JPH07213877A - Inorganic xerogel film, its production and gas separating membrane made of the same - Google Patents
Inorganic xerogel film, its production and gas separating membrane made of the sameInfo
- Publication number
- JPH07213877A JPH07213877A JP3288594A JP3288594A JPH07213877A JP H07213877 A JPH07213877 A JP H07213877A JP 3288594 A JP3288594 A JP 3288594A JP 3288594 A JP3288594 A JP 3288594A JP H07213877 A JPH07213877 A JP H07213877A
- Authority
- JP
- Japan
- Prior art keywords
- film
- inorganic
- xerogel
- metal alkoxide
- inorg
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 23
- 239000011248 coating agent Substances 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 13
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 abstract description 16
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000005373 porous glass Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- KPAMAAOTLJSEAR-UHFFFAOYSA-N [N].O=C=O Chemical compound [N].O=C=O KPAMAAOTLJSEAR-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910001872 inorganic gas Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、無機キセロゲル膜およ
びその製造方法ならびに無機キセロゲル膜からなる気体
分離膜に関する。TECHNICAL FIELD The present invention relates to an inorganic xerogel membrane, a method for producing the same, and a gas separation membrane comprising the inorganic xerogel membrane.
【０００２】[0002]
【従来技術とその問題点】金属アルコキシドの溶液を無
機多孔体上に塗布し、６００℃程度の温度で焼成して、
無機キセロゲル膜を製造する方法は、公知である。しか
しながら、この様な公知の方法で得られる無機キセロゲ
ルにおいては、焼成中にゲルの二次粒子が発達し、粒間
空隙としての大きな細孔が形成されるので、均一な微小
細孔を有する構造的に連続した膜は得られない。2. Description of the Related Art A solution of a metal alkoxide is coated on an inorganic porous material and baked at a temperature of about 600.degree.
Methods for producing inorganic xerogel membranes are known. However, in the inorganic xerogel obtained by such a known method, secondary particles of the gel develop during firing and large pores are formed as intergranular voids, so that a structure having uniform micropores is formed. A continuous film cannot be obtained.
【０００３】[0003]
【発明が解決しようとする課題】従って、本発明は、均
一な微小細孔を有する構造的に連続した無機キセロゲル
膜を得ることを主な目的とする。SUMMARY OF THE INVENTION Accordingly, the main object of the present invention is to obtain a structurally continuous inorganic xerogel film having uniform micropores.
【０００４】[0004]
【課題を解決するための手段】本発明者は、従来技術の
問題点を解消乃至軽減するために、研究を重ねた結果、
金属アルコキシドの溶液を無機多孔体上に塗布して無機
キセロゲル膜を製造するに際し、塗膜を特定の条件で熟
成させる場合には、二次粒子の発生を抑制することが可
能となり、上記の目的を達成しうることを見出した。The present inventor has conducted extensive research in order to solve or alleviate the problems of the prior art.
When a solution of a metal alkoxide is applied onto an inorganic porous material to produce an inorganic xerogel film, if the coating film is aged under specific conditions, it becomes possible to suppress the generation of secondary particles, and the above-mentioned object. It has been found that
【０００５】即ち、本発明は、下記の無機キセロゲル膜
の製造方法およびそれにより得られる無機キセロゲル膜
を提供するものである； １．金属アルコキシドの少なくとも１種を含む溶液を無
機多孔体の表面に塗布し、乾燥し、熟成させることを特
徴とする無機キセロゲル膜の製造方法。That is, the present invention provides the following method for producing an inorganic xerogel film and the inorganic xerogel film obtained thereby: A method for producing an inorganic xerogel film, which comprises applying a solution containing at least one kind of metal alkoxide to the surface of an inorganic porous body, drying and aging.
【０００６】２．上記項１に記載の方法により得られた
無機キセロゲル膜。2. An inorganic xerogel film obtained by the method according to item 1.
【０００７】３．上記項１に記載の方法により得られた
無機キセロゲル膜からなる気体分離膜。3. A gas separation membrane comprising an inorganic xerogel membrane obtained by the method according to above item 1.
