JPH03284330A - Production of inorganic asymmetric membrane - Google Patents
Production of inorganic asymmetric membraneInfo
- Publication number
- JPH03284330A JPH03284330A JP8330690A JP8330690A JPH03284330A JP H03284330 A JPH03284330 A JP H03284330A JP 8330690 A JP8330690 A JP 8330690A JP 8330690 A JP8330690 A JP 8330690A JP H03284330 A JPH03284330 A JP H03284330A
- Authority
- JP
- Japan
- Prior art keywords
- inorganic
- asymmetric membrane
- thickness
- support material
- porous
- 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.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000499 gel Substances 0.000 claims abstract description 13
- 229920001817 Agar Polymers 0.000 claims abstract description 12
- 239000008272 agar Substances 0.000 claims abstract description 12
- 239000005373 porous glass Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 32
- 239000000565 sealant Substances 0.000 claims description 17
- 239000010409 thin film Substances 0.000 claims description 12
- 150000002902 organometallic compounds Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 239000011521 glass Substances 0.000 abstract description 34
- 239000011148 porous material Substances 0.000 abstract description 14
- 239000003795 chemical substances by application Substances 0.000 abstract description 8
- 238000007789 sealing Methods 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract 4
- 125000002524 organometallic group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- 239000000919 ceramic Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 2
- JHLCADGWXYCDQA-UHFFFAOYSA-N calcium;ethanolate Chemical compound [Ca+2].CC[O-].CC[O-] JHLCADGWXYCDQA-UHFFFAOYSA-N 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- -1 silicon alkoxide Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004017 vitrification Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 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 1
- 238000000926 separation method Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Filtering Materials (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、無機質非対称膜の製造方法に関し、詳細には
、微細孔を有する多孔質ガラス薄膜を多孔質支持材の表
側表面に被覆してなり、濾過材として使用される無機質
非対称膜を製造する方法であり、特に、化学工業、医薬
品工業、食品工業、醗酵工業など、苛酷な腐食環境下で
使用される無機質非対称膜の製造方法に関する。Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for producing an inorganic asymmetric membrane, and more particularly, the present invention relates to a method for producing an inorganic asymmetric membrane, and in particular, a porous glass thin membrane having micropores is coated on the front surface of a porous support material. This is a method for producing an inorganic asymmetric membrane used as a filtration medium, and particularly relates to a method for producing an inorganic asymmetric membrane used in harsh corrosive environments such as the chemical industry, pharmaceutical industry, food industry, and fermentation industry.
（従来の技術）
従来、濾過材としては、素焼板の如き無機濾過材、酢酸
セルロースの如き有機濾過材がよく知られている。又、
孔径：１〜１０μｍ程度の多孔質セラミックスの板体又
は管体の表面に、ＺｒＣＩ ａの如き無機化合物や、ポ
リアクリル酸の如き有機高分子化合物のコロイド状膜を
形成した所謂ダイナミック膜が、かん水の淡水化用等の
濾過材として好適である事が知られている。(Prior Art) Conventionally, as filter media, inorganic filter media such as clay plates and organic filter media such as cellulose acetate are well known. or,
A so-called dynamic membrane is formed by forming a colloidal membrane of an inorganic compound such as ZrCI a or an organic polymer compound such as polyacrylic acid on the surface of a porous ceramic plate or tube with a pore diameter of about 1 to 10 μm. It is known that it is suitable as a filter material for desalination purposes.
しかしながら、無機濾過材は、微細孔をもつものを薄膜
状に成形するのが困難なため、その用途が制限されると
共に、濾過物質による膜の目づまりを生し易く、又、そ
の洗浄除去が極めて困難であるという問題点がある。有
機濾過材は、耐熱性、耐久性が劣り、特に耐溶剤性が劣
る等の欠点を有している。ダイナミック膜は、水溶液中
で膜を形成するため、気体の分離には使用できないし、
又、ｐｇ安定範囲が４〜１０であるため、強酸性、強ア
ルカリ性の条件下では使用できないという問題点がある
。However, since it is difficult to form inorganic filtration media into a thin film with micropores, its uses are limited, the membrane is easily clogged with filtration substances, and it is extremely difficult to wash and remove it. The problem is that it is difficult. Organic filter media have drawbacks such as poor heat resistance and durability, and particularly poor solvent resistance. Dynamic membranes cannot be used for gas separation because they form a membrane in an aqueous solution.
