JPH01299607A - Inorganic porous membrane - Google Patents
Inorganic porous membraneInfo
- Publication number
- JPH01299607A JPH01299607A JP13082788A JP13082788A JPH01299607A JP H01299607 A JPH01299607 A JP H01299607A JP 13082788 A JP13082788 A JP 13082788A JP 13082788 A JP13082788 A JP 13082788A JP H01299607 A JPH01299607 A JP H01299607A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- porous
- support
- pore diameter
- average pore
- 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 47
- 239000010409 thin film Substances 0.000 claims abstract description 82
- 239000011148 porous material Substances 0.000 claims abstract description 74
- 239000002245 particle Substances 0.000 abstract description 20
- 238000000926 separation method Methods 0.000 abstract description 15
- 238000001914 filtration Methods 0.000 abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 239000010410 layer Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 239000010408 film Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000002356 single layer Substances 0.000 description 7
- 238000010304 firing Methods 0.000 description 6
- 239000003550 marker Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 108010088751 Albumins Proteins 0.000 description 4
- 102000009027 Albumins Human genes 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000009295 crossflow filtration Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920002307 Dextran Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 108010074605 gamma-Globulins Proteins 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000725 suspension Substances 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
- 238000000108 ultra-filtration Methods 0.000 description 2
- ZXUJWPHOPHHZLR-UHFFFAOYSA-N 1,1,1-trichloro-2-fluoroethane Chemical compound FCC(Cl)(Cl)Cl ZXUJWPHOPHHZLR-UHFFFAOYSA-N 0.000 description 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 108010025568 Nucleophosmin Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 229940098773 bovine serum albumin Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000011041 water permeability test Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野）
本発明は濾過、ガス分離等に使用される無機多孔質膜に
関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an inorganic porous membrane used for filtration, gas separation, etc.
（従来技術）
無機多孔質膜の一種類として、１または複数層の多孔質
支持体の一側面に、同支持体の平均細孔径より小さい平
均細孔径を有する多孔質薄膜を一体的に備えてなる複層
構造の無機多孔質膜がある。(Prior art) As a type of inorganic porous membrane, a porous thin film having an average pore diameter smaller than the average pore diameter of the support is integrally provided on one side of one or more layers of porous support. There is an inorganic porous membrane with a multilayer structure.
この種の多孔質膜は用途によって耐熱性、耐食性に優れ
ていることが要求されるが、特に高い濾過精度、分離精
度を要求される場合がある。この場合、濾過膜、分離膜
として機能する多孔質薄膜を所定の平均細孔径に形成し
ても同薄膜にピンホール、クラック等が存在すると濾過
精度、分離精度を著しく低下させることになるため、同
薄膜にピンホール、クラック等が存在しないように注意
することが必要である。This type of porous membrane is required to have excellent heat resistance and corrosion resistance depending on its use, and particularly high filtration accuracy and separation accuracy may be required in some cases. In this case, even if a porous thin film that functions as a filtration membrane or separation membrane is formed to have a predetermined average pore diameter, the presence of pinholes, cracks, etc. in the thin film will significantly reduce the filtration accuracy and separation accuracy. Care must be taken to ensure that there are no pinholes, cracks, etc. in the thin film.
ところで、上記した複層構造の無機多孔質膜に関する発
明等は多数開示されており、かかる発明が開示された刊
行物の一例として特開昭６０−１５６５１０号公報、特
開昭５２−９４５１２号公報を挙げることができる。By the way, many inventions related to the above-mentioned multilayer structure inorganic porous membrane have been disclosed, and examples of publications disclosing such inventions include JP-A-60-156510 and JP-A-52-94512. can be mentioned.
特開昭６０−１５６５１０号公報にはクラックの生じな
い無機半透過膜の製法、具体的には焼結した無機酸化物
からなる多孔質支持体に無機膜形成コーティング材料の
懸濁液をコーティングして加熱することからなる製法が
開示されている。また、かかる製法において、多孔質支
持体の適確性は同支持体が有する孔寸法（平均細孔径）
により定まり、孔寸法が大きいと懸濁液中のゾル粒子が
同支持体内に侵入して膜を形成し得ないこと、好ましい
孔寸法として代表径０．１〜０．５μｍを挙げている。JP-A-60-156510 discloses a method for producing an inorganic semi-permeable membrane that does not cause cracks, specifically, a porous support made of a sintered inorganic oxide is coated with a suspension of an inorganic membrane-forming coating material. A manufacturing method is disclosed which consists of heating at In addition, in this manufacturing method, the suitability of the porous support is determined by the pore size (average pore diameter) of the support.
If the pore size is large, the sol particles in the suspension will not be able to penetrate into the support and form a film, and a typical diameter of 0.1 to 0.5 μm is cited as a preferable pore size.
さらにまた、かかる製法においてはクラックの発生を抑
制するなめ、コーテイング膜の乾燥に長時間乾燥、複雑
な超臨界乾燥等を採用し、かつ焼成時微速な昇温手段を
採用している。かかる製法により、多孔質支持体上にγ
−アルミナからなる多孔質薄膜が被覆された限外濾過膜
を得ている。Furthermore, in this manufacturing method, in order to suppress the occurrence of cracks, long-time drying, complicated supercritical drying, etc. are used for drying the coating film, and a means for raising the temperature at a slow rate during firing is used. By this production method, γ is deposited on a porous support.
- An ultrafiltration membrane coated with a porous thin film of alumina is obtained.
一方、特開昭５２−９４５７２号公報には複層構造の無
機多孔質膜において、多孔質支持体の平均細孔径は多孔
質薄膜の平均細孔径のｌθ〜２００．０００倍、好まし
くは２００〜２０，０００倍である旨開示されている。On the other hand, JP-A-52-94572 discloses that in an inorganic porous membrane having a multilayer structure, the average pore diameter of the porous support is lθ to 200.000 times, preferably 200 to 200.000 times, the average pore diameter of the porous thin film. It is disclosed that it is 20,000 times larger.
