JPH0398627A - Preparation of ceramic filter - Google Patents
Preparation of ceramic filterInfo
- Publication number
- JPH0398627A JPH0398627A JP23774989A JP23774989A JPH0398627A JP H0398627 A JPH0398627 A JP H0398627A JP 23774989 A JP23774989 A JP 23774989A JP 23774989 A JP23774989 A JP 23774989A JP H0398627 A JPH0398627 A JP H0398627A
- Authority
- JP
- Japan
- Prior art keywords
- support
- thin film
- porous
- coating
- gel layer
- 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
- 239000000919 ceramic Substances 0.000 title claims abstract description 17
- 239000010409 thin film Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 25
- 239000011148 porous material Substances 0.000 claims abstract description 25
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims description 50
- 239000011248 coating agent Substances 0.000 claims description 46
- 239000000565 sealant Substances 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 27
- 238000010304 firing Methods 0.000 abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010408 film Substances 0.000 abstract description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract description 3
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 229910052682 stishovite Inorganic materials 0.000 abstract description 3
- 229910052905 tridymite Inorganic materials 0.000 abstract description 3
- 150000004703 alkoxides Chemical class 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 238000007789 sealing Methods 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000012528 membrane Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 230000002093 peripheral effect Effects 0.000 description 5
- 102000004169 proteins and genes Human genes 0.000 description 5
- 108090000623 proteins and genes Proteins 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000003618 dip coating Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 229920005646 polycarboxylate Polymers 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000009295 crossflow filtration Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001732 thrombotic effect Effects 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は限外濾過膜、精密濾過膜等に使用されるセラミ
ックフィルタに関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a ceramic filter used for ultrafiltration membranes, precision filtration membranes, etc.
（従来技術〉
従来各種の分野に使用される濾過膜として、機械的強度
が高く、かつ耐熱性および耐蝕性に優れたセラミックフ
ィルタがある。かかるセラミックフィルタにおいては、
非処理流体の透過時の流通抵抗を可能なかぎり小さくす
るため、細孔径の大きな多孔質支持体の一側または両測
に￥ｉ過能を有する薄膜を固着した複層構造のフィルタ
が一般であり、上記薄膜は被処理流体の種類により選定
される．本発明が対象とする限外濾過膜、精密濾過膜等
に適した無機多孔質膜においては、上記薄膜として細孔
径がＩＡ〜１０００＾の範囲にあるものが選定されるべ
きものである。また、かかるセラミックフィルタにおい
ては端部を透して被処理液と濾液との接触、混合を避け
るため、端部を封止剤により無孔化されることが多い。(Prior Art) Ceramic filters that have high mechanical strength and excellent heat resistance and corrosion resistance are conventionally used as filtration membranes in various fields. In such ceramic filters,
In order to minimize the flow resistance during permeation of untreated fluids, filters with a multi-layer structure are generally used, in which a thin film with a high capacity is fixed to one or both sides of a porous support with a large pore diameter. Yes, the thin film mentioned above is selected depending on the type of fluid to be treated. In inorganic porous membranes suitable for ultrafiltration membranes, precision filtration membranes, etc. targeted by the present invention, those having pore diameters in the range of IA to 1000^ should be selected as the above-mentioned thin membranes. Further, in such ceramic filters, the ends are often made non-porous with a sealant in order to avoid contact and mixing of the liquid to be treated and the filtrate through the ends.
しかして、多孔質支持体の一側に薄膜を形成するには、
薄膜形成成分の粉体のスラリーを多孔質支持体の一側に
コーティングしてこれを焼成する手段が採られるが、ス
ラリー中の粒子が大きいことからかかる手段にて形成さ
れる薄膜の細孔径は大きく、上記した範囲の細孔径を有
する薄膜を形成することは難しい．このため、かかる極
めて微細な細孔径を有する多孔質膜を製造する方法とし
て、特開昭５９−５９２２３号公報および特開昭６０−
１８０９７９号公報に示された方法が提案されている。Therefore, to form a thin film on one side of a porous support,
A method of coating one side of a porous support with a slurry of powder of the thin film-forming component and firing it is adopted, but since the particles in the slurry are large, the pore size of the thin film formed by this method is It is difficult to form a thin film with large pore diameters within the above range. For this reason, as a method for manufacturing a porous membrane having such extremely fine pore diameters, Japanese Patent Laid-Open Nos. 59-59223 and 60-60
A method disclosed in Japanese Patent No. 180979 has been proposed.
前者の方法は、多孔質体の細孔中に液状のアルミニウム
アルコラートまたはアルミニウムキレーｌ・を含浸させ
た後、加水分解してベーマイｌ・・ゲルとしその後焼成
する方法であり、また後者の方法は多孔質体の細孔中に
上記化合物を加水分解して得たアルミナゾルを含浸させ
た後、乾燥および焼成する方法である。これら両者の方
法はいずれも多孔質体中の大径の細孔にアルミナゲルを
充填して微細な細孔を残存させようとするものである．
また、有機金属化合物を加水分解しまたはシリカ微粉を
分散させて得たゾル液を基材の表面にコーティングして
ゲル層を形成し、これを焼成して超微細な細孔のガラス
状薄膜を形成する方法が刊行物「応用物理第５５巻第７
号第６９３頁〜第６９６頁」に示されている。The former method involves impregnating liquid aluminum alcoholate or aluminum chelate into the pores of a porous material, and then hydrolyzing it to form a boehmite gel. This is a method in which the pores of a porous body are impregnated with alumina sol obtained by hydrolyzing the above compound, followed by drying and firing. Both of these methods attempt to fill large pores in a porous material with alumina gel to leave fine pores.