Furthermore, since the pg stability range is 4 to 10, there is a problem that it cannot be used under strongly acidic or strongly alkaline conditions.
かかる問題点を解決すべく種々検討され、その結果、無
機質同志が複合されてなり、非対称の構造を有する濾過
材（以鋒、無機質非対称膜という）が開発されている９
例えば、特公平１−２３１６２号公報には、多孔質セラ
ミックスの表面に、孔径：５〜１０００人の多孔質シリ
カガラス層を０．１〜１００μ園の厚さに積層してなる
濾過材及びその製造方法が提案されている。該製造方法
は、多孔質セラミックスの表面に、シリコンアルキシド
を含有する溶液を塗布し、乾燥後、加熱処理してガラス
化するものである。尚、上記溶液の塗布は、多孔質セラ
ミックスを上記溶液に浸漬する方法により行われている
。Various studies have been conducted to solve these problems, and as a result, a filtration material (referred to as an inorganic asymmetric membrane) has been developed that is made of a composite of inorganic materials and has an asymmetric structure.
For example, Japanese Patent Publication No. 1-23162 describes a filter material in which a porous silica glass layer with a pore size of 5 to 1000 pores is laminated to a thickness of 0.1 to 100 μm on the surface of porous ceramics, and its A manufacturing method is proposed. In this manufacturing method, a solution containing silicon alkoxide is applied to the surface of porous ceramics, and after drying, the solution is heated and vitrified. The solution is applied by dipping porous ceramics in the solution.
かかる無機質非対称膜によれば、無機質で構成されてい
るので、耐熱性及び耐久性に優れ、又、強酸性、強アル
カリ性の条件下で使用に耐え得るようになる。又、ガラ
ス層（膜）の厚みを小さくする事により、濾過物質によ
る目づまりを生じ難いものにし得る。Since such an inorganic asymmetric membrane is made of inorganic material, it has excellent heat resistance and durability, and can withstand use under strongly acidic and strongly alkaline conditions. Furthermore, by reducing the thickness of the glass layer (membrane), clogging due to filter substances can be made less likely to occur.
（発明が解決しようとする課Ｈ）
ところが、従来の無機質非対称膜の製造方法においては
、多孔質セラミックス表面にシリコンアルキシド含有溶
液を塗布する際、塗布溶液がセラミックスの孔に侵入し
易く、セラミックス中に含浸するので、加熱処理後はセ
ラミックスの多孔質部の有効部分が少なくなると共に、
実質的なガラス層の厚み（セラミックス表面上のガラス
層厚とセラミックス中の含浸ガラス層厚との和）が大き
くなり、その結果得られる無機質非対称膜は濾過物質に
よる目づまりが生じ易いものになるという問題点がある
。(Problem H to be solved by the invention) However, in the conventional method for producing an inorganic asymmetric membrane, when applying a silicon alkoxide-containing solution to the surface of a porous ceramic, the coating solution easily enters the pores of the ceramic, causing After heat treatment, the effective part of the porous part of the ceramic decreases and
The actual thickness of the glass layer (the sum of the thickness of the glass layer on the ceramic surface and the thickness of the impregnated glass layer in the ceramic) increases, and the resulting inorganic asymmetric membrane becomes more likely to be clogged by filter substances. There is a problem.
又、たとえ上記実質的ガラス層厚を小さくし得たとして
も、前記塗布溶液の含浸厚ば不均一であると共に、極め
て再現性に乏しいので、含浸ガラス層厚を均一に、且つ
一定にすることが極めて難しく、その結果得られる無機
質非対称膜は濾過機能の再現性が乏しくなるという問題
点がある。Further, even if the above-mentioned substantial glass layer thickness can be reduced, the impregnated thickness of the coating solution is not uniform and has extremely poor reproducibility, so it is necessary to make the impregnated glass layer thickness uniform and constant. is extremely difficult, and the resulting asymmetric inorganic membrane has the problem of poor reproducibility of filtration function.