（発明が解決しようとする課題）
ところで、複層構造の無機多孔質膜における多孔質薄膜
のピンホール、クラックは同薄膜の形成時に発生する。(Problems to be Solved by the Invention) By the way, pinholes and cracks in a porous thin film in an inorganic porous film having a multilayer structure occur during the formation of the thin film.
一般に、多孔質薄膜は微小粒子のゾル液を多孔質支持体
の一側に担持させ乾燥、焼成することにより形成される
。この場合、担持されたゾル液は多孔質支持体の細孔径
内に侵入するとともに、その表面にて濃縮現象が生じて
薄膜となるが、ゾル液中の粒子が局部的に支持体内に吸
込まれるとピンホールが発生し、また薄膜が局部的に厚
くなるとその後の乾燥、焼成時の熱収縮によりクラック
が発生する。本発明者は、特に多孔質支持体における最
大気孔径の細孔部分ではゾル液中の粒子が侵入し易いた
め、ピンホール、クラックが発生し易いとの知見を得て
いる。Generally, a porous thin film is formed by supporting a sol solution of microparticles on one side of a porous support, drying, and baking. In this case, the supported sol liquid enters the pore size of the porous support, and a concentration phenomenon occurs on the surface to form a thin film, but the particles in the sol liquid are locally sucked into the support. If the thin film is thickened locally, cracks will occur due to thermal shrinkage during drying and firing. The present inventor has obtained the knowledge that particles in the sol liquid tend to penetrate particularly into the pore portions of the porous support having the maximum pore diameter, so that pinholes and cracks are likely to occur.
従って、多孔質薄膜の形成時にピンホール、クラックの
発生を防止するには、多孔質支持体の最大気孔径を薄膜
との関係で規定することが必要である。しかしながら、
従来技術においては、上記したごとく支持体単独、また
は支持体および薄膜の平均細孔径に着目された例はある
が、支持体の最大気孔径について着目された例はなく、
薄膜にはピンホール、クラックが不可避的に存在してい
る。薄膜にピンホール、クラックが存在している場合に
は濾過精度、分離精度が低いことは勿論であるが、多孔
質膜の酸、アルカリ洗浄、スチーム殺菌時等に薄膜が支
持体から剥離するおそれがある。Therefore, in order to prevent pinholes and cracks from occurring during the formation of a porous thin film, it is necessary to define the maximum pore diameter of the porous support in relation to the thin film. however,
In the prior art, as mentioned above, there are examples in which attention has been focused on the average pore diameter of the support alone or the support and a thin film, but there is no example that has focused on the maximum pore diameter of the support.
Pinholes and cracks inevitably exist in thin films. If there are pinholes or cracks in the thin film, it goes without saying that the filtration accuracy and separation accuracy will be low, but there is also a risk that the thin film will peel off from the support during acid or alkali cleaning or steam sterilization of the porous membrane. There is.
従って、本発明の目的は、多孔質支持体の最大気孔径を
規定することにより多孔質薄膜でのピンホール、クラッ
クの発生を防止し、多孔質膜の濾過精度、分離精度を著
しく向上させることにある。Therefore, an object of the present invention is to prevent the occurrence of pinholes and cracks in a porous thin membrane by regulating the maximum pore diameter of the porous support, and to significantly improve the filtration accuracy and separation accuracy of the porous membrane. It is in.
（課題を解決するための手段）
本発明は、ｌまたは複数層の多孔質支持体の一側面に、
同支持体の平均細孔径より小さい平均細孔径を有する多
孔質薄膜を備えてなる無機多孔質膜において、前記多孔
質薄膜が付着する層の最大気孔径が同薄膜の平均細孔径
の１〜２５０倍であることを特徴とするものである。(Means for Solving the Problems) The present invention provides that on one side of one or more layers of porous support,
In an inorganic porous membrane comprising a porous thin film having an average pore diameter smaller than the average pore diameter of the support, the maximum pore diameter of the layer to which the porous thin film is attached is 1 to 250% of the average pore diameter of the thin film. It is characterized by being twice as large.
本発明において、多孔質支持体は無機質粒子例えばアル
ミナ、ジルコニア、チタニア等のセラミック、ホウケイ
酸ガラス等のガラス、ニッケル等の金属、炭素の焼結体
からなるパイプ状、平板状、ハニカム状等のもので、単
層、２層以上の複層構造のいずれであってもよい、支持
体が複層構造の場合には、多孔質薄膜の付着側に平均細
孔径が漸次小さくなるよう配列する。薄膜は支持体と同
様の材料からなるもので、例えば親水性であるアルミナ
、チタニア等からなる。In the present invention, the porous support is made of inorganic particles such as ceramics such as alumina, zirconia, and titania, glasses such as borosilicate glass, metals such as nickel, and sintered bodies of carbon in the shape of a pipe, plate, honeycomb, etc. The support may have either a single layer structure or a multilayer structure of two or more layers. When the support has a multilayer structure, the pores are arranged so that the average pore diameter becomes gradually smaller on the adhesion side of the porous thin film. The thin film is made of the same material as the support, such as hydrophilic alumina or titania.