In addition, a sol solution obtained by hydrolyzing an organometallic compound or dispersing fine silica powder is coated on the surface of a substrate to form a gel layer, which is then fired to form a glass-like thin film with ultra-fine pores. The method of forming is described in the publication ``Applied Physics Vol.
No. 693-696.
一方多孔質支持体の端部を封止剤にて無孔化するには、
各種の封止剤のスラリーを上記した端部にコーティング
してこれを焼成する方法が採られ、また封止剤としては
耐蝕性に優れていること、有害組或を含まないこと等か
らＢ２０３・Ｎａ２０、Ｓｉ０２・Ａｌ２０，等が用い
られる。これらの封止剤はコーティング後の焼成温度が
高いほど耐蝕性に優れたものとなり、一般に焼成温度は
１０００℃〜１５００℃である。On the other hand, to make the ends of the porous support non-porous with a sealant,
A method is adopted in which a slurry of various sealants is coated on the above-mentioned ends and then fired.B203 is also used as a sealant because it has excellent corrosion resistance and does not contain harmful components. Na20, Si02.Al20, etc. are used. The higher the firing temperature after coating, the more excellent the corrosion resistance of these sealants becomes, and the firing temperature is generally 1000°C to 1500°C.
（発明が解決しようとする課題〉
ところで、上記した両公報に示された方法においては同
公報にも明記されているように、多孔質体中の大径の細
孔内へのアルミナゲルの充填が十分には行えないととも
に乾燥または焼成時の収縮によりアルミナゲルにひび割
れが生じ易く、ビンホール、クラック等の発生が多くて
目的とする濾過能を有するフィルタは得られないことが
多い。(Problems to be Solved by the Invention) By the way, in the methods shown in both of the above-mentioned publications, as specified in the same publication, it is necessary to fill alumina gel into large-diameter pores in a porous body. In addition, the alumina gel tends to crack due to shrinkage during drying or firing, and a filter having the desired filtration performance cannot be obtained in many cases due to the occurrence of bottle holes, cracks, etc.
また、上記した刊行物に示された所謂ゾルーゲル法によ
る薄膜の形成には、ゾル液中のコロイド粒子がＩＯＡ〜
ＩＯＯＯＡと超微粒であることがら基材として無孔質ま
たは超微細な細孔の基材が用いられ、細孔径の大きな多
孔質支持体の表面にゾル液をコーティングしてゲル層を
形戒することは難しく、かつゾル液に多孔質支持体を浸
漬するディップコーティングによりゾル液をコーティン
グしてゲル層を形戒し得るが、その後焼或により形戊さ
れた薄膜と支持体との結合強度がかならずしも十分では
なく、かつコーティング後支持体をゾル液から引上げる
際にコーティングされたゾル液が垂れ下がり、支持体の
両端部においてはゲル層の厚みに大きな差が生じる．従
って、ゾルーゲル法によるディップコーティングによっ
て薄膜を形戒する方法を採る場合には以下の工程を採る
ことになる。すなわち、
（１）多孔質支持体の一側にゾル液をコーティングして
ゲル層を形或する。In addition, in forming a thin film by the so-called sol-gel method shown in the above-mentioned publication, colloidal particles in the sol solution are
Because IOOOA has ultrafine particles, a nonporous or ultrafine pore base material is used as the base material, and a gel layer is formed by coating the surface of the porous support with a large pore size with a sol solution. Although it is difficult to form a gel layer by coating a porous support with a sol solution by dip coating, the bond strength between the formed thin film and the support is reduced by subsequent baking. This is not always sufficient, and when the support is pulled up from the sol solution after coating, the coated sol solution hangs down, resulting in a large difference in the thickness of the gel layer at both ends of the support. Therefore, when a method of forming a thin film by dip coating using the sol-gel method is adopted, the following steps are taken. That is, (1) one side of a porous support is coated with a sol solution to form a gel layer.
（′；Ａゲル層を焼威して薄膜を形成する。(';A Burn out the gel layer to form a thin film.
（３）得られた多孔質膜の両端部を所定長さ切断して、
切断後の両端部に封止剤のスラリーをコーティングする
。(3) Cut both ends of the obtained porous membrane to a predetermined length,
Coat both ends of the cut with a slurry of sealant.
（４）コーティングした封止剤を焼或して無孔化する。(4) Burning the coated sealant to make it non-porous.
しかしながら、かかる方法においては、（２）工程のゲ
ル層の焼成温度は微細孔の大きさおよび薄膜の剥離強度
の点から３００℃〜８００℃が好ましく、一方０）工程
の封止剤の焼或温度は好適な封ＩＩ：．剤の耐蝕性の点
から１０００℃〜１５００℃が好ましいことから、薄膜
および封止剤の特性の少なくとも一方を犠牲にした焼成
温度を採らざるを得ない。However, in this method, the firing temperature of the gel layer in the step (2) is preferably 300°C to 800°C from the viewpoint of the size of the micropores and the peel strength of the thin film, while the firing temperature of the sealant in the step 0) is preferably 300°C to 800°C. The temperature is set to a suitable seal II:. Since 1000° C. to 1500° C. is preferable from the viewpoint of corrosion resistance of the agent, the firing temperature must be set at a sacrifice of at least one of the characteristics of the thin film and the sealant.
