions strike a metal target on a support, which has the advantage of rapid generation of metal film and easy control of thickness. Has a very difficult problem. Pyrolysis is a method in which metal molten salt is injected into a gas at a high temperature to thermally decompose and powder of metal oxide is formed and thinned. In solution deposition, metal particles formed by the reaction of an organometallic precursor with hydrogen on the surface of the support are supported. It is deposited to produce a palladium-based composite film.
한편 무전해 도금법은 전극이나 전기를 사용치 않고 선택적인 환원반응에 의해 금속염 용액으로부터 금속을 석출시켜 지지체 위에 코팅하는 방법인데, 지지체 막 내면이나 작은 구멍 내부까지 균일하게 도금되고, 세라믹과 같은 부도체에도 직접 코팅할 수 있으며, 그 제조방법이 비교적 간단하고 용이하며 저렴한 장치비용으로 팔라듐 복합막의 제조가 가능하다는 장점이 있어 팔라듐 복합막 제조에 많이 이용되고 있다. On the other hand, electroless plating is a method of depositing a metal from a metal salt solution and coating it on a support by a selective reduction reaction without using an electrode or electricity. It can be directly coated, its manufacturing method is relatively simple, easy and has the advantage of manufacturing a palladium composite film at a low device cost has been widely used in the manufacture of palladium composite film.
그러나, 팔라듐 복합막의 제조과정에서 지지체 위에 코팅되는 팔라듐 박막은 핀홀과 같은 결함이 발생할 수 있으며 이와 같은 결함은 기체에 대한 분리 선택도에 큰 영향을 미쳐 분리막 성능을 저하시킬 수 있다. 즉, 지지체 위의 팔라듐은 입자형태의 박막으로 코팅 또는 도금되는데, 이 입자들 사이에서 미세한 틈이나 서로 덩어리지는 현상으로 인하여 핀홀의 결함이 생길 수 있다. 이러한 결함은 제조조건의 확립에 따라 다소 줄일 수 있으나 팔라듐 입자들이 물리적인 결합력으로 이루어져 있기 때문에 근본적으로 팔라듐 입자들간의 결합력이 약하여 완전하게 결함을 제거하는데 한계가 있다. 또한 약한 결합력으로 인하여 결국 분리막의 내구성이 약화되고 이것은 막분리 성능의 저하로 연결될 수 있다.However, the palladium thin film coated on the support during the manufacturing process of the palladium composite membrane may cause defects such as pinholes, and such defects may greatly affect the separation selectivity for gas, thereby degrading the membrane performance. That is, the palladium on the support is coated or plated with a thin film in the form of particles, and pinhole defects may occur due to a small gap or agglomeration between the particles. These defects can be reduced somewhat according to the establishment of manufacturing conditions, but since the palladium particles are made of physical bonding force, the bonding strength between the palladium particles is fundamentally limited to completely remove the defect. In addition, due to the weak bonding force, the durability of the separator is eventually weakened, which may lead to a decrease in membrane separation performance.
공지된 기술로서는 질산 또는 그 혼합용액을 에칭제로서 팔라듐 분리막에 적용하여 분리막의 핀홀이나 결함을 제거할 수 있는 방법을 제시하고 있다[미국특허[US 6,419,728 B1]. 또한, 염화제2철 수용액을 호일(foil) 팔라듐막을 에칭하여 수소가스의 우수한 분리성능을 확보할 수 있다는 것이 알려져 있으며[국제 공개특허 WO 03/031037 A1], 이 밖에 염산(HCl)이나 불산(HF) 등도 금속물질에 에칭효과가 있어서 팔라듐 분리막의 에칭공정에 활용될 수 있음이 알려져 있다. As a known technique, a method of removing pinholes or defects of a separator by applying nitric acid or a mixed solution thereof to the palladium separator as an etchant is disclosed [US Pat. No. 6,419,728 B1]. In addition, it is known that the ferric chloride aqueous solution can be etched in a foil palladium film to ensure excellent separation performance of hydrogen gas [International Patent Publication WO 03/031037 A1], hydrochloric acid (HCl) or hydrofluoric acid ( HF) is also known to have an etching effect on the metal material can be used in the etching process of the palladium separator.