本発明はこの様な事情に着目してなされたものであって
、その目的は従来のものがもつ以上のような問題点を解
消し、実質的ガラス層厚を小さくし得ると共に、含浸ガ
ラス層厚を均一に且つ一定にし得る無機質非対称膜の製
造方法を擾供しようとするものである。The present invention has been made in view of these circumstances, and its purpose is to solve the above-mentioned problems of the conventional ones, to reduce the substantial thickness of the glass layer, and to reduce the thickness of the impregnated glass layer. The present invention aims to provide a method for manufacturing an asymmetric inorganic membrane that can have a uniform and constant thickness.
（課題を解決するための手段）
上記目的を達成するために、本発明に係る無機質非対称
膜の製造方法は、次のような構成としている。(Means for Solving the Problems) In order to achieve the above object, the method for manufacturing an inorganic asymmetric membrane according to the present invention has the following configuration.
即ち、請求項１に記載の無機質非対称膜の製造方法は、
微細孔を有する多孔質ガラス薄膜を多孔質支持材の表側
表面に被覆してなる無機質非対称膜を製造するに際し、
多孔質支持材の裏側表面から温水に可溶性の封孔剤溶液
を含浸し、冷却固化した後、該支持材の表側表面に有機
金属化合物含有溶液を塗布し、ゲル化した後、前記固化
した封孔剤を温水で再溶解して除去し、前記ゲルを加熱
処理してガラス化することを特徴とする無ｍ質非対称膜
の製造方法である。That is, the method for manufacturing an inorganic asymmetric membrane according to claim 1,
When producing an inorganic asymmetric membrane in which the front surface of a porous support material is coated with a porous glass thin film having micropores,
After impregnating the back surface of the porous support material with a sealant solution soluble in warm water and solidifying it by cooling, an organometallic compound-containing solution is applied to the front surface of the support material, and after gelling, the solidified sealant solution is applied. This is a method for producing an asymmetric asymmetric membrane, characterized in that the pore agent is redissolved with warm water to remove it, and the gel is vitrified by heat treatment.
請求項２に記載の無機質非対称膜の製造方法は、前記封
孔剤が寒天である請求項１に記載の無機質非対称膜の製
造方法である。The method for manufacturing an inorganic asymmetric membrane according to claim 2 is the method for manufacturing an inorganic asymmetric membrane according to claim 1, wherein the sealing agent is agar.
（作 用）
本発明に係る無ｍ質非対称膜の製造方法は、前記の如く
、先ず、多孔質支持材の裏側表面から温水に可溶性の封
孔剤溶液を含浸し、固化するようにしている。、該含浸
は、温水に溶解した封孔剤の溶液中に多孔質支持材を浸
漬する方法により行い得る。このとき、多孔質支持材の
裏側を下にして配置すると共に、封孔剤溶液の深さを一
定にすると、含浸深さを容易番こ一定にし得る。そのた
め、多孔質支持材中において固化した封孔剤層の厚み（
多孔質支持材の裏側表面からの深さ）を一定にし得る。(Function) As described above, the method for producing the asymmetric asymmetric membrane according to the present invention includes first impregnating the back surface of the porous support material with a sealant solution soluble in warm water and solidifying it. . , the impregnation can be carried out by immersing the porous support material in a solution of the sealant dissolved in warm water. At this time, if the porous support material is placed with its back side down and the depth of the sealant solution is constant, the impregnation depth can be easily kept constant. Therefore, the thickness of the sealant layer solidified in the porous support material (
The depth from the back surface of the porous support material can be constant.
上記封孔剤溶液の固化後、多孔質支持材の表側表面に有
機金属化合物含有溶液を塗布するようにしている。この
とき、該溶液は多孔質支持材中に含浸するが、該含浸の
進行は固化した封孔剤層により防止される。そのため、
前記の如く、固化封孔剤層の厚みを一定にしておくと、
該含浸深さを一定にし得る。又、多孔質支持材の厚みに
比し、固化封孔剤層の厚みを少し小さくしておくと、そ
れに対応して該含浸深さ（有機金属化合物含有溶液の含
浸深さ）を小さくし得る。従って、多孔質支持材中での
ゲル（固形状物質）の厚みを、均一に、且つ所要の大き
さ（：薄さ）に調整し得る。After solidification of the sealant solution, an organic metal compound-containing solution is applied to the front surface of the porous support material. At this time, the solution impregnates the porous support material, but the progress of the impregnation is prevented by the solidified sealant layer. Therefore,
As mentioned above, if the thickness of the solidified sealant layer is kept constant,
The impregnation depth can be constant. Furthermore, if the thickness of the solidified sealant layer is made slightly smaller than the thickness of the porous support material, the impregnation depth (the impregnation depth of the organometallic compound-containing solution) can be correspondingly reduced. . Therefore, the thickness of the gel (solid substance) in the porous support material can be adjusted to be uniform and to a desired size (thinness).