また、これらの方法とは別に以下の工程を採ることも考
えられる。すなわち、
（１’）多孔質支持体の両端部に封止剤のスラリーをコ
ーティングする。In addition to these methods, the following steps may also be considered. (1') Coating a sealant slurry on both ends of the porous support.
（２′）コーティングした封止剤を焼成して無孔化する
。(2') The coated sealant is fired to make it non-porous.
（３′）端部を無孔化された多孔質支持体の一側にゾル
液をコーティングしてゲル層を形戒する。(3') A gel layer is formed by coating one side of the porous support whose ends are made non-porous with a sol solution.
（４′）ゲル層を焼成して薄膜を形成する。(4') Burn the gel layer to form a thin film.
しかしながら、かかる方法においてはデイツブコーティ
ング法に起因して特に薄膜の無孔化部位との境の結合が
弱く、当該部位にクラツクや薄膜の剥離が発生する．
従って、本発明の目的はこれらの問題に対処しようとす
るもので、限外濾過膜、精密濾過膜等に有効なセラミッ
クフィルタの製造方法を提供することにある．
（課題を解決するための手段）
本発明は、セラミックの多孔質支持体の一側にコロイド
粒子のゲル層を前駆体とする孔径１＾〜１０００＾の細
孔を有するセラミックの薄膜を備え、端部が封止剤にて
無孔化されているセラミックフィルタの製造方法であり
、下記（１）〜（４）の工程を備えていることを特徴と
するものである。However, in this method, due to the date coating method, the bond between the thin film and the non-porous region is particularly weak, and cracks or peeling of the thin film occur at the region. Therefore, an object of the present invention is to address these problems and to provide a method for manufacturing a ceramic filter that is effective for ultrafiltration membranes, microfiltration membranes, and the like. (Means for Solving the Problems) The present invention includes a ceramic thin film having pores with a pore diameter of 1^ to 1000^ using a gel layer of colloidal particles as a precursor on one side of a ceramic porous support, This is a method for manufacturing a ceramic filter whose end portions are made non-porous with a sealant, and is characterized by comprising the following steps (1) to (4).
（１）前記多孔質支持体の端部に封止剤のスラリーをコ
ーティングする。(1) Coating the end of the porous support with a sealant slurry.
（２）コーティングされた封止剤を焼成して前記多孔質
支持体の端部を無孔化する。(2) Burning the coated sealant to make the ends of the porous support non-porous.
（３）端部を無孔化された多孔質支持体の一側に有機バ
インダーを含有する前記コロイド粒子のゾル液を供給し
、同支持体の両側間の圧力差によりコーティングして前
記コロイド粒子のゲル層を形成する．
（４）前記ゲル層を焼成して薄膜を形成する．しかして
、本発明において封止剤としてはＳＩ０２＾１２０３を
主成分とするフリットが好ましく、その好ましい焼成温
度は１０００℃〜１５００℃である．また、ゾル液は金
属アルコキシド等有機金属化合物を適宜の溶媒中で加水
分解することにより、また金属水酸化物、無機質微粉を
適宜の溶媒に分散させて形戒される。有機バインダーは
セラミックの成形分野で使用される結合剤、粘結剤等が
好適で、具体的にはポリビニルアルコール、ポリエチレ
ングリコール、メチルセルロース、デンプン等を挙げる
ことができる。かかるゾル液をコーティングして形或さ
れたゲル層の好ましい焼或温度は３００゜Ｃ〜８００゜
Ｃである。(3) A sol solution of the colloidal particles containing an organic binder is supplied to one side of a porous support whose end has been made non-porous, and the colloidal particles are coated by a pressure difference between both sides of the support. Form a gel layer. (4) The gel layer is fired to form a thin film. Therefore, in the present invention, a frit containing SI02^1203 as a main component is preferred as the sealant, and its preferred firing temperature is 1000°C to 1500°C. Further, a sol solution is prepared by hydrolyzing an organometallic compound such as a metal alkoxide in an appropriate solvent, or by dispersing a metal hydroxide or an inorganic fine powder in an appropriate solvent. Suitable organic binders include binders and binders used in the field of ceramic molding, and specific examples include polyvinyl alcohol, polyethylene glycol, methyl cellulose, and starch. The preferred firing temperature of the gel layer formed by coating with such a sol solution is 300°C to 800°C.
（発明の作用・効果）
本発明の製造方法においては、ゾル液を多孔質支持体の
一側に供給し、同支持体の両側間の圧力差を利用してコ
ーティングしてゲル層を形成するものであるが、一般に
ゾル液をかかる方法により支持体にコーティングすると
、支持体の細孔径が大きいためゾル液中のコロイド粒子
が支持体を透過してコーティング不能であるか、または
コーティングの歩留まりが非常に悪い。しかしながら、
本発明においては有機バインダーを含むゾル液を使用し
ているため、ゾル液中のコロイド粒子は支持体の表面に
付着してゲル層を形成するとともに、支持体の両側間の
圧力差により支持体の表面に開口する細孔内に侵入し、
ゲル層はその裏側に支持体の表面に侵入した強度の高い
結合状態となる。(Operations and Effects of the Invention) In the production method of the present invention, a sol solution is supplied to one side of a porous support, and a gel layer is formed by coating using the pressure difference between both sides of the support. However, when a support is coated with a sol by such a method, the colloidal particles in the sol pass through the support due to the large pore size of the support, making coating impossible or reducing the coating yield. Very bad. however,
In the present invention, since a sol containing an organic binder is used, the colloidal particles in the sol adhere to the surface of the support to form a gel layer, and the pressure difference between both sides of the support causes the colloid particles to adhere to the surface of the support. penetrates into the pores that open on the surface of
The gel layer penetrates the surface of the support on its back side and forms a highly bonded state.
