JPH0231823A - Production of inorganic porous film - Google Patents
Production of inorganic porous filmInfo
- Publication number
- JPH0231823A JPH0231823A JP17995688A JP17995688A JPH0231823A JP H0231823 A JPH0231823 A JP H0231823A JP 17995688 A JP17995688 A JP 17995688A JP 17995688 A JP17995688 A JP 17995688A JP H0231823 A JPH0231823 A JP H0231823A
- Authority
- JP
- Japan
- Prior art keywords
- porous
- thin film
- suspension
- support
- film
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000000725 suspension Substances 0.000 claims abstract description 32
- 238000007654 immersion Methods 0.000 claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 18
- 239000010409 thin film Substances 0.000 claims description 38
- 239000012528 membrane Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 4
- 239000010954 inorganic particle Substances 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 6
- 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 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 10
- 239000010408 film Substances 0.000 description 9
- 230000002093 peripheral effect Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- -1 specifically Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 108010025899 gelatin film Proteins 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008131 herbal destillate Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000013020 steam cleaning Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration 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の
製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for manufacturing an inorganic porous membrane used for filtration, gas separation, etc.
無機多孔質膜の一種類として、１または複数層の多孔質
支持体の少くとも一側面に同支持体の平均細孔径より小
さい平均細孔径０．１μｍ以下の多孔質薄膜を備えた無
機多孔質膜がある。この種の多孔質膜は各種の濾過、ガ
ス分離用の膜として使用されるが、かかる用途において
は多孔質薄膜内にピンホール、クラック等が存在しない
ことが肝要である。多孔質薄膜内にピンホール、クラッ
ク等が存在していると、濾過精度、分離精度が低下する
ことは勿論であり、また同薄膜の目詰り等による膜性能
の低下時の再生手段である酸、アルカリ洗浄、殺菌手段
であるスチーム洗浄等によりピンホール、クラック等が
増大して濾過精度、分離精度を一層低下させるとともに
、耐食性を大きく損わせることになる。As a type of inorganic porous membrane, an inorganic porous membrane is provided with a porous thin film having an average pore diameter of 0.1 μm or less, which is smaller than the average pore diameter of the support, on at least one side of one or more layers of porous support. There is a membrane. This type of porous membrane is used as a membrane for various types of filtration and gas separation, but in such applications it is important that there are no pinholes, cracks, etc. in the porous thin membrane. If pinholes, cracks, etc. exist in the porous thin membrane, it goes without saying that filtration accuracy and separation accuracy will decrease, and acid, which is a means of regeneration when the membrane performance deteriorates due to clogging, etc. , alkaline cleaning, steam cleaning as a sterilization means, etc., increase pinholes, cracks, etc., further reducing filtration accuracy and separation accuracy, and significantly impairing corrosion resistance.
ところで、上記した複層構造の無機多孔質膜に関する技
術はすでに多数開示されており、かかる技術を開示する
刊行物の一例として特開昭６０−１５６５１０号公報を
挙げることができる。Incidentally, many technologies related to the above-mentioned multilayer structure inorganic porous membranes have already been disclosed, and Japanese Patent Application Laid-open No. 156510/1983 can be cited as an example of a publication disclosing such technologies.
同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（ゾル液）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
。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。The publication describes a method for producing a crack-free inorganic semi-permeable membrane, specifically, coating a porous support made of sintered inorganic oxide with a suspension (sol solution) of an inorganic membrane-forming coating material and heating it. A method of manufacturing is disclosed. By this manufacturing method, an ultrafiltration membrane in which a porous thin film made of γ-alumina is coated on a porous support is obtained.
しかして、同公報には、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）により定まる旨記載さ
れ、好ましい平均細孔径として０．１０μｖａ −０，
５０ｉｆ ＩＩＩを挙げている。多孔質＊Ｍについては
膜厚が２０μｍ以下である旨、またコーティングゾル液
については媒体中の分散相の濃度が０．０１ｗｔ％〜２
５ｗｔ％である旨記載されている。However, the publication states that the suitability of a porous support is determined by the pore size (average pore diameter) of the support, and the preferred average pore diameter is 0.10 μva -0,
50if III is listed. For porous *M, the film thickness is 20 μm or less, and for coating sol, the concentration of the dispersed phase in the medium is 0.01 wt% to 2.