【０００８】４．金属アルコキシドの少なくとも１種と
金属イオンの少なくとも１種を含む溶液を無機多孔体の
表面に塗布し、乾燥し、熟成させることを特徴とする無
機キセロゲル膜の製造方法。4. A method for producing an inorganic xerogel film, which comprises applying a solution containing at least one kind of metal alkoxide and at least one kind of metal ion to the surface of an inorganic porous body, drying and aging.
【０００９】５．上記項４に記載の方法により得られた
無機キセロゲル膜。5. An inorganic xerogel film obtained by the method according to item 4.
【００１０】６．上記項４に記載の方法により得られた
無機キセロゲル膜からなる気体分離膜。6. A gas separation membrane comprising an inorganic xerogel membrane obtained by the method according to item 4.
【００１１】本発明において使用する金属アルコキシド
としては、特に限定されるものではないが、テトラメチ
ルシリケート、テトラエチルシリケート、ジルコニウム
テトラプロポキシド、チタンテトラブトキシド、アルミ
ニウムイソプロポキシド、アルミニウムブトキシド、ト
リメチルボラート、トリエチルボラートなどが例示され
る。これらの金属アルコキシドは、単独或いは２種以上
を混合して、溶液の状態で使用する。The metal alkoxide used in the present invention is not particularly limited, but tetramethyl silicate, tetraethyl silicate, zirconium tetrapropoxide, titanium tetrabutoxide, aluminum isopropoxide, aluminum butoxide, trimethyl borate, Examples include triethyl borate and the like. These metal alkoxides are used singly or as a mixture of two or more kinds in a solution state.
【００１２】金属アルコキシド溶液として水系溶液を使
用する場合には、金属アルコキシド１モルに対し、通常
水１〜５モル程度、アルコール１０〜３０モル程度、酸
０．０１〜０．１モル程度を配合して調製する。When an aqueous solution is used as the metal alkoxide solution, usually about 1 to 5 mol of water, about 10 to 30 mol of alcohol, and about 0.01 to 0.1 mol of acid are mixed with 1 mol of the metal alkoxide. And prepare.
【００１３】金属アルコキシド水系溶液の調製に使用す
るアルコールとしては、特に限定されないが、メチルア
ルコール、エチルアルコール、プロパノールなどが挙げ
られる。酸としても、特に限定されないが、硝酸、塩酸
などが挙げられる。The alcohol used for preparing the aqueous solution of metal alkoxide is not particularly limited, and examples thereof include methyl alcohol, ethyl alcohol, propanol and the like. The acid is also not particularly limited, but nitric acid, hydrochloric acid, etc. may be mentioned.
【００１４】金属アルコキシド溶液として非水系溶液を
使用する場合には、テトラヒドロフラン、クロロホル
ム、アセトンなどの有機溶媒に金属アルコキシドを溶解
させて使用する。非水系溶液を使用する場合には、金属
アルコキシド１モルに対し、有機溶媒１０〜３０モル程
度を配合して調製する。When a non-aqueous solution is used as the metal alkoxide solution, the metal alkoxide is dissolved in an organic solvent such as tetrahydrofuran, chloroform or acetone before use. When a non-aqueous solution is used, it is prepared by mixing 10 mol of an organic solvent with 1 mol of a metal alkoxide.
【００１５】金属アルコキシドの溶液には、金属イオン
を配合しておくことにより、無機キセロゲル膜の構造を
より強固なものとすることができ、膜の耐久性を高める
ことができる。また、金属イオンを配合しておく場合に
は、膜の耐久性が改善されるとともに、無機多孔体から
なる基板上に無機キセロゲル膜を形成させた複合状態で
使用する際に、基板と無機キセロゲル膜との密着性も、
改善される。この様な金属としては、具体的にクロム、
マンガン、鉄、コバルト、銅、亜鉛、ランタン、マグネ
シウムなどが例示される。溶液中での金属イオンの濃度
は、金属アルコキシド１モルに対し、０．１〜１モル程
度である。By incorporating a metal ion into the solution of the metal alkoxide, the structure of the inorganic xerogel film can be made stronger and the durability of the film can be enhanced. Also, when metal ions are blended, the durability of the film is improved, and when used in a composite state in which an inorganic xerogel film is formed on a substrate made of an inorganic porous material, the substrate and the inorganic xerogel are used. Adhesion to the film is also
Be improved. Specific examples of such a metal include chromium,
Examples include manganese, iron, cobalt, copper, zinc, lanthanum, magnesium and the like. The concentration of the metal ion in the solution is about 0.1 to 1 mol with respect to 1 mol of the metal alkoxide.