また支持体の両側間の圧力差を利用してゾル液を支持体
の一側にコーティングする方法は、従来のディップコー
ティング法に比較して一定の品質のゲル層を形或し易く
、かつ大型の支持体に対しても容易にコーティングし得
るため、この種無機多孔質膜の量産化に適している。In addition, the method of coating one side of the support with a sol solution using the pressure difference between both sides of the support makes it easier to form a gel layer of constant quality than the conventional dip coating method, and It is suitable for mass production of this type of inorganic porous membrane because it can be easily coated on supports such as .
従って、かかるゾル液のコーティング法を採用すればゲ
ル層を焼成してなる薄膜も全長にわたって均等で、ゾル
液のコーティングに先立って多孔質支持体の端部を封止
剤により無孔化しておくことができ、これにより前工程
である封止剤の焼成温度を最適の１０００℃〜１５００
℃という高温にすることができ、かつ後工程であるゲル
層の焼成温度を最適の３００℃〜８００℃という中程度
の温度にすることができて、優れたセラミックフィルタ
が得られる。この場合薄膜の多孔質支持体への結合強度
が高いので、薄膜の無孔化部位との境の結合強度も当然
に高く、当該部位にクラックや薄膜の剥離が発生するこ
とはない。Therefore, if such a sol coating method is adopted, the thin film obtained by firing the gel layer will be uniform over the entire length, and the ends of the porous support should be made nonporous with a sealant before coating with the sol solution. As a result, the firing temperature of the sealant in the previous step can be adjusted to the optimum temperature of 1000°C to 1500°C.
It is possible to raise the temperature to a high temperature of 300°C to 800°C, and the firing temperature of the gel layer, which is a post-process, can be set to the optimum temperature of 300°C to 800°C, resulting in an excellent ceramic filter. In this case, since the bonding strength of the thin film to the porous support is high, the bonding strength at the boundary between the thin film and the non-porous region is naturally high, and cracks and peeling of the thin film do not occur at the site.
（実施例）
以下本発明を図面に基づいて説明するに、第１図にはゾ
ル液の多孔質支持体へのコーティング装置が示され、第
２図および第３図は本発明に係るセラミックフィルタお
よびこれに対応する比較例に係るセラミックフィルタの
断面の電子顕微鏡写真、第４図および第５図はこれらフ
ィルタの表面の電子顕微鏡写真である。(Example) The present invention will be explained below based on the drawings. Fig. 1 shows a coating device for coating a porous support with a sol solution, and Figs. 2 and 3 show a ceramic filter according to the present invention. 4 and 5 are electron micrographs of the surfaces of these filters.
（１）コーティング装置
第１図に示すコーティング装置ＩＯは特開昭６１−２３
８３１５号公報に示された装置に類似するもので、圧力
容器１１内に筒状の多孔質支持体Ａの保持機１ｉｆ４
１ ０ ａを収容してなる。保持機構ｌＯａは上下一対
の支持板１２ａ、１２ｂと複数の連結ボルト１３ａ、１
３ｂ・・・とを備え、これらの連結ボルト１３ａ、１３
ｂ・・・にて両支持板１２ａ、１２ｂを互いに連結する
ことにより、支持体Ａが両支持板１２ａ、１２ｂにて挟
持される．下側支持板１２ａにはコーティング液Ｂを収
容するタンク１４に接続する供給バイブ１５ａが接続さ
れており、同バイプ１５ａは支持体Ａの下端部にて開口
し供給ボンブ１５ｂの駆動によりタンク１４内のコーテ
ィング液Ｂを支持体Ａに供給する。なお、供給パイブ１
５ａには排出パイプ１５ｃが接続されており、同パイプ
１５ｃはコーティング作業終了後支持体Ａ内のコーティ
ング液Ｂをタンク１４内に排出する。(1) Coating device The coating device IO shown in FIG.
This device is similar to the device shown in Japanese Patent No. 8315, and includes a holder 1if4 of a cylindrical porous support A in a pressure vessel 11.
It accommodates 10a. The holding mechanism lOa includes a pair of upper and lower support plates 12a, 12b and a plurality of connecting bolts 13a, 1.
3b..., and these connecting bolts 13a, 13
By connecting both support plates 12a and 12b to each other at b..., support body A is held between both support plates 12a and 12b. A supply vibrator 15a connected to a tank 14 containing coating liquid B is connected to the lower support plate 12a. Coating liquid B is supplied to support A. In addition, supply pipe 1
A discharge pipe 15c is connected to 5a, and the pipe 15c discharges the coating liquid B in the support A into the tank 14 after the coating operation is completed.