It is stated that it is 5 wt%.
上記した複層構造の無機多孔質膜を製造する一手段とし
て、１または複数層の多孔質支持体を無機物粒子を含む
懸濁液中に浸濁した後同懸濁液中から引上げて、前記多
孔質支持体の少くとも一側面に前記無機物粒子を主体と
する薄膜を形成し、次いで乾燥、焼成する製造方法があ
る。上記公報に開示された製造方法もかかる製造方法と
基本的には同様であり、多孔質支持体の懸濁液中での浸
漬時間を２秒とし、好ましくは１〜５秒である旨述べて
いる。As one means for producing the above-mentioned multi-layered inorganic porous membrane, one or more layers of porous support are immersed in a suspension containing inorganic particles and then pulled out of the suspension. There is a manufacturing method in which a thin film mainly composed of the inorganic particles is formed on at least one side of a porous support, and then dried and fired. The production method disclosed in the above-mentioned publication is basically the same as this production method, and states that the immersion time of the porous support in the suspension is 2 seconds, preferably 1 to 5 seconds. There is.
本発明者は、上記した製造方法において多孔質薄膜内に
ピンホール、クラック等を発生させる要因に多孔質支持
体の懸濁液中での浸漬時間、懸濁液中からの引上げ速度
があることを見い出し、これらの浸漬時間および引上げ
速度を的確に制御することによりピンホール、クラック
等の発生を防止し得る旨の知見を得た。従って、本発明
の目的はかかる製造方法において、上記した浸漬時間、
引上げ速度を制御することによりピンホール、クラック
等の発生を解消することにある。The present inventor has discovered that the factors that cause pinholes, cracks, etc. to occur in the porous thin film in the above manufacturing method include the immersion time of the porous support in the suspension and the rate of pulling it out of the suspension. They discovered that pinholes, cracks, etc. can be prevented by accurately controlling the dipping time and pulling speed. Therefore, the object of the present invention is to provide such a manufacturing method with the above-mentioned immersion time,
The purpose is to eliminate the occurrence of pinholes, cracks, etc. by controlling the pulling speed.
なお、上記した公報に開示された製造方法においては浸
漬時間のみが開示されているが、浸漬時間（接触時間）
が１〜５秒程度では小形状の支持体での薄膜の形成状態
を制御することができるとしても、大形状の支持体（例
えば長さ１ｍのパイプ状支持体）での薄膜の形成状態を
制御することは不可能である。In addition, in the manufacturing method disclosed in the above-mentioned publication, only the immersion time is disclosed, but the immersion time (contact time)
Even if it is possible to control the formation of a thin film on a small support for 1 to 5 seconds, it is difficult to control the formation of a thin film on a large support (for example, a pipe-shaped support with a length of 1 m). It is impossible to control.
［課題を解決するための手段］
本発明は上記した複層構造の無機多孔質膜の製造方法に
おいて、前記多孔質支持体の懸濁液中での浸漬時間を５
秒以上とし、かつ懸濁液中からの引上げ速度を０．０１
ｍ／秒以上とすることを特徴とするものである。[Means for Solving the Problems] The present invention provides a method for producing an inorganic porous membrane having a multilayer structure described above, in which the immersion time of the porous support in the suspension is 5.
seconds or more, and the pulling speed from the suspension is 0.01
m/sec or more.
本発明において、多孔質支持体はアルミニウム、ジルコ
ニウム１、チタニウム等の酸化物、炭化物、窒化物等の
セラミック、ホウケイ酸ガラス等のガラス、ニッケル等
の金属からなり、パイプ状、平板状、ハニカム状、モノ
リス状等適宜の形状の単層または複層構造のものであり
、その厚みは０．５〜２ｍｍである。また、支持体の平
均細孔径については、支持体が単層である場合には０．
０５〜３μｍ、複層である場合には主層０．１〜３０μ
ｍ、副層（中間層）力月μｍ以下であり、中間層の厚み
は１０〜１５０μｍである。In the present invention, the porous support is made of ceramics such as oxides, carbides, and nitrides such as aluminum, zirconium 1, and titanium, glasses such as borosilicate glass, and metals such as nickel, and is shaped like a pipe, plate, or honeycomb. It has a monolayer or multilayer structure in an appropriate shape such as a monolith, and has a thickness of 0.5 to 2 mm. In addition, the average pore diameter of the support is 0.0 when the support is a single layer.