【００１６】本発明による無機キセロゲル膜は、上記の
様な金属アルコキシドの溶液を無機多孔体の表面に塗布
し、乾燥し、熟成させることにより、製造される。The inorganic xerogel film according to the present invention is produced by applying the solution of the metal alkoxide as described above to the surface of the inorganic porous material, drying and aging.
【００１７】無機多孔体の材質としては、シリカ系セラ
ミックス、シリカ系ガラス、アルミナ系セラミックスな
どが挙げられる。無機多孔体における細孔径は、特に限
定されないが、平均細孔径として、通常１ｎｍ〜１μｍ
程度であることが好ましく、４ｎｍ〜０．２μｍ程度で
あることがより好ましくい。Examples of the material of the inorganic porous material include silica-based ceramics, silica-based glass, alumina-based ceramics and the like. The pore size of the inorganic porous material is not particularly limited, but is usually 1 nm to 1 μm as the average pore size.
It is preferably about 4 nm to 0.2 μm, and more preferably about 4 nm to 0.2 μm.
【００１８】無機多孔体に対する金属アルコキシドの塗
布方法は、均一な塗膜が形成される限り、特に限定され
ないが、通常ディッピング法、スプレー法、スピン法な
どが採用される。塗膜の均一性の観点からは、ディッピ
ング法がより好ましい。The method for applying the metal alkoxide to the inorganic porous material is not particularly limited as long as a uniform coating film is formed, but usually a dipping method, a spray method, a spin method or the like is adopted. From the viewpoint of the uniformity of the coating film, the dipping method is more preferable.
【００１９】無機多孔体に対する金属アルコキシド溶液
の塗布厚さは、膜の用途などにより適宜決定すればよい
が、通常０．１〜１０μｍ程度であり、より好ましくは
１〜５μｍ程度である。The coating thickness of the metal alkoxide solution on the inorganic porous material may be appropriately determined depending on the use of the film, etc., but is usually about 0.1 to 10 μm, more preferably about 1 to 5 μm.
【００２０】無機多孔体表面に金属アルコキシド溶液の
塗膜を形成した後、乾燥する。乾燥は、塗膜表面が接触
により大きく変形しない程度まで行えば良い。乾燥条件
は、溶液の種類、濃度、塗膜の厚さなどにより変わりう
るので、特に限定されるものではないが、通常室温乃至
５０℃程度で１〜１０分間程度である。After forming a coating film of the metal alkoxide solution on the surface of the inorganic porous material, it is dried. The drying may be performed to such an extent that the surface of the coating film is not significantly deformed due to contact. The drying conditions are not particularly limited as they may vary depending on the type and concentration of the solution, the thickness of the coating film, etc., but are usually room temperature to about 50 ° C. and about 1 to 10 minutes.
【００２１】本発明においては、次いで無機多孔体上に
形成した塗膜を熟成させる。この塗膜の熟成工程は、均
一な微小細孔を有し、構造的に連続した均質な無機キセ
ロゲル膜を形成させるための必須の要件である。より具
体的には、上記の様にして乾燥した塗膜を０℃程度から
１００℃程度の温度で１時間〜２週間程度保持する。熟
成は、温度が高いほど短時間で終了する。一般的には、
１００℃では１〜２時間程度で終了し、室温近傍では１
〜２週間程度を要する。従って、金属アルコキシドの種
類、無機キセロゲル膜の用途などに応じて、上記の範囲
内で適切な条件を採用すればよい。In the present invention, the coating film formed on the inorganic porous material is then aged. The aging step of this coating film is an essential requirement for forming a structurally continuous and homogeneous inorganic xerogel film having uniform micropores. More specifically, the coating film dried as described above is kept at a temperature of about 0 ° C. to 100 ° C. for about 1 hour to 2 weeks. The aging is completed in a shorter time as the temperature is higher. In general,
It takes about 1 to 2 hours at 100 ° C, and 1 at room temperature.
It takes about 2 weeks. Therefore, appropriate conditions may be adopted within the above range depending on the type of metal alkoxide, the use of the inorganic xerogel film, and the like.