（発明の作用・効果）
本発明者の知見によれば、複層構造の無機多孔質膜にお
いては多孔質支持体の最大気孔径が多孔質薄膜の平均細
孔径の１〜２５０倍の場合、薄膜にピンホール、クラッ
クが発生しないことを確認している。かかる多孔質膜に
おいて、薄膜の平均細孔径は用途に基づいて設定される
とともに使用する原料の粒径、膜成形法により調節する
ことができる。このため、予じめ設定された薄膜の平均
細孔径の１〜２５０倍の最大気孔径を有する多孔質支持
体を選定し、同支持体の一側面に上記薄膜を形成すれば
同薄膜は実質的にピンホール、クラックが存在しないも
のとなる。従って、かがる多孔質膜は設定された極めて
高い濾過精度、分離精度を備え、ピンホール、クラック
等の影響を受けることがない。(Operations and Effects of the Invention) According to the findings of the present inventors, in an inorganic porous membrane with a multilayer structure, when the maximum pore diameter of the porous support is 1 to 250 times the average pore diameter of the porous thin film, We have confirmed that there are no pinholes or cracks in the thin film. In such a porous membrane, the average pore diameter of the thin membrane is set based on the intended use and can be adjusted by the particle size of the raw materials used and the membrane forming method. For this reason, if a porous support having a maximum pore diameter of 1 to 250 times the preset average pore diameter of the thin film is selected and the thin film is formed on one side of the support, the thin film will be substantially There will be no pinholes or cracks. Therefore, the porous membrane has extremely high filtration accuracy and separation accuracy, and is not affected by pinholes, cracks, etc.
しかして、多孔質支持体に関しては平均細孔径Ｄａｖの
多孔質体の単層構造のもの、同多孔質体の一側面にこれ
より小さい平均細孔径Ｄ’ａｖの多孔質体を付着した複
Ｎ構造のものであり、複層構造の場合各層は互いに同じ
組成で熱膨張が同一または近似“することが好ましい、
多孔質支持体の平均細孔径Ｄａｖ、Ｄ’ａｖは多孔質薄
膜の平均細孔径ｄａｙより大きいものであるが、薄膜の
平均細孔径ｄａｖにより好ましい範囲が異なる。例えば
、限外濾過やガス分離等に用いる多孔質膜における薄膜
のｄａｙは０．１μｍ以下であることが必要であり、こ
の場合の単層構造の支持体のＤａｙは０．０５μｍ〜３
μｍであることが好ましく、複層構造の支持体のＤａｖ
は０．１ μｍ 〜３０μｍ、Ｄ’ａｖは１．ｕｎ以下
であることが好ましい、また、精密濾過に用いる多孔質
膜における薄膜のｄａｖは０．１μｍ〜１０μｍである
が、この場合の単層構造の支持体のＤａｖは０．５μｍ
〜３０μｍであることが好ましく、複層構造の支持体の
Ｄａｖは３ Ａｉｍ 〜３０μｍ 、 Ｄ’ａｖは０．
５ μｍ 〜１０．ｃｚｍであることが好ましい。支持
体のＤａｙ、Ｄ’ａｖにおける下限値は流体の拡散抵抗
を無視できる限界から、またそれらの上限値は支持体の
強度、薄膜の製膜性等から決定される。なお、複層構造
の支持体は単層構造の支持体に比較して薄膜の厚みを薄
くでき、流体の拡散抵抗を小さくできる利点がある。As for the porous support, there are single-layer structures made of a porous material with an average pore diameter Dav, and double-layer structures with a porous material having a smaller average pore diameter D'av attached to one side of the same porous material. In the case of a multilayer structure, it is preferable that each layer has the same composition and thermal expansion that is the same or similar.
The average pore diameters Dav and D'av of the porous support are larger than the average pore diameter day of the porous thin film, but the preferred range differs depending on the average pore diameter dav of the thin film. For example, the day of a thin film in a porous membrane used for ultrafiltration, gas separation, etc. must be 0.1 μm or less, and in this case, the day of a support with a single layer structure is 0.05 μm to 3
Dav of the multilayer structure support is preferably μm.
is 0.1 μm to 30 μm, and D'av is 1. In addition, the DAV of the thin film in the porous membrane used for precision filtration is preferably 0.1 μm to 10 μm, but in this case, the DAV of the single-layer structure support is 0.5 μm.
It is preferable that it is ~30 μm, and the Dav of the multilayer structure support is 3 Aim ~30 μm, and the D'av is 0.
5 μm ~10. Preferably, it is czm. The lower limit values for Day and D'av of the support are determined from the limit where the diffusion resistance of the fluid can be ignored, and their upper limits are determined from the strength of the support, the film formability of the thin film, etc. Note that, compared to a support having a single layer structure, a support having a multilayer structure has the advantage that the thickness of the thin film can be made thinner, and the diffusion resistance of the fluid can be reduced.
多孔質支持体の細孔率（気孔率）は２５ＶＯ１％〜４５
ｖｏ１％であることが好ましく 、２５ ｖｏ１％未
満の場合には多孔質薄膜の密着性が問題となり、かつ４
５ｖｏ１％を超えると支持体としての強度が問題となる
。また、支持体の膜厚は強度上９．５ｍｍ〜２ｍｍ程度
が好ましく、かつ複層構造における中間層の膜厚は拡散
抵抗上１０μｍ〜１５０μｍ程度が好ましい。かかる支
持体は圧縮成形、鋳込成形、押出成形等公知の方法で成
形されたパイプ状、平板状、ハニカム状成形体を焼成し
て形成される。The porosity (porosity) of the porous support is 25VO1% to 45
It is preferable that the amount of vol.
If it exceeds 5vol%, the strength as a support becomes a problem. Further, the thickness of the support is preferably about 9.5 mm to 2 mm in terms of strength, and the thickness of the intermediate layer in a multilayer structure is preferably about 10 μm to 150 μm in terms of diffusion resistance. Such a support body is formed by firing a pipe-shaped, flat plate-shaped, or honeycomb-shaped molded body formed by a known method such as compression molding, casting molding, or extrusion molding.