05-3μm, main layer 0.1-30μm if multilayer
m, the thickness of the sublayer (intermediate layer) is less than μm, and the thickness of the intermediate layer is 10 to 150 μm.
本発明において、多孔質薄膜はチタン、ジルコニウム、
ハフニウム、ニオブ、タンタル、アルミニウム、ケイ素
の酸化物、炭化物、窒化物等の無機物からなり、平均細
孔径が０．１μｍ以下のものである。多孔質支持体が複
層構造である場合、薄膜は少くとも中間層の一側面に形
成される。なお、多孔質支持体の少くとも一側面とは、
同支持体が例えばパイプ状である場合には内周面、外周
面、内外側周面を意味し、平板状である場合には片側面
、両側面を意味し、ハニカム状およびモノリス状である
場合には外周面、多数の内孔の内周面の一部または全部
、内外側周面を意味する。In the present invention, the porous thin film includes titanium, zirconium,
It is made of inorganic materials such as hafnium, niobium, tantalum, aluminum, and silicon oxides, carbides, and nitrides, and has an average pore diameter of 0.1 μm or less. When the porous support has a multilayer structure, the thin film is formed on at least one side of the intermediate layer. Note that at least one side of the porous support is
For example, when the support is pipe-shaped, it means the inner peripheral surface, outer peripheral surface, inner and outer peripheral surfaces, and when it is flat, it means one side, both sides, honeycomb shape and monolith shape. In this case, it means the outer circumferential surface, part or all of the inner circumferential surfaces of a large number of inner holes, and the inner and outer circumferential surfaces.
本発明において、薄膜の形成に用いる懸濁液は主として
水を溶媒とするハイドロゾル液で、アルコキシド、アシ
レート、キレート等の化合物の加水分解懸濁液、金属塩
の加水分解懸濁液、金属水酸化物および微粒金属酸化物
のコロイド懸濁液等が採用される。これらの各懸濁液の
ＰＨは１〜４、濃度（ゾル粒子／溶媒・・・モル比）は
１／４０〜ｌ／３０００であり、かつ粘度は１〜５ＣＰ
である。薄膜の形成時における懸濁液中での浸漬時間は
５秒以上、懸濁液中からの引上げ速度は０．０１ｍ／ｓ
ｅｃ以上であるが、薄膜の１回当たりの担持厚みはＯｊ
〜５μｍとし、必要により薄膜の形成を複数回行って所
定の膜厚とする。なお、この場合薄膜の乾燥、焼成は１
回の薄膜の形成ごとに行う。In the present invention, the suspension used to form a thin film is a hydrosol liquid mainly using water as a solvent, such as a hydrolyzed suspension of compounds such as alkoxides, acylates, and chelates, a hydrolyzed suspension of metal salts, and a hydrolyzed suspension of metal hydroxides. Colloidal suspensions of metal oxides and fine particles of metal oxides are employed. The pH of each of these suspensions is 1 to 4, the concentration (sol particles/solvent... molar ratio) is 1/40 to 1/3000, and the viscosity is 1 to 5CP.
It is. The immersion time in the suspension when forming the thin film is 5 seconds or more, and the pulling speed from the suspension is 0.01 m/s.
ec or more, but the supporting thickness per thin film is Oj
~5 μm, and if necessary, the thin film is formed multiple times to obtain a predetermined film thickness. In this case, the drying and baking of the thin film takes 1
This is done every time the thin film is formed.
［発明の作用・効果コ
本発明においては、多孔質支持体の懸濁液中への浸漬時
間、懸濁液中からの引上げ速度を規定することにより、
多孔質支持体の少くとも一側面に濃縮ゲル化した薄膜が
均一に担持され、かつ同薄膜の均一性を損うことなく引
上げられる。これにより、同薄膜は乾燥、焼成時に不均
一な収縮が生じることがなく、薄膜内でのピンホール、
クラック等の発生が防止される。[Operations and Effects of the Invention] In the present invention, by specifying the immersion time of the porous support in the suspension and the rate of pulling it out of the suspension,
A concentrated gelled thin film is uniformly supported on at least one side of the porous support, and is pulled up without impairing the uniformity of the thin film. As a result, the thin film will not shrink unevenly during drying and baking, and pinholes within the thin film will not occur.