一方、上側支持板１２ｂにはタンク１４上に臨む流出バ
イプ１６ａが接続されており、同パイブ１６ａは支持体
Ａの上端部に開口し支持体Ａからオーバーフローするコ
ーティング液Ｂをタンク１４内へ還流させる。また、圧
力容器１１の一側上部には真空ボンプ１７ａに接続した
排気バイブ１７ｂが接続され、真空ボンプ１７ａの駆動
により圧力容器１１内が所望の圧力に減圧される。圧力
容器１１の一側には水量計１７ｃが取付けられており、
同水量計１７ｃはコーティング作業時支持体Ａを透過し
て圧力容器１１内に流出する水量を表示する．
当該コーティング装置においては、流出パイプ１６ａが
有する絞り弁１６ｂを全開にした状態にてボンプ１５ｂ
を駆動してコーティング液Ｂを支持体Ａ内に供給し、コ
ーティング液Ｂが支持体Ａの上端部に達した時点で真空
ボンプ１７ａを駆動させて圧力容器１１内を減圧にする
とともに、絞り弁１６ｂを所定量絞ってコーティング液
Ｂを支持体Ａ内を加圧状態で上方へ循環させる。これに
より、支持体Ａの内外側に圧力差が生じ、この圧力差に
よりコーティング液Ｂ中の水分が支持体Ａを透過して圧
力容器１１内に流出し、この間コーティング液Ｂ中の薄
膜形成成分が支持体Ａの内周面に担持されて薄膜が形戒
される。なお、薄膜の膜厚は圧力容器ｌｌ内に流出する
水量に比例するため、水量計１７ｃにて表示される水量
に基づいて膜厚が調整される。薄膜の膜厚が所定の厚さ
になった時点で、供給ボンブ１５ｂを停止した後、絞り
弁１６ｂを全開とし、かつ排出パイブ１５ｃが有する開
閉弁１５ｄを開放し、その後減圧脱水を数分間行い真空
ポンブ１７ａの駆動を停止させる．これにより、支持体
Ａ内のコーティング液Ｂが排出パイブ１５ｃを通してタ
ンク１４内へ排出され、コーティング作業が終了する．
なお、本発明においてはコーティング液Ｂとしてゾル液
を使用するものであり、支持体Ａの内周面にはゾル液中
のコロイド粒子が担持されてゲル層が形成される．
（２］多孔質支持体Ａ
ａｌ ：平均粒子径３０μｍのアルミナを主成分とする
焼成された円筒体（外径３０ｍｍ、内径２４ｍｍ、長さ
５００ｍｎ＋ 、最大気孔径７μｍ〉の内周面に、平均
粒子径３，０μｍのアルミナを主成分とする粒体に有機
バインダーを添加して調製した水分８０ｗｔ％のスラリ
ーを第１図に示す装置を用いてコーティングして中間層
を形成し、これを１５００℃で焼成して千均細孔径ｌＪ
ｉｍとする．
ａ２ ：支持体ａ１の両端部に封止剤のスラリーをコー
ティングし、これを１３００℃で焼成して両端部を無孔
化する。On the other hand, an outflow pipe 16a facing above the tank 14 is connected to the upper support plate 12b, and the pipe 16a opens at the upper end of the support A to recirculate the coating liquid B overflowing from the support A into the tank 14. let Further, an exhaust vibrator 17b connected to a vacuum pump 17a is connected to the upper part of one side of the pressure vessel 11, and the pressure inside the pressure vessel 11 is reduced to a desired pressure by driving the vacuum pump 17a. A water meter 17c is attached to one side of the pressure vessel 11.
The water meter 17c displays the amount of water that passes through the support A and flows into the pressure vessel 11 during the coating operation. In the coating apparatus, the pump 15b is opened while the throttle valve 16b of the outflow pipe 16a is fully opened.
is driven to supply the coating liquid B into the support A, and when the coating liquid B reaches the upper end of the support A, the vacuum pump 17a is driven to reduce the pressure inside the pressure vessel 11, and the throttle valve is activated. 16b is squeezed by a predetermined amount to circulate the coating liquid B upward within the support A under pressure. This creates a pressure difference between the inside and outside of the support A, and due to this pressure difference, water in the coating liquid B permeates through the support A and flows into the pressure vessel 11, and during this time, the thin film forming components in the coating liquid B is supported on the inner circumferential surface of support A to form a thin film. Note that since the thickness of the thin film is proportional to the amount of water flowing out into the pressure vessel 11, the thickness is adjusted based on the amount of water displayed by the water meter 17c. When the thickness of the thin film reaches a predetermined thickness, the supply bomb 15b is stopped, the throttle valve 16b is fully opened, and the on-off valve 15d of the discharge pipe 15c is opened, and then dehydration is performed under reduced pressure for several minutes. Stop driving the vacuum pump 17a. As a result, the coating liquid B in the support A is discharged into the tank 14 through the discharge pipe 15c, and the coating operation is completed. In the present invention, a sol liquid is used as the coating liquid B, and the colloidal particles in the sol liquid are supported on the inner peripheral surface of the support A to form a gel layer. (2) Porous support A al: A fired cylindrical body mainly composed of alumina with an average particle size of 30 μm (outer diameter 30 mm, inner diameter 24 mm, length 500 m+, maximum pore diameter 7 μm) on the inner peripheral surface An intermediate layer was formed by coating a slurry with a water content of 80 wt% prepared by adding an organic binder to particles mainly composed of alumina with a particle size of 3.0 μm using the apparatus shown in FIG. Calcinate at ℃ to obtain 1,000 uniform pore diameter lJ
Let's say im. a2: Both ends of the support a1 are coated with a sealant slurry, and this is fired at 1300° C. to make both ends non-porous.