多孔質支持体の最大気孔径に関しては、同支持体の最大
気孔径Ｄｍａｘ、Ｄ’ｍａｘ（Ｄｍａｘ−−・単層構造
、Ｄ’１ｌｌｌＬＸ ・・・複層構造の中間Ｍ）が多孔
質薄膜の平均細孔径の１〜２５０倍であり、この範囲は
薄膜にピンホール、クラックを発生させない条件である
。但し、複層構造の支持体においてはＤｍａｘ≧Ｄ’ｍ
ａｘの関係にある。なお、本発明において最大気孔径は
後述する公知のバブルポイント法により測定している。Regarding the maximum pore diameter of the porous support, the maximum pore diameter Dmax, D'max (Dmax - single layer structure, D'1llllLX...middle M of multilayer structure) of the support is the same as that of the porous thin film. It is 1 to 250 times the average pore diameter, and this range is a condition under which pinholes and cracks do not occur in the thin film. However, in the case of a support with a multilayer structure, Dmax≧D'm
It is in the relationship of ax. In the present invention, the maximum pore diameter is measured by the well-known bubble point method described below.
支持体のＤｍａｘ、 Ｄ’ｍａｘと薄膜のｄａＶとの関
係の好ましい範囲は薄膜のｄａｖの値によって異なる。The preferred range of the relationship between Dmax and D'max of the support and daV of the thin film varies depending on the value of dav of the thin film.
これらの比Ｄｍａｘ／ｄａｙ、Ｄ’ｍａｘ／ｄａｖは薄
膜のｄａｙが０．１μｍ未満の場合１〜１００．ｄａｙ
が０゜１μｍ〜１０μｍの場合１〜２５である。これら
の範囲においては、薄膜にピンホール、クラックを生じ
させることなく極めて薄くできて濾過、分離の精度およ
び効率を著しく向上させることができる薄膜ｄａｖの値
によりＤｍａｘ／ｄａｙ、 Ｄ’ｍａｘ／ｄａｙの範囲
が異なるのは、主として同薄膜の調整法の違いによるも
のである。These ratios Dmax/day and D'max/dav are 1 to 100. day
is 1 to 25 when is 0°1 μm to 10 μm. In these ranges, Dmax/day and D'max/day are determined by the value of the thin film dav, which can be made extremely thin without producing pinholes or cracks, and can significantly improve the accuracy and efficiency of filtration and separation. The difference in range is mainly due to differences in the preparation method for the same thin film.
ｄａｖの値が０．１μｍ未満の多孔質薄膜を調製する一
般的な方法としては、粒径０．４μｍ以下の微小粒子を
含むコロイド水溶液を湿式法にてコーティングするか、
気相法や圧縮成形法等による乾式法にてコーティングす
る方法が採られる。例えば湿式法にてコーティングする
場合、多孔質支持体をコロイド水溶液に浸漬すると同水
溶液は支持体の細孔の毛管吸引力にて支持体表面に引付
けられて濃縮現象が起る。コロイド水溶液中のゾル粒子
は水分濃度のわずかな変化でゲル化して支持体上に均一
に付着される。微小粒径のゾル粒子では侵入可能な細孔
が存在していても均一に製膜が可能である。乾式法で製
膜する場合においても、微小粒子は表面エネルギーが大
きいため支持体上に容易に付着凝集し、同様の効果を示
すものである。A general method for preparing a porous thin film with a dav value of less than 0.1 μm is to coat a colloidal aqueous solution containing microparticles with a particle size of 0.4 μm or less by a wet method, or
A dry coating method such as a vapor phase method or a compression molding method is used. For example, when coating by a wet method, when a porous support is immersed in an aqueous colloid solution, the aqueous solution is attracted to the surface of the support by the capillary suction force of the pores of the support, causing a concentration phenomenon. Sol particles in a colloidal aqueous solution gel with a slight change in water concentration and are uniformly deposited on a support. With sol particles having a minute particle size, even if there are pores that can be penetrated, uniform film formation is possible. Even in the case of forming a film by a dry method, fine particles easily adhere and aggregate on the support because of their large surface energy, and exhibit the same effect.
これに対して、ｄａｙの値が０．１μｍ〜１０μｍの場
合には粒径０．４μｍ以上の比較的粒径が大きくて表面
エネルギーの小さい粒子を使用することから、粒子の支
持体の侵入を出来るかぎり阻止するには、粒子径と支持
体の最大気孔径とを比較的近似した値にする必要がある
。On the other hand, when the day value is 0.1 μm to 10 μm, particles with a relatively large particle size of 0.4 μm or more and low surface energy are used, which prevents the particles from penetrating the support. In order to prevent this as much as possible, it is necessary to make the particle size and the maximum pore size of the support relatively similar.
なお、本発明にかかる多孔質膜においては、多孔質支持
体の最大気孔径Ｄｍａｘ、 Ｄ’ｍａｘと多孔質薄膜と
の膜厚ｔ、支持体の平均細孔径Ｄａｖ 、 Ｄ’ａｖと
薄膜の平均細孔径ｄａｙとの関係を規定することが好ま
しい、支持体の最大気孔径と薄膜の膜厚との比Ｄｍａｘ
／ｌ、Ｄ’ｍａｘ／ｌの下限はピンホールの発生を防止
するため、かつその上限はクラックの発生を防止するた
めに有効であって、上記比Ｄｍａｘ／ｌ、Ｄ’ｍａｘ／
ｌは１〜５の範囲にあることが好ましい。薄膜を数回に
分けて担持させる場合には、すでに担持されている薄膜
を中間層としてその最大気孔径を考慮することが好まし
い。また、支持体の平均細孔径と薄膜の平均細孔径との
比Ｄａｙ／ｄａｙ、Ｄ’ａｖ／ｄａｖは支持体に対する
薄膜の密着性に関係し、量比は１〜２００倍であること
が好ましい、かかる比のさらに好ましい範囲は薄膜のｄ
ａｖにより異なり、ｄａｖが０．１ 、ｔｚｍ未溝の場
合１〜５０．ｄａｙが０．１ μｖａ 〜ＩＱμｍの場
合ｌ〜ｌＯであることが好ましい。In the porous membrane according to the present invention, the maximum pore diameter Dmax of the porous support, D'max and the film thickness t of the porous thin film, the average pore diameter Dav of the support, D'av and the average of the thin film. The ratio Dmax between the maximum pore diameter of the support and the thickness of the thin film, which preferably defines the relationship with the pore diameter day.