【００２２】上記の様にして得られた無機キセロゲル膜
は、無機多孔体上に塗膜として存在する複合材料として
使用することが可能であり、また無機多孔体から分離し
て単独の膜として使用することも可能である。前者の場
合には、無機多孔体が基板としての機能を発揮する。後
者の場合には、さらに他の基材と複合化して使用しても
良い。The inorganic xerogel film obtained as described above can be used as a composite material existing as a coating film on an inorganic porous material, or can be separated from the inorganic porous material and used as a single film. It is also possible to do so. In the former case, the inorganic porous material exhibits the function as a substrate. In the case of the latter, you may use it combining with another base material further.
【００２３】本発明による無機キセロゲル膜は、三次元
の金属−酸素結合からなるネットワーク構造を有してい
る。この様な無機キセロゲル膜は、気体の選択的透過
膜、パーベイパレーション膜などとして有用である。The inorganic xerogel film according to the present invention has a three-dimensional network structure composed of metal-oxygen bonds. Such an inorganic xerogel film is useful as a gas selective permeation film, a pervaporation film, or the like.
【００２４】本発明による無機キセロゲル膜を気体の選
択的透過膜として使用する場合には、二酸化炭素、二酸
化硫黄、二酸化窒素、硫化水素などの酸性ガス類、水
素、ヘリウムなどの分子径の小さなガスの分離に好適で
ある。When the inorganic xerogel membrane according to the present invention is used as a gas selective permeable membrane, acidic gases such as carbon dioxide, sulfur dioxide, nitrogen dioxide and hydrogen sulfide, and gases having a small molecular diameter such as hydrogen and helium. It is suitable for the separation of
【００２５】[0025]
【発明の効果】本発明によれば、下記の様な顕著な効果
が達成される。According to the present invention, the following remarkable effects are achieved.
【００２６】（１）従来法による無機キセロゲル膜に比
して、より均一な微小細孔を有する構造的に連続した均
質な無機キセロゲル膜が得られる。(1) A structurally continuous and homogeneous inorganic xerogel film having more uniform fine pores can be obtained as compared with the inorganic xerogel film obtained by the conventional method.
【００２７】（２）得られる無機キセロゲル膜は、強固
である。(2) The resulting inorganic xerogel film is strong.
【００２８】（３）無機多孔体を基材とする複合体とし
ての形態で使用する場合には、基材と無機キセロゲル膜
との密着性が高い。(3) When used in the form of a composite having an inorganic porous material as a base material, the adhesion between the base material and the inorganic xerogel film is high.
【００２９】（４）金属イオンを併用する場合には、上
記（２）および（３）の効果がより一層改善される。(4) When metal ions are used in combination, the effects (2) and (3) are further improved.
【００３０】（５）本発明による無機キセロゲル膜は、
気体分離膜として、公知の無機気体分離膜に比して、気
体分離性能が著しく高い。例えば、二酸化炭素−窒素の
分離において、従来の無機気体分離膜の透過係数比（Ｐ
CO2／ＰN2 ）は、２程度であったのに対し、本発明によ
る無機キセロゲル膜の透過係数比（ＰCO2／ＰN2 ）は、
１００程度にも達した。 （６）本発明による無機キセロゲル膜は、炭素−炭素結
合からなる高分子系気体分離膜に比して、耐熱性に優れ
ている。(5) The inorganic xerogel film according to the present invention comprises:
As a gas separation membrane, the gas separation performance is remarkably higher than that of a known inorganic gas separation membrane. For example, in the separation of carbon dioxide-nitrogen, the permeability coefficient ratio (P
CO 2 / PN 2 ) was about 2, whereas the permeability coefficient ratio (PCO 2 / PN 2 ) of the inorganic xerogel membrane according to the present invention was
It has reached about 100. (6) The inorganic xerogel membrane according to the present invention is excellent in heat resistance as compared with the polymer-based gas separation membrane composed of carbon-carbon bonds.
【００３１】[0031]
【実施例】以下に実施例を示し、本発明の特徴とすると
ころをより一層明確にする。EXAMPLES Examples will be shown below to further clarify the features of the present invention.
【００３２】なお、以下の実施例において、各種ガスの
透過性試験は、室温で供給ガス圧１気圧の条件下に膜を
透過してくる気体の流量を質量流量計により測定し、透
過速度を求めることにより行った。In the following examples, various gas permeation tests were carried out by measuring the flow rate of gas passing through the membrane at room temperature under a feed gas pressure of 1 atm with a mass flow meter to determine the permeation rate. It was done by asking.