ａ，：支持体ａ１の内周面に、平均粒子径０．６μｍの
アルミナを主成分とする粉体に有機バインダーを添加し
て調製した水分９５ｗｔ％のスラリーを第１図に示す装
置を用いてコーティングし第２の中間層を形成し、これ
を１４００℃で焼成して平均細孔径０．２μｍとする．
ａ４：支持体ａ３の両端部に封止剤のスラリーをコーテ
ィングし、これをｌ３００℃で焼成して両端部を無孔化
する。なお、これらのコーティング方法においてはコー
ティングに先立って支持体を水中で３時間煮沸して脱泡
し、また圧力容器１１内の真空度を７３０ｍｍＨｇ〜７
４０＋＊ｍ｝Ｉｇ 、懸濁液の支持体の内周面に対する
液圧を２ｋｇ／ｃｏ＋２、その流動接触時間を１分２０
秒間とするとともに、懸濁液排出後上記真空下で５分間
減圧脱水している．また、支持体ａｌ 、ａ３について
は後述する薄膜形成後に両端部に封止剤のスラリーをコ
ーティングし、これを１３００℃で焼成して両端部を無
孔化している．
（３）封止剤のスラリー
封止剤としてＳ ｉ０２・ＡＩ２０３を主成分とするフ
リ？トを用い、この平均粒子径０．５μｍの粉体６０ｗ
ｔ％と、有機バインダーであるポリカルボン酸アンモニ
ウム０．５ｗｔ％およびメチルセルロース０．５ｗｔ％
とを水に添加してスラリーを調製した。a,: A slurry with a moisture content of 95 wt % prepared by adding an organic binder to powder mainly composed of alumina with an average particle size of 0.6 μm was applied to the inner peripheral surface of the support a1 using the apparatus shown in FIG. A second intermediate layer is formed by coating, and this is fired at 1400°C to give an average pore diameter of 0.2 μm. a4: Both ends of support a3 are coated with a sealant slurry, and this is fired at 1300°C to make both ends non-porous. In addition, in these coating methods, prior to coating, the support is boiled in water for 3 hours to defoam, and the degree of vacuum in the pressure vessel 11 is set to 730 mmHg to 7.
40+*m}Ig, the liquid pressure of the suspension against the inner peripheral surface of the support is 2 kg/co+2, and the fluid contact time is 1 minute 20
After discharging the suspension, the suspension was dehydrated under reduced pressure for 5 minutes under the vacuum described above. Further, for the supports al and a3, both ends were coated with a sealant slurry after forming a thin film as described later, and this was baked at 1300°C to make both ends non-porous. (3) Encapsulant slurry A sealant containing Si02/AI203 as the main component? 60w of this powder with an average particle size of 0.5μm
t%, organic binder ammonium polycarboxylate 0.5wt% and methylcellulose 0.5wt%
was added to water to prepare a slurry.
（４１薄膜原料
ｂＩ ：平均粒子径０．８μｍのアルミナを主戒分とす
る粉体と有機バインダー（ポリカルボン酸アンモニウム
ｌｗｔ％、ポリアクリル酸アンモニウムＬｗｔ％）を添
加した水分９５ｗｔ％のスラリー
ｂ２：平均粒子径０．１μｍのチタニアを主成分とする
粉体とポリカルボン酸アンモニウム２Ｗｔ％を添加した
水分９８ｗｔ％のスラリーｂ３：ＴｉＯ■換算で０．０
５ｗｔ％のＴｉ０２系ゾル液で、有機バインダーである
ポリビニルアルコール０．５ｗｔ％、消泡剤であるｎ−
オクチルアルコール０．０５ｗｔ％を含有する水分９９
．４ｗｔ％のゾル液（なお、かかるゾル液は下記の方法
により調製）。(41 Thin film raw material bI: Slurry b2 with a water content of 95 wt%, containing powder mainly containing alumina with an average particle size of 0.8 μm and an organic binder (ammonium polycarboxylate lwt%, ammonium polyacrylate Lwt%): Slurry b3 with a water content of 98 wt%, containing powder mainly composed of titania with an average particle size of 0.1 μm and 2 wt% ammonium polycarboxylate: 0.0 in terms of TiO■
5wt% Ti02-based sol solution, 0.5wt% polyvinyl alcohol as an organic binder, and n- as an antifoaming agent.
Water containing 0.05wt% octyl alcohol99
．． 4 wt% sol solution (this sol solution was prepared by the method below).
チタニウムイソブロポキシド０．５５５ｍｌをイオン？
換水５５．５ｍｏｌ中に添加して約８５℃の温度で０．
５時間加水分解し、次いでこれに硝酸０．１ｍｏｌを添
加してＴｉＯ■をコロイド粒子とする ４．４ｗｔ％の
ゾル液とし、その後約９８℃で１．５一時間加熱してイ
ソプロビルアルコールを飛散させるとともに、これを稀
釈してＯｊ７ｗｔ％のゾル液となし、このゾル液を原液
として上記のごとく調製した。Ionize 0.555ml of titanium isopropoxide?
It was added to 55.5 mol of replaced water and heated to 0.5 mol at a temperature of about 85°C.
Hydrolyzed for 5 hours, then added 0.1 mol of nitric acid to form a 4.4 wt% sol solution to make TiO into colloidal particles, and then heated at about 98°C for 1.5 hours to dissolve isopropyl alcohol. While scattering, this was diluted to obtain a sol solution of Oj7wt%, and this sol solution was prepared as a stock solution as described above.