又、多孔質支持材の表面（表側表面）上のゲル層の厚み
は、特公平１−２３１６２号公報に記載の方法の場合と
同様、比較的自由に制御し得る。Further, the thickness of the gel layer on the surface (front side surface) of the porous support material can be controlled relatively freely as in the method described in Japanese Patent Publication No. 1-23162.
上記ゲル化後、前記多孔質支持材中の固化した封孔剤を
温水で再溶解して除去するようにしているので、多孔質
支持材は本来有する多孔質状態に戻り、濾過機能をもつ
ようになる。尚、上記封孔剤の温水での再溶解除去は、
該封孔剤が温水に可溶性であるので、容易に行い得る。After the above-mentioned gelation, the solidified sealant in the porous support material is redissolved with warm water and removed, so that the porous support material returns to its original porous state and has a filtration function. become. In addition, the above sealant can be redissolved and removed with warm water.
Since the pore sealing agent is soluble in hot water, this can be easily carried out.
かかる温水に可溶性の封孔剤としては、例えば寒天があ
る。寒天は、入手が容易であり、温水に溶解し、冷却す
ると固化し、温水で再溶解する性質があり、前記封孔剤
として好適である。Examples of such hot water-soluble sealants include agar. Agar is easily available, dissolves in hot water, solidifies when cooled, and redissolves in hot water, and is suitable as the sealant.
前記多孔質支持材中及び表面上のゲルは、加熱処理して
ガラス化するようにしている。このとき、ゲル層の厚み
を前記の如く調整しておくと、多孔質支持材中及び表面
上のガラス層の厚みを、均一に且つ所要の薄さにし得る
。The gel in and on the surface of the porous support material is vitrified by heat treatment. At this time, if the thickness of the gel layer is adjusted as described above, the thickness of the glass layer in the porous support material and on the surface can be made uniform and as thin as required.
従って、寞質的ガラス層厚を小さくし得ると共に、含浸
ガラス層厚を均一に且つ一定にし得るようになる。又、
ガラスは無機質であり、耐酸性及び耐アルカリ性に優れ
、又、強度及び耐熱性も比較的硬れている。そのため、
本発明に係る無機質非対称膜の製造方法によれば、目づ
まりが生じ難く、又、濾過機能の再現性に優れると共に
、耐熱性及び耐久性に優れ、又、強酸性、強アルカリ性
の条件下で使用に耐え得る無機質非対称膜が得られるよ
うになる。Therefore, it is possible to reduce the physical glass layer thickness and to make the impregnated glass layer thickness uniform and constant. or,
Glass is an inorganic substance, has excellent acid resistance and alkali resistance, and is relatively hard in strength and heat resistance. Therefore,
According to the method for producing an inorganic asymmetric membrane according to the present invention, clogging does not easily occur, the filtration function is excellent in reproducibility, heat resistance and durability are excellent, and it can be used under strongly acidic and strongly alkaline conditions. It becomes possible to obtain an inorganic asymmetric membrane that can withstand
尚、前記有機金属化合物含有溶液のゲル化及びガラス化
は、ゾル−ゲル・プロセスにより進行するものである。Note that the gelation and vitrification of the organometallic compound-containing solution proceed by a sol-gel process.
即ち、有機金属化合物含有溶液は、ゾルの状態を経てゲ
ル（シェリー状固形物）に変化し、該ゲルを加熱すると
ガラス化する。該ゾル及びゲルの状態のときに薄膜等の
種々の形状にし得、そのため極めてＭＷ、の小さい多孔
質ガラス薄膜を得ることができる。That is, the organometallic compound-containing solution changes from a sol state to a gel (sherry-like solid), and when the gel is heated, it becomes vitrified. When in the sol or gel state, it can be formed into various shapes such as a thin film, and therefore a porous glass thin film with an extremely small MW can be obtained.