【００３３】実施例１ テトラエチルシリケート１モルに対し、水１モル、硝酸
０．０１モルおよびエタノール２０モルを加えて調製し
た溶液１００ｍｌを室温で８時間撹拌して、均一な溶液
を得た。Example 1 100 ml of a solution prepared by adding 1 mol of water, 0.01 mol of nitric acid and 20 mol of ethanol to 1 mol of tetraethyl silicate was stirred at room temperature for 8 hours to obtain a uniform solution.
【００３４】得られた溶液に多孔質ガラス管（ＳｉＯ2
約９７％−Ｂ2Ｏ3約３％、外径５ｍｍ、内径４ｍｍ、平
均細孔径４ｎｍ〜０．１μｍ）をディップコーティング
し、室温で３分間乾燥した後、得られた塗膜を１００℃
で２時間熟成させた。同様の操作を６回繰り返すことに
より、多孔質ガラス管表面に厚さ約２μｍのキセロゲル
膜を形成させた。A porous glass tube (SiO 2
About 97% -B 2 O 3 about 3%, outer diameter 5 mm, inner diameter 4 mm, average pore diameter 4 nm to 0.1 μm) was dip-coated and dried at room temperature for 3 minutes.
Aged for 2 hours. By repeating the same operation 6 times, a xerogel film having a thickness of about 2 μm was formed on the surface of the porous glass tube.
【００３５】得られた膜は、均質で且つ透明であった。The film obtained was homogeneous and transparent.
【００３６】この膜による室温での二酸化炭素、窒素、
ヘリウムおよび二酸化硫黄の透過速度は、それぞれ１．
１４×１０-5、１．３３×１０-7、１．０８×１０-6お
よび１．１１×１０-5（ｃｍ3（ＳＴＰ）・ｃｍ-2・ｃ
ｍＨｇ-1・ｓ-1）であり、透過速度比は、ＰCO2／ＰN2
＝８５．１、ＰHe／ＰN2＝８．１およびＰSO2／ＰN2＝
８３．４であった。With this membrane, carbon dioxide, nitrogen at room temperature,
The permeation rates of helium and sulfur dioxide are 1.
14 × 10 −5 , 1.33 × 10 −7 , 1.08 × 10 −6 and 1.11 × 10 −5 (cm 3 (STP) · cm −2 · c
mHg −1 · s −1 ), and the transmission rate ratio is PCO 2 / PN 2
= 85.1, PHe / PN 2 = 8.1 and PSO 2 / PN 2 =
It was 83.4.
【００３７】実施例２ テトラエチルシリケート１モルに対し、水１モル、硝酸
０．０１モル、エタノール２０モルおよび硫酸銅０．２
５モルを加えて調製した溶液１００ｍｌを室温で８時間
撹拌して、均一な溶液を得た。Example 2 1 mol of water, 1 mol of nitric acid, 20 mol of ethanol and 0.2 mol of copper sulfate per 1 mol of tetraethyl silicate.
100 ml of the solution prepared by adding 5 mol was stirred at room temperature for 8 hours to obtain a uniform solution.
【００３８】得られた溶液に多孔質ガラス管（ＳｉＯ2
約９７％−Ｂ2Ｏ3約３％、外径５ｍｍ、内径４ｍｍ、平
均細孔径４ｎｍ〜０．１μｍ）をディップコーティング
し、室温で３分間乾燥した後、得られた塗膜を１００℃
で２時間熟成させた。同様の操作を６回繰り返すことに
より、多孔質ガラス管表面に厚さ約２μｍのキセロゲル
膜を形成させた。形成された膜には、銅イオンが均一に
分散しており、青色で透明であった。A porous glass tube (SiO 2
About 97% -B 2 O 3 about 3%, outer diameter 5 mm, inner diameter 4 mm, average pore diameter 4 nm to 0.1 μm) was dip-coated and dried at room temperature for 3 minutes.
Aged for 2 hours. By repeating the same operation 6 times, a xerogel film having a thickness of about 2 μm was formed on the surface of the porous glass tube. Copper ions were uniformly dispersed in the formed film, which was blue and transparent.