Occurrence of cracks, etc. is prevented.
しかして、浸漬時間は５秒以上必要とし、好ましくは５
〜６０秒である。浸漬時間が５〜６０秒であるときには
、多孔質支持体の少くとも一側面で形成されるゲル膜の
膜厚は時間に影響されず均一な薄膜となるが、浸漬時間
が５秒未満であるときには、ゲル膜の膜厚が時間に影響
され易く不均一な薄膜となる。この場合、多孔質支持体
の細孔内の空気が懸濁液の侵入により気泡となるが、浸
漬時間が短かいと気泡が十分に脱気し得すに薄膜内に欠
陥を生じさせる。この傾向は大形状の支持体において特
に顕著である。一方、浸漬時間が６０秒を超える場合に
は、支持体の少くとも一側面にて一旦濃縮ゲル化したゲ
ル膜が懸濁液へ移行したり、懸濁液が支持体の細孔内に
侵入して局部的にゲル化して、薄膜の膜厚が不均一にな
ってピンホール、クラック等の発生原因となり、かつ多
孔質膜としての使用時の濾過抵抗を増大させる。浸漬時
間のより好ましい範囲は５〜１５秒であり、この範囲内
においては、懸濁液の支持体の細孔内への侵入が極力抑
えられるため支持体における濾過抵抗が増大せず、多孔
質膜としての濾過効率、分離効率が向上する。Therefore, the immersion time needs to be 5 seconds or more, preferably 5 seconds or more.
~60 seconds. When the immersion time is 5 to 60 seconds, the thickness of the gel film formed on at least one side of the porous support is not affected by time and becomes a uniform thin film, but when the immersion time is less than 5 seconds. Sometimes, the thickness of the gel film is easily influenced by time, resulting in a non-uniform thin film. In this case, the air in the pores of the porous support becomes bubbles due to the intrusion of the suspension; however, if the immersion time is short, the bubbles cannot be sufficiently degassed, causing defects in the thin film. This tendency is particularly noticeable in large-sized supports. On the other hand, if the immersion time exceeds 60 seconds, the gel film that has been concentrated and gelled on at least one side of the support may turn into a suspension, or the suspension may enter the pores of the support. This causes local gelation, which makes the thickness of the thin film non-uniform, causing pinholes, cracks, etc., and increases filtration resistance when used as a porous membrane. A more preferable range of the immersion time is 5 to 15 seconds, and within this range, the penetration of the suspension into the pores of the support is suppressed as much as possible, so the filtration resistance of the support does not increase, and the porous The filtration efficiency and separation efficiency of the membrane are improved.
多孔質支持体の懸濁液中からの引上げ速度に関しては、
引上げ速度が０．０１ｍ／ｓｅｃ以上であれば支持体の
少くとも一側面にて濃縮ゲル化した薄膜は均一性を損う
ことなく引上げられ、がっ膜厚は引上げ速度によらずほ
ぼ一定となる。引上げ速度が０．０１＊／ｓｅｃ未満の
場合には薄膜の膜厚が不均一になる。この現象は、支持
体の表面が粗いため引上げ時の薄膜のわずかなすり落が
大きな担持環となって現われるものと思われる。なお、
引上げ速度は等速か否かを問わないが、等速の方が薄膜
に対する応力が小さい点で好ましい、また、支持体が大
形状の場合浸漬時間を５〜６０秒に規定するには、引上
げ速度を０．０５ｍ／ｓｅｃ以上にすることが好ましい
、支持体の長さに関しては、長さ５００ＩＩ＋以上のも
のにも適用でき、最大長さ１５００ｍｍまでのものに適
用できる。なお、支持体の懸濁液中への引下げ速度は特
に限定されないが、０．０１ｍ／ｓｅｃ以上が好ましい
。Regarding the rate of pulling the porous support out of the suspension,
If the pulling speed is 0.01 m/sec or more, the thin film that has become a concentrated gel on at least one side of the support can be pulled up without impairing its uniformity, and the thickness of the film is almost constant regardless of the pulling speed. Become. If the pulling rate is less than 0.01*/sec, the thickness of the thin film will be non-uniform. This phenomenon appears to be due to the roughness of the surface of the support, which causes the thin film to slightly rub off during pulling, resulting in large supporting rings. In addition,
It does not matter whether the pulling speed is constant or not, but uniform speed is preferable because the stress on the thin film is small.Also, when the support is large in shape, in order to specify the immersion time to 5 to 60 seconds, Regarding the length of the support, the speed is preferably 0.05 m/sec or more, the support can be applied to lengths of 500II+ or more, and can be applied to those with a maximum length of 1500 mm. Note that the speed at which the support is lowered into the suspension is not particularly limited, but is preferably 0.01 m/sec or more.