그러나 상기한 바와 같이 산이나 그 수용액을 사용하여 에칭을 수행할 경우에는 얼마간의 에칭효과는 있으나 그 정도가 상대적으로 약하기 때문에, 보다 강한 에칭효과를 얻기 위해서 고농도의 산용액을 사용하거나, 에칭공정을 여러번 반복 실시해야하는 문제점이 있다.However, as described above, when etching using an acid or an aqueous solution thereof, there is some etching effect, but the degree is relatively weak. Therefore, in order to obtain a stronger etching effect, a high concentration of an acid solution or an etching process is used. There is a problem that must be repeated several times.
따라서, 상기한 방법으로 제조되는 팔라듐 복합막에서 지지체 위에 코팅 또는 도금된 팔라듐 입자들간의 간극 또는 틈을 메움과 동시에 강한 결합력의 향상시킬 수 있는 제조방법의 개발이 필요하다. Therefore, there is a need for the development of a manufacturing method capable of improving the strong bonding force at the same time as filling the gap or gap between the palladium particles coated or plated on the support in the palladium composite film prepared by the above method.
이에 본 발명자들은 상기와 같은 기존의 팔라듐 복합막의 제조방법이 안고 있는 문제점을 해결하기 위해 노력하였으며, 기존의 다양한 방법으로 제조된 팔라듐 복합막을 4가 금속염화물을 이용하여 에칭함으로써 팔라듐 또는 팔라듐 합금 입자들 간의 간극 또는 핀홀이 메워질 수 있음을 알게되었다.Accordingly, the present inventors have endeavored to solve the problems of the conventional method of manufacturing a palladium composite film as described above, and palladium or palladium alloy particles by etching a palladium composite film prepared by various methods using tetravalent metal chloride. It has been found that the gap or pinhole of the liver may be filled.
또한, 상기한 4가 금속염화물을 이용한 에칭처리에 의하여 팔라듐 박막을 구성하는 금속 입자간의 연결이 증대되고 이를 다시 열처리함으로써 팔라듐 복합막의 치밀성 및 내구성이 높아지며, 지지체 위에 코팅된 팔라듐 박막의 안정성이 향상되어 수소기체에 대한 선택도가 증가되고, 질소기체의 투과속도가 적어짐을 알게 되어 본 발명을 완성하였다.In addition, the connection between the metal particles constituting the palladium thin film by the etching process using the tetravalent metal chloride is increased and heat treatment again to increase the density and durability of the palladium composite film, the stability of the palladium thin film coated on the support is improved The present invention was completed by increasing the selectivity for hydrogen gas and decreasing the permeation rate of nitrogen gas.
따라서, 본 발명은 질소기체에 대한 수소기체의 선택적인 분리투과능이 증가하며 질소기체의 흐름이 최소화되도록 하는 개선된 수소기체 분리용 팔라듐 복합막의 제조방법을 제공하는데 그 목적이 있다. Accordingly, an object of the present invention is to provide a method for producing an improved hydrogen gas separation palladium composite membrane for increasing the selective separation permeability of hydrogen gas to nitrogen gas and minimizing the flow of nitrogen gas.
본 발명은 다공성 지지체 표면을 팔라듐 박막으로 코팅하여 제조된 수소기체 분리용 팔라듐 복합막을 제조하는 방법에 있어서, 상기 제조된 팔라듐 복합막을 4가 금속염화물 용액으로 에칭한 후 300 ∼ 500 ℃ 범위에서 열처리하는 수소기체 분리용 팔라듐 복합막의 제조방법을 특징으로 한다.The present invention is a method for producing a hydrogen gas separation palladium composite membrane prepared by coating the surface of the porous support with a palladium thin film, the palladium composite membrane is etched with a tetravalent metal chloride solution and then heat-treated at 300 ~ 500 ℃ range It is characterized by a method for producing a hydrogen gas separation palladium composite membrane.