【００３９】この膜による室温での二酸化炭素、窒素、
ヘリウムおよび二酸化硫黄の透過速度は、それぞれ１．
２７×１０-5、１．２９×１０-7、１．２６×１０-6お
よび１．１７×１０-5（ｃｍ3（ＳＴＰ）・ｃｍ-2・ｃ
ｍＨｇ-1・ｓ-1）であり、透過速度比は、ＰCO2／ＰN2
＝９８．７、ＰHe／ＰN2＝９．８およびＰSO2／ＰN2＝
９０．６と高い値を示した。With this membrane, carbon dioxide, nitrogen at room temperature,
The permeation rates of helium and sulfur dioxide are 1.
27 × 10 −5 , 1.29 × 10 −7 , 1.26 × 10 −6 and 1.17 × 10 −5 (cm 3 (STP) · cm −2 · c
mHg −1 · s −1 ), and the transmission rate ratio is PCO 2 / PN 2
= 98.7, PHe / PN 2 = 9.8 and PSO 2 / PN 2 =
It showed a high value of 90.6.
【００４０】実施例３ 実施例１および実施例２で得られた２種の無機キセロゲ
ル膜を使用して、実施例１と同様にして二酸化炭素と窒
素との分離を行った。透過速度比と製造後経過日数との
関係を図１に示す。Example 3 Carbon dioxide and nitrogen were separated in the same manner as in Example 1 using the two types of inorganic xerogel membranes obtained in Examples 1 and 2. The relationship between the transmission rate ratio and the number of days elapsed after production is shown in FIG.
【００４１】図１から明らかな様に、銅イオンを含む場
合（実施例２；○で示す）には、銅イオンを含まない場
合（実施例１；●で示す）に比して、膜の耐久性が高ま
り、長期にわたって高い気体分離能を維持することが明
らかである。As is apparent from FIG. 1, when the copper ion is contained (Example 2; indicated by ◯), the film of the film is formed more than when the copper ion is not contained (Example 1; indicated by ●). It is apparent that the durability is increased and the high gas separation ability is maintained for a long time.
【００４２】実施例４ ジルコニウムテトラプロポキシド１モルに対しテトラヒ
ドロフラン２０モルを加えた溶液１００ｍｌを０℃で８
時間撹拌した後、多孔質ガラス管（実施例１で使用した
ものと同様）にディップコートし、冷蔵庫中で２週間保
持し、加水分解させて、無機キセロゲル膜を形成させ
た。Example 4 100 ml of a solution prepared by adding 20 mol of tetrahydrofuran to 1 mol of zirconium tetrapropoxide was heated at 0 ° C. for 8 hours.
After stirring for a period of time, a porous glass tube (similar to that used in Example 1) was dip-coated, kept in a refrigerator for 2 weeks, and hydrolyzed to form an inorganic xerogel film.
【００４３】この膜による室温での二酸化炭素、窒素、
ヘリウムおよび二酸化硫黄の透過速度は、それぞれ１．
２８×１０-5、１．３１×１０-7、１．２７×１０-6お
よび１．１７×１０-5（ｃｍ3（ＳＴＰ）・ｃｍ-2・ｃ
ｍＨｇ-1・ｓ-1）であり、透過速度比は、ＰCO2／ＰN2
＝９７．６、ＰHe／ＰN2＝９．７およびＰSO2／ＰN2＝
８９．４であった。With this membrane, carbon dioxide, nitrogen at room temperature,
The permeation rates of helium and sulfur dioxide are 1.
28 × 10 −5 , 1.31 × 10 −7 , 1.27 × 10 −6 and 1.17 × 10 −5 (cm 3 (STP) · cm −2 · c
mHg −1 · s −1 ), and the transmission rate ratio is PCO 2 / PN 2
= 97.6, PHe / PN 2 = 9.7 and PSO 2 / PN 2 =
It was 89.4.
【図１】実施例１および実施例２で得られた２種の無機
キセロゲル膜の経時的な耐久性を示すグラフである。1 is a graph showing the durability of two types of inorganic xerogel films obtained in Examples 1 and 2 over time.
Claims (6)
溶液を無機多孔体の表面に塗布し、乾燥し、熟成させる
ことを特徴とする無機キセロゲル膜の製造方法。1. A method for producing an inorganic xerogel film, which comprises coating a surface of an inorganic porous material with a solution containing at least one kind of metal alkoxide, followed by drying and aging.