The lower limit of /l, D'max/l is effective for preventing the occurrence of pinholes, and the upper limit is effective for preventing the occurrence of cracks, and the above ratios Dmax/l, D'max/
It is preferable that l is in the range of 1 to 5. When supporting the thin film in several parts, it is preferable to consider the maximum pore diameter of the thin film that has already been supported as an intermediate layer. Furthermore, the ratio Day/day and D'av/dav between the average pore diameter of the support and the average pore diameter of the thin film are related to the adhesion of the thin film to the support, and the quantitative ratio is preferably 1 to 200 times. , a more preferable range of such ratio is d of the thin film.
Varies depending on av, dav is 0.1, 1 to 50 if tzm is not grooved. When day is 0.1 μva to IQ μm, it is preferably l to lO.
なお、多孔質薄膜の原料は耐熱性、耐食性に優れた無機
質粒子であって、その比表面積が数ｍ２／ｇ〜数１００
ｍ２／ｇであることが好ましい、また、耐食性の不要な
ガス分離用の膜においてはγ−アルミナも好ましいが、
耐食性が要求されるその他の用途の膜においてはα−ア
ルミナ、チタニア、ジルコニア等が特に好ましい。薄膜
は支持体上に形成された後、焼成等の熱処理に付されて
安定化される。The raw material for the porous thin film is an inorganic particle with excellent heat resistance and corrosion resistance, and its specific surface area ranges from several m2/g to several 100 m2/g.
m2/g is preferable, and γ-alumina is also preferable for gas separation membranes that do not require corrosion resistance.
For films for other uses where corrosion resistance is required, α-alumina, titania, zirconia, etc. are particularly preferred. After the thin film is formed on the support, it is stabilized by being subjected to heat treatment such as baking.
（実施例）
（１）多孔質支持体の調整
各種粒径の電融アルミナに無機バインダー、有機バイン
ダーを添加して混練坏土を調製し、押出成形法にて外径
１０ｍｍ、内径７ｍｍ 、長さ１５０ｍｎ＋のバイブを
形成し、これを乾燥後１５００℃で３時間焼成した。こ
れにより、粒径の相違に起因する各種の平均細孔径を有
する単層構造の多孔質支持体を得た。これら支持体のい
くつかの内側面にα−アルミナの微粉からなる解膠した
スラリーを塗布し、乾燥後１０００〜１３００℃で３時
間焼成して複層構造の多孔質体を得た。新たに形成され
た層を中間層といいその膜厚は３０μｍであり、かつ同
中間層の平均細孔径Ｄ’ａｖは微粉の粒度、焼成温度に
て調整した。得られた支持体の特性を第１表に示す。同
表の特性中履大気孔径Ｄｍａｘ、 Ｄ’ｍａｘの値はバ
ブルポイント法により測定したもの、平均細孔径Ｄａｖ
、Ｄ’ａｖ値は水銀圧入法により測定したものである。(Example) (1) Adjustment of porous support A kneaded clay was prepared by adding an inorganic binder and an organic binder to fused alumina of various particle sizes. A vibrator with a length of 150 m+ was formed, and after drying, it was fired at 1500° C. for 3 hours. As a result, porous supports having a single layer structure having various average pore diameters due to differences in particle diameter were obtained. A peptized slurry of α-alumina fine powder was applied to the inner surfaces of some of these supports, dried, and then fired at 1000 to 1300° C. for 3 hours to obtain a porous body with a multilayer structure. The newly formed layer is called an intermediate layer, and its thickness is 30 μm, and the average pore diameter D'av of the intermediate layer is adjusted by the particle size of the fine powder and the firing temperature. The properties of the obtained support are shown in Table 1. The values of the characteristic medium pore diameter Dmax and D'max in the same table are those measured by the bubble point method, and the average pore diameter Dav
, D'av values were measured by mercury porosimetry.
第１表
（２最大気孔径の測定（バブルポイント法）パイプ状の
各多孔質支持体を予め測定用液体内に１時間以上浸漬し
、その後５０ｔｏｒｒ以下の減圧下で支持体内の気泡を
脱気する。脱気処理された支持体はその筒部両端を密閉
状態にして測定装置の液体槽内に設置し、その後支持体
の内孔内へ空気を徐々に加圧して付与し、気泡が最初に
発生した時点の空気圧Ｐ（発泡圧）を読み取る。この発
泡圧Ｐから最大気孔径を下記の式にて算出する。Table 1 (2 Measurement of maximum pore diameter (bubble point method)) Each pipe-shaped porous support is immersed in a measurement liquid for at least 1 hour, and then air bubbles in the support are degassed under reduced pressure of 50 torr or less. The degassed support is placed in the liquid tank of the measuring device with both ends of its cylindrical part sealed, and then air is gradually pressurized and applied into the inner hole of the support to remove air bubbles. The air pressure P (foaming pressure) generated at the moment is read.The maximum pore diameter is calculated from this foaming pressure P using the following formula.
なお、一般にθ・０．Ｐ＞＞ｈＳであるため上記式は簡
略化される。測定に使用する液体は最大気孔径が０．４
２μｍ以上の支持体については水、０．４２μｍ未満の
支持体についてはトリクロロフルオロエタンである。In general, θ・0. Since P>>hS, the above equation is simplified. The liquid used for measurement has a maximum pore diameter of 0.4
Water is used for supports of 2 μm or more, and trichlorofluoroethane is used for supports of less than 0.42 μm.