이와 같은 본 발명을 상세하게 설명하면 다음과 같다.The present invention will be described in detail as follows.
본 발명은 다공성 지지체에 팔라듐 또는 팔라듐을 포함하는 합금이 코팅된 팔라듐 복합막을 제조한 후 상기 팔라듐 복합막을 4가 금속염화물 용액으로 에칭한 후 열처리하는 후처리 공정을 포함하여 수소기체 분리용 팔라듐 복합막을 제조하는 방법이다. 본 발명에 의하면 기존의 다양한 방법으로 제조된 팔라듐 복합막에서 발생할 수 있는 핀홀 등의 공통적인 결함으로 지적되던 지지체 표면에 코팅된 금속입자들간의 간극을 메워서 팔라듐 복합막의 치밀성을 높일 수 있게되어 수소기체에 대한 선택성이 높아지게 되고 질소의 흐름이 최소화되는 효과를 나타낸다. 또한 상기한 에칭처리 이후 열처리에 의하여 팔라듐 복합막의 치밀성 및 수소기체 선택성 향상 뿐만 아니라 팔라듐 박막의 안정성이 높아져서 내구성이 향상되는 부가적인 효과도 기대할 수 있는 개선된 수소기체 분리용 팔라듐 복합막의 제조방법을 제공한다.The present invention provides a palladium composite membrane for hydrogen gas separation, including a post-treatment step of preparing a palladium composite membrane coated with an alloy including palladium or palladium on a porous support and then etching the palladium composite membrane with a tetravalent metal chloride solution. It is a method of manufacturing. According to the present invention, it is possible to increase the density of the palladium composite membrane by filling gaps between the metal particles coated on the surface of the support, which has been pointed out as a common defect such as pinholes that may occur in conventional palladium composite membranes manufactured by various methods. This increases the selectivity to gas and minimizes the flow of nitrogen. In addition, an improved method of preparing a palladium composite membrane for separation of hydrogen gas can be expected not only to improve the density and hydrogen gas selectivity of the palladium composite membrane by heat treatment after the etching treatment but also to increase the stability of the palladium thin film, thereby improving durability. do.
이하 본 발명의 수소기체 분리용 팔라듐 복합막의 제조방법을 편의상 현재 가장 많이 적용되고 있는 무전해 도금법에 적용하는 방법을 중심으로 하여 구체적으로 설명하겠으나, 본 발명이 무전해 도금법에만 적용되는 것은 아니며, 다양한 방법의 공지된 수소기체 분리용 팔라듐 복합막의 제조방법에 적용될 수 있다.Hereinafter, the method of manufacturing the hydrogen gas separation palladium composite membrane of the present invention will be described in detail with reference to the method of applying the electroless plating method which is currently most applied for convenience, but the present invention is not applied only to the electroless plating method. The method can be applied to a known method for preparing a palladium composite membrane for hydrogen gas separation.
다공성 지지체 위에 팔라듐을 박막으로 코팅시키는 무전해 도금법은 먼저 전구체인 금속화합물의 활성화(sensitization and activation)과정에 의해 다공성 지지체 위에 팔라듐 핵(seed)을 생성시키고, 그 후에 선택적인 환원반응에 의해 금속염 용액으로부터 금속을 석출시켜 본격적으로 팔라듐 박막을 형성시키는 과정으로 이루어진다.The electroless plating method of coating a thin film of palladium on the porous support first generates a palladium seed on the porous support by sensitization and activation of the precursor metal compound, and then a metal salt solution by selective reduction reaction. Precipitating a metal from the metal to form a palladium thin film in earnest.