懸濁液に関しては、水を溶媒とするハイドロゾルが好ま
しく、オルガノゾルの場合には表面張力が小さくて支持
体の細孔内へ侵入し易いとともに、溶媒の蒸気圧が高く
かつ乾燥性であることから好ましくない、また、懸濁液
のｐｈは１〜４であることが好ましく、酸性側では懸濁
粒子が直鎖状ポリマーになり易くて支持体の細孔内へ侵
入し難く、均一な膜厚の薄膜の形成が容易である。Regarding suspensions, hydrosols using water as a solvent are preferred; organosols have a low surface tension and can easily penetrate into the pores of the support, and the vapor pressure of the solvent is high and drying properties. Also, it is preferable that the pH of the suspension is between 1 and 4. On the acidic side, the suspended particles tend to become linear polymers, making it difficult for them to penetrate into the pores of the support, resulting in a uniform film thickness. It is easy to form a thin film.
［実施例］
チタニウムイソプロポキシドを酸の存在下で加水分解し
てアルコラード／水のモル比１／１００のゾル液を得、
これを水で希釈してモル比１１５００の担持ゾル液を調
製した。このゾル液内に主層の内周側に中間層を有する
複層構造のアルミナ質からなるパイプ状の多孔質支持体
を、縦にして担持ゾル液中に浸漬して各時間保持し、同
支持体の内周面に担持ゾル液を担持して薄膜を形成し、
これを担持ゾル液中から各速度で引上げた０次いで、薄
膜を支持体とともに室温で２時間乾燥するとともに１０
０℃で２時間乾燥し、その後４００℃で３時間焼成し、
支持体の内周面に平均細孔径５０Ａの多孔質薄膜を有す
る多孔質膜を得た。なお、多孔質支持体は外径１０ｍ＋
■、内径７ＩＩ＋、長さ５００ｍｍのパイプ状のもので
、主層および中間層の平均細孔径は１．０μｍおよび０
．０８μｍ、これらの最大気孔径は１．５μ■および０
．２５μｍである。[Example] Hydrolyzing titanium isopropoxide in the presence of an acid to obtain a sol liquid with a molar ratio of Alcolade/water of 1/100,
This was diluted with water to prepare a supported sol solution with a molar ratio of 11,500. A pipe-shaped porous support made of alumina with a multilayer structure having an intermediate layer on the inner circumferential side of the main layer is immersed vertically in this sol solution and held for each period of time. A thin film is formed by supporting the supported sol liquid on the inner peripheral surface of the support,
This was pulled up from the supporting sol solution at various speeds.Then, the thin film was dried together with the support at room temperature for 2 hours, and
Dry at 0°C for 2 hours, then bake at 400°C for 3 hours,
A porous membrane having a porous thin film with an average pore diameter of 50A on the inner peripheral surface of the support was obtained. Note that the porous support has an outer diameter of 10 m+
■, pipe-shaped with an inner diameter of 7II+ and a length of 500 mm, and the average pore diameters of the main layer and intermediate layer are 1.0 μm and 0.
．． 08μm, these maximum pore diameters are 1.5μ■ and 0
．． It is 25 μm.