（３）多孔質薄膜の調製
薄膜Ｎｏ、１：市販のアルミナゾル（日産化学株式会社
製、商品名アルミナゾル−２００）をＡｌ２Ｏ，分が５
ｗｔ％含むように水で希釈して担持液とし、これを多孔
質支持体の内側面に塗布する。その後室温で１時間次い
で６０℃で１時間乾燥した後、１００℃／ｈｒの速度で
３８０°Ｃまで昇温してこれを３時間保持した。得られ
た薄膜の平均細孔径ｄａｖは４０Ａである。(3) Preparation of porous thin film Thin film No. 1: Commercially available alumina sol (manufactured by Nissan Chemical Co., Ltd., trade name Alumina sol-200) was mixed with Al2O, min.
A supporting solution is prepared by diluting the solution with water to contain % by weight, and this is applied to the inner surface of the porous support. Thereafter, it was dried at room temperature for 1 hour and then at 60°C for 1 hour, and then heated to 380°C at a rate of 100°C/hr and maintained at this temperature for 3 hours. The average pore diameter dav of the obtained thin film is 40A.
薄膜Ｎｏ、２：チタニウムイソプロポキシドをＴｉＯ２
分で５ｗｔ％含むエタノール水溶液中に水をＴｉＯ２モ
ル比の５倍添加し、これを２時間攪拌して担持液として
多孔質支持体の内側面に塗布する。その後の乾燥、熱処
理は薄膜Ｎ０１１と同様であり、ｄａｙ・５０Ａの薄膜
を得た。Thin film No. 2: Titanium isopropoxide with TiO2
Water is added to an aqueous solution of ethanol containing 5 wt % of TiO2 by 5 times the molar ratio of TiO2, and the mixture is stirred for 2 hours and coated on the inner surface of the porous support as a carrier solution. The subsequent drying and heat treatment were the same as for thin film No. 011, and a thin film of 50 A day was obtained.
薄膜Ｎｏｊ：平均粒径０．１μｍのチタニア微粉を３ｗ
ｔ％含む水溶液に界面活性剤、有機解膠剤を添加し１６
時間攪拌して担持液とし、これを支持体の内側面に塗布
する。その後の乾燥、熱処理については、熱処理である
焼成温度を１０００℃とした以外は薄膜Ｎｏ、１と同様
であり、ｄａｙ・５００Ａの薄膜を得た。Thin film Noj: 3w of titania fine powder with an average particle size of 0.1μm
Adding a surfactant and an organic peptizer to an aqueous solution containing 16%
The mixture is stirred for a period of time to form a carrier solution, which is applied to the inner surface of the support. The subsequent drying and heat treatment were the same as those for thin film No. 1, except that the firing temperature for heat treatment was 1000° C., and a thin film of 500 A day was obtained.
薄膜Ｎｏ’、４：平均粒径０６５μｍのα−アルミナを
用いた以外は薄膜Ｎ００３と同様の調製法を採用して、
ｄａｖ＝２００ＯＡの薄膜を得た。Thin film No', 4: The same preparation method as thin film No. 003 was adopted, except that α-alumina with an average particle size of 065 μm was used.
A thin film with dav=200OA was obtained.
薄膜Ｎｏ、５：平均粒径３μｍのα−アルミナを用いる
とともに焼成温度を１３００℃とした以外は薄膜Ｎｏｊ
と同様の調製法を採用して、ｄａｖ＝１μｍの薄膜を得
た。Thin film No. 5: Thin film No. 5 except that α-alumina with an average particle size of 3 μm was used and the firing temperature was 1300°C.
A thin film with dav=1 μm was obtained using the same preparation method.
なお、得られた薄膜の平均細孔径ｄａｖは水銀圧入法ま
たはガス吸着法により測定した。The average pore diameter dav of the obtained thin film was measured by mercury intrusion method or gas adsorption method.
（４）多孔質膜の膜性能試験
各種の多孔質支持体の内側面に各種の多孔質薄膜を形成
してなる複層構造の多孔質膜につき、下記の純水透水量
、クロスフロー濾過、耐食性の各試験を行い第２表に示
す結果を得た。(4) Membrane performance test of porous membranes For porous membranes with a multilayer structure formed by forming various porous thin films on the inner surface of various porous supports, the following pure water permeability, cross flow filtration, Corrosion resistance tests were conducted and the results shown in Table 2 were obtained.
純水透水量試験：蒸留水を０．５〜５ｋｇ／ｃｍ２の圧
力にて多孔質膜の一方側面から他方側面へ透過させ、単
位膜面積、単位時間、単位圧力光たりの透水量を算出す
る。Pure water permeability test: Distilled water is permeated from one side of the porous membrane to the other side at a pressure of 0.5 to 5 kg/cm2, and the permeation amount per unit membrane area, unit time, and unit pressure light is calculated. .
クロスフロー濾過試験＋ １１００ｐｐのマーカーを含
む水溶液（マーカーが蛋白質である場合は緩衝液）を２
．５ｍ／ｓｅｃの速度、入口圧３ ｋｇ／ｃｍ２にて多
孔質膜の内孔を循環させるクロスフロー濾過を行い透過
液の分析を行ってマーカーの阻止率を算出する。なお、
マーカーとしては薄膜のｄａｙの値に対応して牛血清ア
ルブミン（平均分子量６５．０００）、γ−グロブリン
（平均分子量１５６．０００＞、ブルーデキストラン（
平均分子量２００万）、ユニホームラテックス（粒径１
．１μｍ）を用いた。Cross-flow filtration test
．． Cross-flow filtration is performed by circulating the inner pores of the porous membrane at a speed of 5 m/sec and an inlet pressure of 3 kg/cm2, and the permeate is analyzed to calculate the rejection rate of the marker. In addition,
As markers, bovine serum albumin (average molecular weight 65.000), γ-globulin (average molecular weight 156.000>), blue dextran (
average molecular weight 2 million), uniform latex (particle size 1
．． 1 μm) was used.