팔라듐 복합막의 제조에 사용되는 다공성 지지체로는 0.01 ∼ 1.0 ㎛ 범위의 기공크기를 갖는 세라믹, 유리질 및 스텐레스 스틸 등을 사용할 수 있으며, 평판, 중공사막 및 튜브 등의 다양한 형태의 것을 사용할 수 있다. 상기한 다공성 지지체 중에서도 세라믹은 고온에서 내구성이 우수하여 복합막의 지지체로 널리 이용되고 있다. 또한, 사용되는 다공성 지지체에 있어, 그 기공크기가 0.01 ㎛ 미만이면 기공크기가 너무 작아 다공성 지지체로서의 역할이 어렵고, 1.0 ㎛를 초과하면 기공의 크기가 너무 커서 지지체 표면에 위에 팔라듐 금속을 균일하게 도금하기가 어렵고, 이에 따라 분리막의 결함이 발생할 수 있으므로, 가능한 기공크기가 0.01 ∼ 1.0 ㎛ 범위인 다공성 지지체를 사용하는 것이 바람직하다.As the porous support used in the preparation of the palladium composite membrane, ceramics, glass and stainless steel having a pore size in the range of 0.01 to 1.0 μm may be used, and various forms such as flat plates, hollow fiber membranes, and tubes may be used. Among the porous supports described above, ceramics have excellent durability at high temperatures and are widely used as supports for composite membranes. In addition, in the porous support used, if the pore size is less than 0.01 μm, the pore size is too small to serve as a porous support, and if it exceeds 1.0 μm, the pore size is so large that the palladium metal is uniformly plated on the support surface. Since it is difficult to do so and defects of the separator may occur, it is preferable to use a porous support having a pore size in the range of 0.01 to 1.0 μm.
상기한 다공성 지지체 위에 박막으로 코팅되는 금속은 팔라듐 단독 또는 팔라듐의 합금을 사용할 수 있는데, 이때 팔라듐 합금에 사용되는 금속으로는 은(Ag), 구리(Cu), 철(Fe), 티타늄(Ti), 이트륨(Y) 및 루테늄(Ru) 등 중에서 선택된 1 종 또는 그 이상을 사용할 수 있다. The metal coated with the thin film on the porous support may use palladium alone or an alloy of palladium, wherein the metal used for the palladium alloy is silver (Ag), copper (Cu), iron (Fe), and titanium (Ti). Or one or more selected from yttrium (Y) and ruthenium (Ru).
팔라듐 복합막을 제조하기 위해서는 우선 먼저 지지체를 SnCl2 의 수화물 및 산을 함유하는 증감제 용액과, PdCl2와 산 등을 함유하는 활성화 용액에 침적한 후에 증류수에 세척하는 과정을 약 10회 반복하면 흑갈색을 띠는 팔라듐의 핵(seed)이 다공성 지지체 위에 생성된다. 여기에 PdCl2, EDTA(에틸렌디아민테트라아세트산), NH4OH, N2H4, 산 등을 함유하는 무전해 도금용액으로 약 50 ℃ 정도의 온도에서 처리하면 하이드라진의 환원작용에 의해 금속이 석출되면서 다공성 지지체의 표면에 팔라듐이 도금되며, 상기한 무전해 도금 용액에 코팅하는 공정을 수회 반복실시하면 팔라듐을 다층으로 코팅할 수 있다.In order to prepare a palladium composite membrane, first, the support is immersed in a sensitizer solution containing a hydrate and an acid of SnCl 2 , an activation solution containing PdCl 2 and an acid, and then washed in distilled water for about 10 times. Seeds of palladium are formed on the porous support. In addition, an electroless plating solution containing PdCl 2 , EDTA (ethylenediaminetetraacetic acid), NH 4 OH, N 2 H 4 , acid, etc., is treated at a temperature of about 50 ° C. to precipitate metals due to reduction of hydrazine. While palladium is plated on the surface of the porous support, the palladium may be coated in multiple layers by repeatedly performing the coating process on the electroless plating solution.
본 발명의 수소기체 분리용 팔라듐 복합막의 제조방법에 있어서 가장 특징적인 부분은 다공성 지지체 위에 팔라듐 박막이 코팅된 팔라듐 복합막을 4가 금속염화물 용액으로 에칭한 다음 열처리하는 공정이다. The most characteristic part of the method for preparing a hydrogen gas separation palladium composite membrane of the present invention is a step of etching a palladium composite membrane coated with a tetravalent metal chloride solution on a porous support with a tetravalent metal chloride solution followed by heat treatment.