前記有機金属化合物含有溶液は、有機金属化合物を必ず
含有する溶液であり、更に無機塩を含有せることかでき
る。溶媒としてはアルコール及び／又は水を使用できる
。上記有機金属化合物としては金属アルコキシドが代表
的であるが、特に限定されるものではない、金属アルコ
キシドには、例えばナトリウムエトキシド、カルシウム
エトキシド、オクチル酸イツトリウム及びシリコンエト
キシドがある。The organometallic compound-containing solution is a solution that necessarily contains an organometallic compound, and may further contain an inorganic salt. Alcohol and/or water can be used as a solvent. The organometallic compound is typically a metal alkoxide, but is not particularly limited. Examples of the metal alkoxide include sodium ethoxide, calcium ethoxide, yttrium octylate, and silicon ethoxide.
前記ガラス化後のガラス組成は、前記有機金属化合物、
無機塩の種類により変化させ得る。例えば、アルカリ土
類金属の酸化物（Ｒ”Ｏ） 、金属の酸化物（ＨＯ）及
びＳｉＯ□を含有するガラスが得られる。このとき、５
ｉ０２はガラスの骨格構造を形成し、Ｒ１０及び問はガ
ラスを安定化して耐熱性、耐食性及び強度を向上する作
用がある。The glass composition after vitrification includes the organometallic compound,
It can be changed depending on the type of inorganic salt. For example, a glass containing alkaline earth metal oxide (R”O), metal oxide (HO) and SiO□ can be obtained.
i02 forms the skeletal structure of the glass, and R10 and Q stabilize the glass to improve its heat resistance, corrosion resistance, and strength.
（実施例）
１羞ＩＬＬ
実施例１に係る無機質非対称膜の製造過程の概要を第１
〜４図に示す。(Example) 1. An overview of the manufacturing process of the inorganic asymmetric membrane according to Example 1 is given below.
- Shown in Figure 4.
先ず、容量：１００ｍ１のビー力にて、封孔剤として寒
天を温水で熔解して、寒天溶液を作った。第１図に示す
如く、該寒天溶液（２）をガラス板（３）（厚み＝５１
１幅：３００ｍｍ、長さ：３００ｍｍ）上に流延した０
次いで、細孔径：５０μ−の多孔質アルミナ板（１）（
厚み：２’ｗｍ、輻：１００ｍ霧、長さ：１００ｍｍ）
を、上記ガラス板（３）上に置き、該アルミナ板（１）
の下側表面から寒天溶液（２）を含浸させた後、冷却し
て寒天（２）を同化した。First, an agar solution was prepared by dissolving agar as a sealing agent in warm water at a beer force of 100 ml. As shown in Fig. 1, the agar solution (2) was placed on a glass plate (3) (thickness = 51
1 Width: 300mm, Length: 300mm)
Next, a porous alumina plate (1) with a pore diameter of 50 μ-
Thickness: 2'wm, convergence: 100m fog, length: 100mm)
is placed on the glass plate (3), and the alumina plate (1) is placed on the glass plate (3).
After impregnating the agar solution (2) from the lower surface of the tube, it was cooled to assimilate the agar (2).
次に、第２図に示す如く、シリコンテトラエトキシド：
ＩＯｍｏｌ、 ８５％リンｆｌ！ ： １ ｍｏｌ、
エタノール： ２０ｗｏ ｌ 、水：５ｍｏｌからな
る有機金属化合物含有溶液（４）を、前記支持材（１）
の上側表面に塗布した後、常温下に置いて１０分間風乾
してゲル化させた。Next, as shown in Figure 2, silicon tetraethoxide:
IOmol, 85% phosphorus fl! : 1 mol,
An organometallic compound-containing solution (4) consisting of 20 vol of ethanol and 5 mol of water was added to the support material (1).
After applying it to the upper surface, it was left at room temperature and air-dried for 10 minutes to form a gel.
上記ゲル化後、第３図に示す如く、前記固化した寒天（
２）を温水（５）で溶解して除去し、その後乾燥して温
水（５）を除去した。After the gelation, the solidified agar (
2) was dissolved and removed with hot water (5), and then dried to remove the hot water (5).
次に、上記乾燥後のものを、電熱器により５００℃で１
０分間加熱し、前記ゲルをガラス化した。Next, the dried product was heated to 500°C for 1 hour using an electric heater.