キセロゲル膜。2. An inorganic xerogel film obtained by the method according to claim 1.
キセロゲル膜からなる気体分離膜。3. A gas separation membrane comprising an inorganic xerogel membrane obtained by the method according to claim 1.
イオンの少なくとも１種を含む溶液を無機多孔体の表面
に塗布し、乾燥し、熟成させることを特徴とする無機キ
セロゲル膜の製造方法。4. A method for producing an inorganic xerogel film, which comprises coating a solution containing at least one kind of metal alkoxide and at least one kind of metal ion on the surface of an inorganic porous body, drying and aging.
キセロゲル膜。5. An inorganic xerogel film obtained by the method according to claim 4.
キセロゲル膜からなる気体分離膜。6. A gas separation membrane comprising an inorganic xerogel membrane obtained by the method according to claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6032885A JP2642860B2 (en) | 1994-02-04 | 1994-02-04 | Inorganic xerogel membrane, method for producing the same, and gas separation membrane comprising inorganic xerogel membrane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6032885A JP2642860B2 (en) | 1994-02-04 | 1994-02-04 | Inorganic xerogel membrane, method for producing the same, and gas separation membrane comprising inorganic xerogel membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07213877A true JPH07213877A (en) | 1995-08-15 |
| JP2642860B2 JP2642860B2 (en) | 1997-08-20 |
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ID=12371339
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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|---|---|
| JP (1) | JP2642860B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001034382A1 (en) * | 1999-11-10 | 2001-05-17 | Matsushita Electric Works, Ltd. | Aerogel substrate and method for preparing the same |
| US6699797B1 (en) | 2002-12-17 | 2004-03-02 | Intel Corporation | Method of fabrication of low dielectric constant porous metal silicate films |
| JP2005118767A (en) * | 2003-09-26 | 2005-05-12 | Japan Fine Ceramics Center | Hydrogen-selective gas separation membrane, hydrogen-selective gas separation material, and methods for producing them |
| JP2007503995A (en) * | 2003-09-04 | 2007-03-01 | コリア リサーチ インスティテュートオフ゛ ケミカル テクノロシ゛ー | Titania composite membrane for water / alcohol separation and method for producing the same |
| JP2009520594A (en) * | 2005-12-22 | 2009-05-28 | アレバ エヌペ | Gas separation membrane containing a silica-based microporous silica layer doped with trivalent elements |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102154549B1 (en) * | 2019-05-03 | 2020-09-10 | 인하대학교 산학협력단 | Polyimide xerogel separator with amino-fuctionalized hollow mesoporous silica particels and manufacturing method of the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03284330A (en) * | 1990-03-29 | 1991-12-16 | Shinko Pantec Co Ltd | Production of inorganic asymmetric membrane |
-
1994
- 1994-02-04 JP JP6032885A patent/JP2642860B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03284330A (en) * | 1990-03-29 | 1991-12-16 | Shinko Pantec Co Ltd | Production of inorganic asymmetric membrane |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001034382A1 (en) * | 1999-11-10 | 2001-05-17 | Matsushita Electric Works, Ltd. | Aerogel substrate and method for preparing the same |
| US6740416B1 (en) | 1999-11-10 | 2004-05-25 | Matsushita Electric Works, Ltd. | Aerogel substrate and method for preparing the same |
| US6699797B1 (en) | 2002-12-17 | 2004-03-02 | Intel Corporation | Method of fabrication of low dielectric constant porous metal silicate films |
| JP2007503995A (en) * | 2003-09-04 | 2007-03-01 | コリア リサーチ インスティテュートオフ゛ ケミカル テクノロシ゛ー | Titania composite membrane for water / alcohol separation and method for producing the same |
| JP2005118767A (en) * | 2003-09-26 | 2005-05-12 | Japan Fine Ceramics Center | Hydrogen-selective gas separation membrane, hydrogen-selective gas separation material, and methods for producing them |
| JP2009520594A (en) * | 2005-12-22 | 2009-05-28 | アレバ エヌペ | Gas separation membrane containing a silica-based microporous silica layer doped with trivalent elements |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2642860B2 (en) | 1997-08-20 |
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