耐食性試験：多孔質膜を９０℃のＨＣＩ水溶液（ＰＨ・
０）、ＮａＯＨ水溶液（Ｐ）Ｉ＝１４）に１６８時間浸
漬し、薄膜におけるピンホール、クラックの有無を走査
型電子顕微鏡にて観察する。Corrosion resistance test: The porous membrane was exposed to a 90°C HCI aqueous solution (PH
0), NaOH aqueous solution (P)I=14) for 168 hours, and the presence or absence of pinholes and cracks in the thin film was observed using a scanning electron microscope.
第２表において、
＊ｌ、＊２．＄３：支持体が中間層を有する複層構造で
ある場合（支持体Ｎｏ、３〜Ｎｏ、６）はＤ’ｎ＋ａｘ
。In Table 2, *l, *2. $3: When the support has a multilayer structure with an intermediate layer (support No. 3 to No. 6), D'n+ax
.
Ｄ’ａｖの値
＊４：耐食性試験前後のピンホール、クラックの有無
＊５：マーカーとしてアルブミンを使用＊６：マーカー
としてγ−グロブリンを使用＊７：マーカーとしてブル
ーデキストランを使用＊８：マーカーとしてユニホーム
ラテックスを使用
（以下余白）
／
／
／
／
／
／
／
／
／
平均細孔径ｄａｖが４０人の薄膜を備えた多孔質膜Ｎｏ
、Ｉ〜Ｎｏ、４において、Ｎ０９１およびＮ０９２とＮ
０１３およびｎｏ、４とを比較した場合最大気孔径Ｄｍ
ａｘの相違により前者のアルブミン阻止率が高く、９９
％以上にも達している。また、多孔質膜Ｎｏ、 １とＮ
ｏ、２とを比較した場合、膜厚の薄い薄膜を備えたＮ０
１１は透水量、透過液量ともに大きくて効果的な濾過、
分離が可能である。なお、多孔質膜Ｎｏ、１．Ｎｏ、２
の薄膜成分はγ−アルミナであるため耐アルカリ性に劣
るが、同腹Ｎｏ、１．Ｎｏ、２は耐アルカリ性が要求さ
れない例えばガス分離等の用途に有効である。D'av value *4: Presence or absence of pinholes and cracks before and after corrosion resistance test *5: Albumin is used as a marker *6: γ-globulin is used as a marker *7: Blue dextran is used as a marker *8: As a marker Using uniform latex (blank below) / / / / / / / / / Porous membrane No. with a thin film with an average pore diameter dav of 40 people
, I~No, 4, N091 and N092 and N
Maximum pore diameter Dm when comparing 013 and no. 4
Due to the difference in ax, the former has a higher albumin inhibition rate, 99
It has reached more than %. In addition, porous membrane No. 1 and N
o, 2, N0 with a thin film has a thin film thickness.
11 is effective filtration with large permeation amount and permeation liquid amount;
Separation is possible. Note that porous membrane No. 1. No, 2
Since the thin film component is γ-alumina, it has poor alkali resistance, but No. 1. No. 2 is effective for applications where alkali resistance is not required, such as gas separation.
平均細孔径ｄａｖが５０人の薄膜を備えた多孔質膜Ｎｏ
、５〜Ｎｏ、９から明らかなようにＤｍａｘ／ｄａｙ、
Ｄ’ｍａｘ／ｄａｖを適正な範囲に規定することにより
、ピンホールおよびクラックが無くてアルブミンをほぼ
完全に阻止できる多孔質膜Ｎ０１５〜Ｎ０１８を得るこ
とができる。これらの多孔質膜においては、支持体が中
間層を有する複層構造であって薄膜の厚みを薄くでき、
特に中間層の平均細孔径Ｄ’ａｖが０．１μｍ以下でか
つ薄膜の厚みが１μｍ以下のものＮｏ、？、Ｎｏ、８は
、透過液量が多くて極めて効率よく濾過、分離を行うこ
とができる。耐食性試験においては多孔質膜Ｎｏ、５〜
ＮＯ３８にピンホール、クラックの発生が認められない
のに対し、ＮＯ１９ではクラックが増大して薄膜に局部
的は剥離現象が認められかつアルブミンの阻止率が２％
までに低下した。Porous membrane No. with a thin film with an average pore diameter dav of 50
, 5 to No. 9, Dmax/day,
By defining D'max/dav within an appropriate range, porous membranes N015 to N018 that are free from pinholes and cracks and can almost completely block albumin can be obtained. In these porous membranes, the support has a multilayer structure with an intermediate layer, and the thickness of the thin membrane can be reduced.
Particularly, the intermediate layer has an average pore diameter D'av of 0.1 μm or less and a thin film thickness of 1 μm or less. , No. 8 has a large amount of permeate and can perform extremely efficient filtration and separation. In the corrosion resistance test, porous membrane No. 5~
While no pinholes or cracks were observed in NO38, cracks increased in NO19, and local peeling was observed in the thin film, and the albumin rejection rate was 2%.
It has declined to.
平均細孔径５００ Ａ以上の薄膜Ｎｏ、 １０〜Ｎｏ、
Ｉ４においてはいずれもＤｍａｘ／ｄａｖ、Ｄ’ｍａｘ
／ｄａｖが適正な範囲に規定されているため、ピンホー
ル、クラックが認められず、各マーカーに対する阻止率
がほぼ完全である。また、これらの多孔質膜は耐食性試
験によっても膜性能に何等の変化も認められなかった。Thin film with an average pore diameter of 500 A or more No. 10 to No.