본 발명에서 팔라듐 복합막을 에칭시에 사용하는 4가 금속염화물의 용액은 4가 금속의 염화물이 물 또는 알코올에 용해된 것으로서, 상기한 4가 금속염화물의 구체적인 예를 들면, TiCl4, VCl4, SnCl4, PtCl4, SeCl4 , SiCl4, TeCl4, WCl4 및 ZrCl4 등이 있다. 상기한 4가 금속염화물 용액은 저온, 바람직하게는 5 ℃ 이하의 저온에서 물 또는 알코올을 용매로 하여 0.05 ∼ 0.8 몰농도 범위인 것을 사용하는데, 바람직하기로는 0.1 ∼0.2 몰농도인 것을 사용하는 것이 좋다. 이때, 상기한 금속염화물 용액의 몰농도가 0.05 미만이거나 0.8을 초과할 경우에는 에칭효과가 없거나 과하여 팔라듐 복합막의 성능을 개선할 수 없거나 악화시킬 수 있다.In the present invention, the solution of the tetravalent metal chloride used for etching the palladium composite film is a chloride of the tetravalent metal dissolved in water or alcohol. Specific examples of the tetravalent metal chloride described above include TiCl 4 , VCl 4 , SnCl 4 , PtCl 4 , SeCl 4 , SiCl 4 , TeCl 4 , WCl 4 and ZrCl 4 . The tetravalent metal chloride solution described above is used in the range of 0.05 to 0.8 molar concentration using water or alcohol as a solvent at low temperature, preferably 5 ° C. or lower, and preferably in the range of 0.1 to 0.2 molar concentration. good. At this time, when the molar concentration of the metal chloride solution is less than 0.05 or more than 0.8, there is no etching effect or excessive performance may not improve or worsen the performance of the palladium composite film.
상기와 같이 제조된 4가 금속염화물 용액에 팔라듐 복합막을 함침(dipping)하여 에칭하는데, 이때 에칭시 온도는 상온일 경우가 특히 바람직하다. 에칭 시간은 5 ∼ 60 분 범위 내에서 가능하나, 바람직하기로는 10 ∼ 20 분이 좋은데, 이때 에칭시간이 너무 짧거나 너무 길면 에칭효과가 없거나 과하여 분리막 성능이 악화될 수 있다. The palladium composite film is immersed in the tetravalent metal chloride solution prepared as described above and then etched, wherein the etching temperature is particularly preferably at room temperature. Etching time is possible within the range of 5 to 60 minutes, preferably 10 to 20 minutes, but if the etching time is too short or too long, there is no etching effect or excessive separator performance may deteriorate.
상기와 같이 4가 금속염화물 용맥으로 에칭한 다음 세척하고, 세척이 완료된 후 300 ∼ 500 ℃에서 증기를 이용하여 2 ∼ 24 시간동안 열처리한다. 이때, 증기 열처리의 온도가 300 ℃ 미만이거나, 500 ℃를 초과하면 열처리 효과를 기대할 수 없으며, 열처리 시간이 상기 범위내에서 처리하는 것이 내구성 향상에 효과적이다.As described above, the tetravalent metal chloride is etched and then washed. After the washing is completed, heat treatment is performed at 300 to 500 ° C. for 2 to 24 hours using steam. At this time, if the temperature of the steam heat treatment is less than 300 ℃ or more than 500 ℃ can not be expected the heat treatment effect, it is effective to improve the durability that the heat treatment time treatment within the above range.
이와 같은 에칭 및 증기 열처리를 통하여 제조된 본 발명의 에칭된 팔라듐 복합막은 다공성 지지체 위에 코팅된 금속 입자들 간의 간극 또는 핀홀 등의 결함이 메워지고 각 금속 입자들간의 결합이 강해져서, 박막의 치밀도가 높아지게 되어 수소기체에 대한 선택적인 분리투과능이 우수하면서 열적 안정성을 나타내며, 오랜 시간동안 분리막의 물성이 유지되는 내구성을 나타낸다. The etched palladium composite membrane of the present invention prepared through such etching and steam heat treatment fills gaps or pinholes between the metal particles coated on the porous support, and bonds between the metal particles become stronger, thereby increasing the density of the thin film. The high permeability and the selective separation permeability for hydrogen gas shows the thermal stability, and shows the durability of maintaining the properties of the membrane for a long time.