（５）スラリー、ゾル液のコーティング動加圧真空法Ｃ
１ ：
第１図に示すコーティング装置を用い、圧力容器１１内
の真空度を７００〜７４０ｍｍ［ｌｇ 、コーティング
液の流速１．５Ｎ２ ／＋ｉｎ、支持体の内周面に対す
る圧力１ｋｇ／ｃｍ２、コーティング液の流動接触時間
を２分としてコーティング液をコーティングする．その
後、コーティング液を排出し減圧脱水を５分間行う。(5) Coating slurry and sol liquid dynamic pressure vacuum method C
1: Using the coating apparatus shown in FIG. 1, the degree of vacuum in the pressure vessel 11 was set to 700 to 740 mm [lg], the flow rate of the coating liquid was 1.5 N2/+in, the pressure on the inner peripheral surface of the support was 1 kg/cm2, and the coating liquid was Coat the coating solution with a flow contact time of 2 minutes. Thereafter, the coating liquid was drained and dehydration was performed under reduced pressure for 5 minutes.
ディップコーティング法Ｃ２ （デイ・ンビング）二
支持体を円筒状ガラス容器に同心的に挿入して、支持体
の両端外周に嵌着した環状のゴム栓をガラス容器の開口
端に嵌着し、支持体の両端のみを開口した状態で支持す
る。かかる支持体をガラス容器と一体に起立状態でコー
ティング液中に浸漬し、１分間経過後引上げる。次いで
、これを室温で４８時間自然乾燥した後４０℃で５時間
、１００℃で１時間乾燥する．
（６）薄膜（焼成体〉の特性
フィルタの薄膜表面および切断面の走査型電子顕微鏡の
写真を撮り、薄膜表面のクラックの有無、膜の剥離の有
無、膜と封止剤間の剥離の有無および膜厚を観察した。Dip coating method C2 Two supports are inserted concentrically into a cylindrical glass container, and annular rubber plugs fitted around the outer periphery of both ends of the support are fitted into the open end of the glass container to support the glass container. Support the body with only both ends open. Such a support is immersed together with a glass container in an upright state in a coating liquid, and pulled out after 1 minute has elapsed. Next, this was naturally dried at room temperature for 48 hours, then at 40°C for 5 hours and at 100°C for 1 hour. (6) Characteristics of the thin film (fired body) Take scanning electron microscope photographs of the thin film surface and cut surface of the filter, and check whether there are cracks on the thin film surface, whether there is peeling of the film, and whether there is peeling between the film and the sealant. and the film thickness was observed.
（７）クロスフロー濾過
被処理液として分画分子量２．５万のα−チモトリシノ
ゲン（ｄ１）、分画分子量４，５万の牛血栓アルブミン
（ｄ２〉をそれぞれ用い、これらの各蛋白質をリン酸塩
緩衝液中に溶解して濃度１００ｐｐｍの２種類の被処理
液を調製した。これらの各被処理液を多孔質膜をフィル
タとする濾過器に循環供給し、循環流速２ｍ／ｓｅ（、
濾過圧力１ｋｇ／ｃ＋ａ２、濾過時間６０分でクロスフ
ロー濾過を行い、母液と濾液との液体クロマトグラフイ
ーのチャートの積分強度から、下記式により阻止率を算
出した．（８）考察
別表および第２図〜第５図の電子顕微鏡の写真から判断
すると、以下のことが明らかである。なお、図において
第２図および第３図は別表のＮ（Ｌ １２、Ｎ［Ｌ１１
のフィルタの断面、第４図および第５図はこれらフィル
タの薄肢表面である。(7) α-thymotrichinogen (d1) with a molecular weight cut-off of 25,000 and bovine thrombotic albumin (d2) with a molecular weight cut-off of 45,000 were used as the cross-flow filtration target liquid, and each of these proteins was phosphorylated. Two types of liquids to be treated with a concentration of 100 ppm were prepared by dissolving them in a salt buffer solution. Each of these liquids to be treated was circulated and supplied to a filter using a porous membrane as a filter, and the circulation flow rate was 2 m/se (,
Cross-flow filtration was performed at a filtration pressure of 1 kg/c+a2 and a filtration time of 60 minutes, and the rejection rate was calculated from the integrated intensity of the liquid chromatography chart of the mother liquor and filtrate using the following formula. (8) Discussion Judging from the attached table and the electron microscope photographs in FIGS. 2 to 5, the following is clear. In addition, in the figures, Figures 2 and 3 refer to N(L12, N[L11
The cross-sections of the filters shown in FIGS. 4 and 5 are thin limb surfaces of these filters.
（１）Ｎｏ．１〜ＮＯ．４においては薄膜の成形粒子が
大きくて蛋白質の阻止能力は全くなく、ＮＯ．５〜Ｎｏ
．８においては薄膜形成粒子は小さいものの蛋白質の阻
止能力が全くないか十分ではない。(1) No. 1~NO. In No. 4, the formed particles of the thin film were large and had no protein blocking ability at all; 5~No
．． Although the thin film-forming particles in No. 8 were small, they had no or insufficient ability to block proteins.
（２ＪＮｏ．９〜Ｎｏ．１２においては薄膜形或にゾル
液を用いているが、最後に封止剤のコーティング層をゲ
ル層の焼成温度より高い温度で焼成しているＮｏ．９お
よびＮｏ．１０には蛋白質の阻止能力が全くない，Ｎｏ
．１１とＮｏ．１２間においてはゾル液のコーティング
法の相違により特性に差が認められ、Ｎｏ．１１では薄
膜の無孔化部位との境にクラックが発生しており、かつ
蛋白質の阻止能力が十分ではない。(In 2J No. 9 to No. 12, a thin film type or a sol solution is used, but in No. 9 and No. 2, the coating layer of the sealant is fired at a temperature higher than the firing temperature of the gel layer at the end.) No. 10 has no protein blocking ability at all.