In I4, both Dmax/dav and D'max
Since /dav is defined within an appropriate range, no pinholes or cracks are observed, and the rejection rate for each marker is almost perfect. Moreover, no change in membrane performance was observed in these porous membranes even in corrosion resistance tests.
Claims (1)
平均細孔径より小さい平均細孔径を有する多孔質薄膜を
備えてなる無機多孔質膜において、前記多孔質薄膜が付
着する層の最大気孔径が同薄膜の平均細孔径の１〜２５
０倍であることを特徴とする無機多孔質膜。In an inorganic porous membrane comprising a porous thin film having an average pore diameter smaller than the average pore diameter of the support on one side of one or more layers of porous support, the layer to which the porous thin film is attached is The maximum pore diameter is 1 to 25 of the average pore diameter of the same thin film.
An inorganic porous membrane characterized by being 0 times larger.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13082788A JPH01299607A (en) | 1988-05-27 | 1988-05-27 | Inorganic porous membrane |
| US07/357,268 US4929406A (en) | 1988-05-27 | 1989-05-26 | Process for producing an inorganic porous membrane |
| DE68928924T DE68928924T2 (en) | 1988-05-27 | 1989-05-26 | Process for the production of a porous inorganic composite membrane |
| EP89305361A EP0344011A1 (en) | 1988-05-27 | 1989-05-26 | Inorganic porous membrane |
| EP95115691A EP0692303B1 (en) | 1988-05-27 | 1989-05-26 | Process for the production of an inorganic porous composite membrane |
| US07/452,241 US4971696A (en) | 1988-05-27 | 1989-12-18 | Inorganic porous membrane |
| JP5272111A JPH06198148A (en) | 1988-05-27 | 1993-10-29 | Production of inorganic porous membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13082788A JPH01299607A (en) | 1988-05-27 | 1988-05-27 | Inorganic porous membrane |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5272111A Division JPH06198148A (en) | 1988-05-27 | 1993-10-29 | Production of inorganic porous membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01299607A true JPH01299607A (en) | 1989-12-04 |
| JPH0457373B2 JPH0457373B2 (en) | 1992-09-11 |
Family
ID=15043633
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13082788A Granted JPH01299607A (en) | 1988-05-27 | 1988-05-27 | Inorganic porous membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01299607A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03267129A (en) * | 1990-03-16 | 1991-11-28 | Ngk Insulators Ltd | Ceramic membrane filter |
| JPH03284329A (en) * | 1990-03-30 | 1991-12-16 | Ngk Insulators Ltd | Ceramic membraneous filter and production thereof |
| WO1995006514A1 (en) * | 1993-09-02 | 1995-03-09 | The Dow Chemical Company | Separation membrane module |
| JP2006503701A (en) * | 2002-10-25 | 2006-02-02 | テクノロジ・アヴァンセ・エ・マンブラン・アンデュストゥリィエル | Tangential filtration membrane and method for producing the same |
| 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 |
| JP2008178810A (en) * | 2007-01-25 | 2008-08-07 | Miyazaki Prefecture | Bubble-free gas dissolving method |
| JP2013056318A (en) * | 2011-09-09 | 2013-03-28 | Toshiba Corp | Microbubble forming device |
| EP4052774A4 (en) * | 2019-12-30 | 2022-11-16 | Shenzhen Senior Technology Material Co., Ltd. | Wet non-woven fabric, preparation method therefor and water treatment membrane containing wet non-woven fabric |
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| JPS5294572A (en) * | 1975-12-29 | 1977-08-09 | Commissariat Energie Atomique | Filter made from inorganic matter |
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| JPS5294572A (en) * | 1975-12-29 | 1977-08-09 | Commissariat Energie Atomique | Filter made from inorganic matter |
| JPS553809A (en) * | 1978-06-23 | 1980-01-11 | Tdk Corp | Dynamic membrane formation supporter and its manufacture |
| JPS5834006A (en) * | 1981-03-30 | 1983-02-28 | グル−プマン・デテユ−ド・プ−ル・レ・セラミ−ク・アルミニユ−ズ | Filter structure, production thereof and ultrafiltration apparatus using same |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03267129A (en) * | 1990-03-16 | 1991-11-28 | Ngk Insulators Ltd | Ceramic membrane filter |
| JPH03284329A (en) * | 1990-03-30 | 1991-12-16 | Ngk Insulators Ltd | Ceramic membraneous filter and production thereof |
| WO1995006514A1 (en) * | 1993-09-02 | 1995-03-09 | The Dow Chemical Company | Separation membrane module |
| JP2006503701A (en) * | 2002-10-25 | 2006-02-02 | テクノロジ・アヴァンセ・エ・マンブラン・アンデュストゥリィエル | Tangential filtration membrane and method for producing the same |
| 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 |
| JP2008178810A (en) * | 2007-01-25 | 2008-08-07 | Miyazaki Prefecture | Bubble-free gas dissolving method |
| JP2013056318A (en) * | 2011-09-09 | 2013-03-28 | Toshiba Corp | Microbubble forming device |
| EP4052774A4 (en) * | 2019-12-30 | 2022-11-16 | Shenzhen Senior Technology Material Co., Ltd. | Wet non-woven fabric, preparation method therefor and water treatment membrane containing wet non-woven fabric |
| JP2022552913A (en) * | 2019-12-30 | 2022-12-20 | シェンチェン シニア テクノロジー マテリアル カンパニー リミテッド | Wet-laid nonwoven fabric, method of making same, and water treatment membrane comprising wet-laid nonwoven fabric |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0457373B2 (en) | 1992-09-11 |
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