The gel was vitrified by heating for 0 minutes.
このようにして第４図に示す如き無機質非対称１！！Ｉ
（７）、即ち、多孔質アルミナ板（多孔質支持材）（１
）の片面に多孔質ガラス薄膜（６）を被覆してなる無機
質非対称Ｉｌ！ （７）を得た。In this way, the inorganic asymmetric 1! shown in FIG. ! I
(7), that is, porous alumina plate (porous support material) (1
) is coated with a porous glass thin film (6) on one side of the inorganic asymmetric Il! (7) was obtained.
上記無機質非対称１１１（７）についてガラス薄膜（６
）の細孔径をＢＥＴ法により測定し、又、断面顕微鏡観
察により厚みを測定した。その結果、ガラス薄膜（６）
の細孔径は２０〜５０人であった。ガラス）！ ｉ （
６）の実質的厚みは５０μ糟、多孔質支持材（１）中の
含浸ガラス層厚は５μｍ、多孔質支持材（１）の表面上
のガラス層厚は４５μｍであった。Regarding the above inorganic asymmetric 111 (7), the glass thin film (6
) was measured by the BET method, and the thickness was measured by cross-sectional microscopic observation. As a result, the glass thin film (6)
The pore size was 20-50 pores. glass)! i (
The substantial thickness of 6) was 50 μm, the thickness of the impregnated glass layer in the porous support material (1) was 5 μm, and the thickness of the glass layer on the surface of the porous support material (1) was 45 μm.
多孔質支持材（１）とガラス薄膜（６）との密着性を、
基盤目試験（ＪＩＳ Ｄ ０２０２）をして調べたとこ
ろ、該密着性は極めて良好であった。The adhesion between the porous support material (1) and the glass thin film (6) is
When examined by a board test (JIS D 0202), the adhesion was found to be extremely good.
直１．１
多孔質支持材表面に塗布する有機金属化合物含有溶液と
して、シリコンテトラエトキシド： １０ｇｒカルシウ
ムエトキシド：２ｇｒ、 ジルコニウムプロポキシド
：２ｇｒ、エタノール： ２０ｇｒ、水：］ｇｒからな
る溶液を使用した。かかる点を除き、実施例１の場合と
同様の方法により、多孔質アルミナ板（多孔質支持材）
の片面に多孔質ガラス薄膜を被覆してなる無機質非対称
膜を得た。次いで、実施例１の場合と同様の試験を行っ
た。その結果、ガラス薄膜の細孔径は２５〜４０人、実
質的厚みは５０μ蒙、多孔質支持材中の含浸ガラス層厚
は５μｍ、多孔質支持材の表面上のガラス層厚は４５μ
蒙であった。又、多孔質支持材とガラス薄膜との密着性
は極めて良好であった。Direction 1.1 As the organometallic compound-containing solution applied to the surface of the porous support material, a solution consisting of silicon tetraethoxide: 10 gr, calcium ethoxide: 2 gr, zirconium propoxide: 2 gr, ethanol: 20 gr, and water:] gr is used. did. A porous alumina plate (porous support material) was prepared in the same manner as in Example 1 except for this point.
An inorganic asymmetric membrane was obtained by coating one side of the membrane with a porous glass thin film. Next, the same test as in Example 1 was conducted. As a result, the pore diameter of the glass thin film is 25-40, the actual thickness is 50 μm, the thickness of the impregnated glass layer in the porous support is 5 μm, and the thickness of the glass layer on the surface of the porous support is 45 μm.
It was Meng. Furthermore, the adhesion between the porous support material and the glass thin film was extremely good.
（発明の効果）
本発明に係る無機質非対称膜の製造方法によれば、実質
的ガラス層厚を小さくし得ると共に、含浸ガラス層厚を
均一に且つ一定にし得るようになる。従って、目づまり
が生じ難く、又、濾過機能の再現性に優れると共に、耐
熱性及び耐久性に優れ、又、強酸性、強アルカリ性の条
件下で使用に耐え得る無機質非対称膜が得られるように
なる。(Effects of the Invention) According to the method for manufacturing an inorganic asymmetric membrane according to the present invention, the substantial glass layer thickness can be reduced, and the impregnated glass layer thickness can be made uniform and constant. Therefore, it becomes possible to obtain an inorganic asymmetric membrane that is less prone to clogging, has excellent reproducibility of filtration function, has excellent heat resistance and durability, and can withstand use under strongly acidic and strongly alkaline conditions. .