이하, 실시예에 의하여 본 발명을 보다 구체적으로 설명하겠는바, 다음 실시예에 의하여 본 발명이 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.
실시예 1Example 1
0.02 ㎛ 기공크기를 가지는 다공성 α-알루미나 지지체 튜브(외경 10 ㎜, 내경 6.7 ㎜, 길이 120 ㎜)를 다음 표 1과 같은 조성을 갖는 증감제(20 ㎖)와 활성화(20 ㎖) 용액에 각각 5 분동안 침적과 세척을 10회 정도 반복하여 세라믹 막 표면에 팔라듐 핵(seed)을 생성시켰다. 핵이 생성된 상기 세라믹 지지체막을 50 ℃에서 1시간 동안 20 ㎖의 다음 표 1의 조성을 갖는 무전해 도금용액에 침적하여 팔라듐 박막이 도금된 팔라듐 복합막을 다량의 증류수로 중성이 유지할 때까지 세척한 후 건조하여 10 ∼ 30 ㎛ 두께를 갖는 팔라듐 복합막을 제조하였다.A porous α-alumina support tube having a pore size of 0.02 μm (outer diameter of 10 mm, inner diameter of 6.7 mm, length of 120 mm) was added to the sensitizer (20 ml) and activation (20 ml) solutions having the composition shown in Table 1, respectively, for 5 minutes. Deposition and washing were repeated about 10 times to generate palladium seed on the ceramic film surface. The nucleated ceramic support membrane was immersed in an electroless plating solution having a composition of 20 ml at 20 ° C. for 1 hour at 50 ° C., and the palladium composite membrane plated with the palladium thin film was washed with a large amount of distilled water until neutrality was maintained. It dried to prepare a palladium composite membrane having a thickness of 10 to 30 ㎛.
상기 제조된 팔라듐 복합막을 티타늄테트라클로라이드(TiCl4) 0.2 몰 농도의 수용액(20 ㎖)에 20 분간 함침하여 에칭한 후에 탈이온화수에서 pH가 7 ∼ 8이 될 때까지 세척하고, 이를 모듈에 장착하여 350 ℃에서 약 8 시간 동안 증기로 열처리를 수행하여 에칭된 팔라듐 복합막을 제조하였다.The prepared palladium composite membrane was immersed in an aqueous solution (20 ml) of 0.2 mol concentration of titanium tetrachloride (TiCl 4 ) for 20 minutes and then etched in deionized water until the pH was 7 to 8, and then mounted on the module. Heat-treated with steam at 350 ° C. for about 8 hours to prepare an etched palladium composite membrane.
열처리 후 질소기체와 수소기체의 투과도를 400 ℃, 0.05 기압에서 측정한 결과, 질소가스에 대한 수소기체의 선택도는 36.9 이었고, 수소의 투과속도는 1.94 cc/min·㎠이었다.After the heat treatment, the permeability of nitrogen gas and hydrogen gas was measured at 400 ° C. and 0.05 atm. As a result, the selectivity of hydrogen gas to nitrogen gas was 36.9, and the permeation rate of hydrogen was 1.94 cc / min · cm 2.
실시예 2Example 2
상기 실시예 1과 동일한 방법으로 팔라듐 복합막을 제조하되, 에칭시 틴클로라이드(SnCl4) 0.2 몰농도의 수용액(20 ㎖)을 사용하였으며, 침적시간은 20 분으로 달리하였다. 에칭된 팔라듐 복합막의 분리투과성능을 300 ℃, 0.25 기압에서 측정한 결과 질소기체에 대한 수소기체의 선택도는 191.1이었고, 수소의 투과속도는 227.5 ㎤/min·㎠ 이었다.A palladium composite film was prepared in the same manner as in Example 1, but an aqueous solution (20 ml) of 0.2 mol of tin chloride (SnCl 4 ) was used during etching, and the deposition time was changed to 20 minutes. The separation permeability of the etched palladium composite membrane was measured at 300 ° C. and 0.25 atmosphere, and the selectivity of hydrogen gas to nitrogen gas was 191.1, and the permeation rate of hydrogen was 227.5 cm 3 / min · cm 2.