多孔質支持体の担持ゾル液中への浸漬時間（ｓｅｅ）、
引上げ速度（ｍ／５ｅｅ）、多孔質薄膜の各部位の膜厚
（μｍ）および膜厚のバラツキ（全σゎ−１・μｍ）、
同薄膜内のピンホール、クラック等の存在状態を別表に
示す、なお、膜厚、ピンホールおよびクラック等の存在
状態は走査型電子顕微鏡の測定に基づくものである。同
表から明らかなように、浸漬時間５〜６０秒、引上げ速
度０．０１ｍ／ｓｅｃ以上の場合（Ｎｏ、２〜Ｎｏ、６
） 、薄膜の膜厚は均一でかつピンホール、クラック等
が存在しないのに対し、浸漬時間が５秒未満の場合（Ｎ
ｏ、り、薄膜の膜厚は不均一であり、また引上げ速度が
０．０１ｍ／ｓｅｃの場合（Ｎｏ、♂）、薄膜の膜厚は
不均一でかつピンホール、クラック等が存在している。Immersion time (see) of the porous support into the supporting sol solution,
Pulling speed (m/5ee), film thickness (μm) of each part of the porous thin film, and variation in film thickness (total σゎ-1 μm),
The presence of pinholes, cracks, etc. in the same thin film is shown in the attached table. The film thickness and the presence of pinholes, cracks, etc. are based on measurements using a scanning electron microscope. As is clear from the table, when the immersion time is 5 to 60 seconds and the pulling speed is 0.01 m/sec or more (No, 2 to No, 6
), the thickness of the thin film is uniform and there are no pinholes, cracks, etc., but if the immersion time is less than 5 seconds (N
o, ri, the film thickness of the thin film is non-uniform, and when the pulling speed is 0.01 m/sec (No, ♂), the film thickness of the thin film is non-uniform and there are pinholes, cracks, etc. .
但し、この場合の支持体の長さは１５０ｍｍであった。However, the length of the support in this case was 150 mm.
なお、Ｎｏ、７の場合は引上げ速度が１．２ｍ／ｓｅｃ
と極めて大きく、薄膜内にピンホール、クラック等が存
在している。In addition, in the case of No. 7, the pulling speed is 1.2 m/sec.
It is extremely large, and there are pinholes, cracks, etc. within the thin film.
（以下余白）(Margin below)
Claims (1)
液中に浸漬した後同懸濁液中から引上げて、前記多孔質
支持体の少くとも一側面に前記無機物粒子を主体とする
薄膜を形成し、次いで乾燥、焼成することからなる平均
細孔径０．１μｍ以下の多孔質薄膜を備えた無機多孔質
膜の製造方法において、前記多孔質支持体の懸濁液中で
の浸漬時間を５秒以上とし、かつ懸濁液中からの引上げ
速度を０．０１ｍ／秒以上とすることを特徴とする無機
多孔質膜の製造方法。One or more layers of porous support are immersed in a suspension containing inorganic particles and then pulled out of the suspension to form a thin film mainly composed of the inorganic particles on at least one side of the porous support. In the method for producing an inorganic porous membrane having a porous thin film with an average pore diameter of 0.1 μm or less, which comprises forming a porous support, followed by drying and firing, the immersion time of the porous support in the suspension is A method for producing an inorganic porous membrane, characterized in that the pulling time from the suspension is 5 seconds or more, and the pulling speed from the suspension is 0.01 m/second or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17995688A JPH0231823A (en) | 1988-07-19 | 1988-07-19 | Production of inorganic porous film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17995688A JPH0231823A (en) | 1988-07-19 | 1988-07-19 | Production of inorganic porous film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0231823A true JPH0231823A (en) | 1990-02-01 |
Family
ID=16074903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17995688A Pending JPH0231823A (en) | 1988-07-19 | 1988-07-19 | Production of inorganic porous film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0231823A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03284329A (en) * | 1990-03-30 | 1991-12-16 | Ngk Insulators Ltd | Ceramic membraneous filter and production thereof |
-
1988
- 1988-07-19 JP JP17995688A patent/JPH0231823A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03284329A (en) * | 1990-03-30 | 1991-12-16 | Ngk Insulators Ltd | Ceramic membraneous filter and production thereof |
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