そのため、化学工業、医薬品工業、食品工業、醗酵工業
など、苛酷な腐食環境下でも充分に使用し得る無機質非
対称膜が得られるようになる。Therefore, it becomes possible to obtain an inorganic asymmetric membrane that can be used satisfactorily even in severe corrosive environments such as in the chemical industry, pharmaceutical industry, food industry, and fermentation industry.
第１〜４図は、実施例１に係る無機質非対称膜の製造過
程の概要を示す断面図である。
（１）−多孔質アルミナ板 （２）−寒天 （３）−ガ
ラス板 （４）−有機金属化合物音を溶液 （５）−
温水（６）−多孔質ガラス蒲ＭＷ （７）−無ＩＲ
質非対称膜第２図
第３図1 to 4 are cross-sectional views showing an overview of the manufacturing process of the inorganic asymmetric membrane according to Example 1. (1)-Porous alumina plate (2)-Agar (3)-Glass plate (4)-Organometallic compound sound solution (5)-
Hot water (6) - Porous glass cap MW (7) - No IR
Quality asymmetric membrane Figure 2 Figure 3
Claims (2)
の表側表面に被覆してなる無機質非対称膜を製造するに
際し、多孔質支持材の裏側表面から温水に可溶性の封孔
剤溶液を含浸し、冷却固化した後、該支持材の表側表面
に有機金属化合物含有溶液を塗布し、ゲル化した後、前
記固化した封孔剤を温水で再溶解して除去し、前記ゲル
を加熱処理してガラス化することを特徴とする無機質非
対称膜の製造方法。(1) When producing an inorganic asymmetric membrane in which the front surface of a porous support material is coated with a porous glass thin film having micropores, a hot water-soluble sealant solution is impregnated from the back surface of the porous support material. After cooling and solidifying, an organometallic compound-containing solution is applied to the front surface of the support material, and after gelling, the solidified sealant is removed by redissolving with warm water, and the gel is heat-treated. A method for producing an inorganic asymmetric membrane, the method comprising vitrifying the inorganic asymmetric membrane.
非対称膜の製造方法。(2) The method for producing an inorganic asymmetric membrane according to claim 1, wherein the sealant is agar.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8330690A JPH03284330A (en) | 1990-03-29 | 1990-03-29 | Production of inorganic asymmetric membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8330690A JPH03284330A (en) | 1990-03-29 | 1990-03-29 | Production of inorganic asymmetric membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03284330A true JPH03284330A (en) | 1991-12-16 |
Family
ID=13798733
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8330690A Pending JPH03284330A (en) | 1990-03-29 | 1990-03-29 | Production of inorganic asymmetric membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03284330A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07213877A (en) * | 1994-02-04 | 1995-08-15 | Agency Of Ind Science & Technol | Inorganic xerogel film, its production and gas separating membrane made of the same |
| WO2003003887A1 (en) * | 2001-07-04 | 2003-01-16 | Frange Co., Ltd. | Filter and filter manufacturing method |
| WO2005023407A3 (en) * | 2003-07-10 | 2006-07-20 | Praxair Technology Inc | Method of forming ion transport membrane structure |
| JP2011125818A (en) * | 2009-12-18 | 2011-06-30 | Research Institute Of Innovative Technology For The Earth | Method for manufacturing composite |
-
1990
- 1990-03-29 JP JP8330690A patent/JPH03284330A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07213877A (en) * | 1994-02-04 | 1995-08-15 | Agency Of Ind Science & Technol | Inorganic xerogel film, its production and gas separating membrane made of the same |
| WO2003003887A1 (en) * | 2001-07-04 | 2003-01-16 | Frange Co., Ltd. | Filter and filter manufacturing method |
| WO2005023407A3 (en) * | 2003-07-10 | 2006-07-20 | Praxair Technology Inc | Method of forming ion transport membrane structure |
| JP2011125818A (en) * | 2009-12-18 | 2011-06-30 | Research Institute Of Innovative Technology For The Earth | Method for manufacturing composite |
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