실시예 3 Example 3
상기 실시예 1과 동일한 방법으로 팔라듐 복합막을 제조하되, 에칭시 바나듐클로라이드(VCl4) 0.2 몰농도의 수용액(20 ㎖)을 사용하였으며, 침적시간은 20 분 수행하였다. 에칭된 팔라듐 복합막의 분리투과성능을 300 ℃, 0.1 기압에서 측정한 결과 질소기체에 대한 수소기체의 선택도는 21.2이었고 수소의 투과속도는 1.0 ㎤/min·㎠이었다.A palladium composite film was prepared in the same manner as in Example 1, but an aqueous solution (20 ml) of 0.2 mol of vanadium chloride (VCl 4 ) was used for etching, and a deposition time was performed for 20 minutes. The separation performance of the etched palladium composite membrane was measured at 300 ° C. and 0.1 atm. As a result, the selectivity of hydrogen gas to nitrogen gas was 21.2 and the permeation rate of hydrogen was 1.0 cm 3 / min · cm 2.
비교예 1Comparative Example 1
상기 실시예 1과 동일한 방법으로 팔라듐 복합막을 제조하되, 에칭 및 열처리 공정은 수행하지 않았다. 제조된 팔라듐 복합막의 분리투과 성능을 300 ℃, 0.25 기압에서 측정한 결과 질소기체에 대한 수소기체의 선택도는 3.1이었고 질소의 투과속도는 118.8 ㎤/min·㎠ 이었다. A palladium composite film was manufactured in the same manner as in Example 1, but the etching and heat treatment processes were not performed. The separation permeability of the prepared palladium composite membrane was measured at 300 ° C. and 0.25 atm. As a result, the selectivity of hydrogen gas to nitrogen gas was 3.1 and the permeation rate of nitrogen was 118.8 cm 3 / min · cm 2.
비교예 2Comparative Example 2
상기 실시예 1과 동일한 방법으로 팔라듐 복합막을 제조하되, 에칭시 티타늄테트라클로라이드 1.0 몰농도의 수용액(20 ㎖)을 사용하여 2 시간 동안 에칭하였다. 에칭된 팔라듐 복합막을 390 ℃, 0.25 기압에서 분리성능을 측정한 결과 질소기체에 대한 수소기체의 선택도는 2.9 이었고 질소의 투과속도는 107.4 ㎤/min·㎠ 이었다.A palladium composite film was prepared in the same manner as in Example 1, but was etched for 2 hours using an aqueous solution (20 mL) of 1.0 mol of titanium tetrachloride. Separation performance of the etched palladium composite membrane was measured at 390 ° C. and 0.25 atm. As a result, the selectivity of hydrogen gas to nitrogen gas was 2.9 and the permeation rate of nitrogen was 107.4 cm 3 / min · cm 2.
비교예 3Comparative Example 3
상기 실시예 1과 동일한 방법으로 팔라듐 복합막을 제조하되, 에칭시 0.2 몰 염산(HCl) 수용액에 1시간 동안 침적하였다. 에칭된 팔라듐 복합막을 420 ℃, 0.15 기압에서 수소기체와 질소기체의 투과분리성능을 측정한 결과 질소기체에 대한 수소기체의 선택도는 2.9이었고, 질소의 투과속도는 127.2 ㎤/min·㎠이었다. A palladium composite film was prepared in the same manner as in Example 1, but was immersed in an aqueous 0.2 mol hydrochloric acid (HCl) solution for 1 hour during etching. As a result of measuring the permeation separation performance of hydrogen gas and nitrogen gas at 420 ° C. and 0.15 atm, the selectivity of hydrogen gas to nitrogen gas was 2.9, and the permeation rate of nitrogen was 127.2 cm 3 / min · cm 2.