．． 11 and no. Differences in properties were observed between No. 12 and No. 12 due to differences in the coating method of the sol solution. In No. 11, cracks were generated at the boundary between the thin film and the nonporous portion, and the protein blocking ability was insufficient.
（３）第２図〜第５図から明らかなようにＮｏ．１１に
おいては薄膜が支持体の表面に貼着されているにすぎず
、薄膜の無孔化部位との境に大きなクラツクが発生して
いる．これに対して、Ｎｏ．１２においては薄膜の裏側
が支持体内に侵入して強固に結合し、かつ薄膜の無孔化
部位との境にクラツクの発生は認められない．
（以下余白〉(3) As is clear from Figures 2 to 5, No. In No. 11, the thin film was merely adhered to the surface of the support, and a large crack occurred at the border of the thin film with the non-porous area. On the other hand, No. In No. 12, the back side of the thin film penetrated into the support and was firmly bonded, and no cracks were observed at the boundary with the nonporous part of the thin film. (Margin below)
第１図は本発明でコーティングに使用するコーティング
装置の概略楕戒図、第２図および第３図は本発明の実施
例および比較例に係るフィルタの断面の電子顕微鏡写真
、第４図および第５図は同フィルタのｒＩｉ膜表面の電
子顕微鏡写真である。
符号の説明
１０・・・コーティング装置、１１・
容器、１２ａ，１２ｂ− − −支持板、・タンク、１
５ｂ・・・供給ポンプ、
・真空ボンブ。
１
１
圧力
４
７ ａFig. 1 is a schematic elliptical diagram of the coating apparatus used for coating in the present invention, Figs. 2 and 3 are electron micrographs of cross sections of filters according to examples and comparative examples of the present invention, and Figs. 4 and 3 are Figure 5 is an electron micrograph of the surface of the rIi film of the same filter. Explanation of symbols 10 Coating device, 11 Container, 12a, 12b -- Support plate, Tank, 1
5b... Supply pump, - Vacuum bomb. 1 1 pressure 4 7 a
Claims (1)
層を前駆体とする孔径１Å〜１０００Åの細孔を有する
セラミックの薄膜を備え、端部が封止剤にて無孔化され
ているセラミックフィルタの製造方法であり、下記（１
）〜（４）の工程を備えていることを特徴とするセラミ
ックフィルタの製造方法。 （１）前記多孔質支持体の端部に封止剤のスラリーをコ
ーティングする。 （２）コーティングされた封止剤を焼成して前記多孔質
支持体の端部を無孔化する。 （３）端部を無孔化された多孔質支持体の一側に有機バ
インダーを含有する前記コロイド粒子のゾル液を供給し
、同支持体の両側間の圧力差によりコーティングして前
記コロイド粒子のゲル層を形成する。 （４）前記ゲル層を焼成して薄膜を形成する。[Scope of Claims] A ceramic thin film having pores with a diameter of 1 Å to 1000 Å made of a gel layer of colloidal particles as a precursor is provided on one side of a porous ceramic support, and the ends are sealed with a sealant. This is a method for manufacturing a porous ceramic filter, and the method is as follows (1)
A method for manufacturing a ceramic filter, comprising the steps of ) to (4). (1) Coating the end of the porous support with a sealant slurry. (2) Burning the coated sealant to make the ends of the porous support non-porous. (3) A sol solution of the colloidal particles containing an organic binder is supplied to one side of a porous support whose end has been made non-porous, and the colloidal particles are coated by a pressure difference between both sides of the support. form a gel layer. (4) Burning the gel layer to form a thin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23774989A JPH0398627A (en) | 1989-09-13 | 1989-09-13 | Preparation of ceramic filter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23774989A JPH0398627A (en) | 1989-09-13 | 1989-09-13 | Preparation of ceramic filter |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0398627A true JPH0398627A (en) | 1991-04-24 |
Family
ID=17019903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23774989A Pending JPH0398627A (en) | 1989-09-13 | 1989-09-13 | Preparation of ceramic filter |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0398627A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009226307A (en) * | 2008-03-21 | 2009-10-08 | Ngk Insulators Ltd | Ceramic filter and manufacturing method of nanofiltration membrane |
| JP2010521284A (en) * | 2007-03-13 | 2010-06-24 | フェニックス アイピーアール リミテッド | Membrane structure and its manufacture and use |
| JP2010527784A (en) * | 2007-05-30 | 2010-08-19 | フェニックス アイピーアール リミテッド | Membrane structure and its manufacture and use |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS618106A (en) * | 1984-03-05 | 1986-01-14 | セラヴエ−ル | Membrane separator and manufacture thereof |
| JPH01218603A (en) * | 1988-02-25 | 1989-08-31 | Kubota Ltd | Production of filtration member |
-
1989
- 1989-09-13 JP JP23774989A patent/JPH0398627A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS618106A (en) * | 1984-03-05 | 1986-01-14 | セラヴエ−ル | Membrane separator and manufacture thereof |
| JPH01218603A (en) * | 1988-02-25 | 1989-08-31 | Kubota Ltd | Production of filtration member |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010521284A (en) * | 2007-03-13 | 2010-06-24 | フェニックス アイピーアール リミテッド | Membrane structure and its manufacture and use |
| JP2010527784A (en) * | 2007-05-30 | 2010-08-19 | フェニックス アイピーアール リミテッド | Membrane structure and its manufacture and use |
| JP2009226307A (en) * | 2008-03-21 | 2009-10-08 | Ngk Insulators Ltd | Ceramic filter and manufacturing method of nanofiltration membrane |
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