상기 표 2에 나타낸 바와 같이,본 발명의 실시예 1 ∼ 3 에 따라 4가 금속염화물 용액으로 에칭된 팔라듐 복합막의 질소기체의 투과속도는 상대적으로 매우 낮아 질소에 대한 수소의 선택도가 높음을 알 수 있다. 즉, 본 발명에서 제시한 것과 같이 4가의 금속염화물을 이용하여 적절한 조건에서 에칭을 수행하면 에칭효과에 의해 금속입자들 사이의 공극(pinhole)이 메워지거나 결함이 제거되어 질소의 흐름이 최소화될 수 있으며, 그 결과로 에칭된 팔라듐 복합막의 질소에 대한 수소의 선택도가 대폭 향상될 수 있음을 알 수 있다. As shown in Table 2, the permeation rate of the nitrogen gas of the palladium composite membrane etched with the tetravalent metal chloride solution according to Examples 1 to 3 of the present invention is relatively very low, indicating that the selectivity of hydrogen to nitrogen is high. Can be. In other words, if etching is performed under appropriate conditions using tetravalent metal chlorides, as described in the present invention, the voids between the metal particles may be filled or defects may be removed by the etching effect, thereby minimizing the flow of nitrogen. As a result, it can be seen that the selectivity of hydrogen to nitrogen of the etched palladium composite film can be significantly improved.
이러한 에칭효과는 무전해 도금법에만 한정되지 않고 화학증착법, 전기도금법, 스퍼터링법, 고온열분해법, 용액침적법 등에 의해 제조된 팔라듐 복합막에도 적용할 수 있다.This etching effect is not limited to the electroless plating method, but can also be applied to palladium composite films produced by chemical vapor deposition, electroplating, sputtering, high temperature pyrolysis, solution deposition, and the like.
이상에서 설명한 바와 같이, 다공성 세라믹 지지체 위에 팔라듐 박막으로 도금하여 팔라듐 복합막을 제조한후 금속염화물로 에칭 및 열처리하는 후처리 방법을 도입함으로써, 팔라듐 박막의 금속 입자들간의 공극 또는 핀홀을 메워주고 결합력을 증대시켜 질소기체에 대한 수소기체의 선택도를 크게 향상시켰다. As described above, by preparing a palladium composite film by plating a palladium thin film on a porous ceramic support and then introducing a post-treatment method of etching and heat-treating with a metal chloride, it fills the voids or pinholes between the metal particles of the palladium thin film and bond strength The increase greatly increased the selectivity of hydrogen gas to nitrogen gas.
본 발명의 수소기체 분리용 팔라듐 복합막의 제조방법은 기존의 팔라듐 복합막의 제조공의 후처리로써 충분히 용이하게 적용할 수 있으며, 이로써 제조된 에칭된 팔라듐 복합막은 고순도 수소 제조를 위한 수소 분리·정제 분야나 촉매 반응기 등에 적용되어 대폭적인 반응효율 향상 및 에너지 절약이 가능하다. The method for producing a palladium composite membrane for separation of hydrogen gas of the present invention can be easily applied as a post-treatment of a conventional palladium composite membrane. The etched palladium composite membrane thus prepared is used in the field of hydrogen separation and purification for high purity hydrogen production. Applied to a catalytic reactor, it is possible to greatly improve reaction efficiency and save energy.
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| KR100622988B1 (en) * | 2004-08-20 | 2006-09-19 | 한국에너지기술연구원 | Preparation Method of Palladium Alloy Composite Membrane for Hydrogen Separation |
| KR100679341B1 (en) * | 2004-09-15 | 2007-02-07 | 한국에너지기술연구원 | Preparation Method of Palladium Alloy Composite Membrane for Hydrogen Separation |
| KR102377403B1 (en) | 2020-03-20 | 2022-03-22 | 주식회사 하이젠에너지 | Hollow fiber membrane and its manufacturing method |
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2003
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