JPH0334970B2 - - Google Patents
Info
- Publication number
- JPH0334970B2 JPH0334970B2 JP25816887A JP25816887A JPH0334970B2 JP H0334970 B2 JPH0334970 B2 JP H0334970B2 JP 25816887 A JP25816887 A JP 25816887A JP 25816887 A JP25816887 A JP 25816887A JP H0334970 B2 JPH0334970 B2 JP H0334970B2
- Authority
- JP
- Japan
- Prior art keywords
- deposited
- layer
- alkoxide
- thickener
- organometallic compound
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 claims description 12
- 150000004703 alkoxides Chemical class 0.000 claims description 10
- 239000002562 thickening agent Substances 0.000 claims description 9
- 238000000108 ultra-filtration Methods 0.000 claims description 9
- 229910052751 metal Chemical class 0.000 claims description 7
- 239000002184 metal Chemical class 0.000 claims description 7
- 238000001471 micro-filtration Methods 0.000 claims description 7
- 150000002902 organometallic compounds Chemical class 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000001223 reverse osmosis Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical group CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011354 acetal resin Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229920006324 polyoxymethylene Polymers 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052729 chemical element Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 235000005985 organic acids Nutrition 0.000 claims 1
- 239000012528 membrane Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 2
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Description
【発明の詳細な説明】
本発明は、微細濾過（microfiltration）、限外
濾過または逆浸透用エレメントの製造方法に係
る。通常は、アルコキシド、有機金属化合物また
は無化もしくは有機の酸の金属塩を加水分解して
対応する化学元素の酸化物または水酸化物粒子の
ゾルを生成し、前記ゾルに増粘剤を添加し、得ら
れたゾルを濾過エレメントに所望される細孔より
荒目の細孔をもつ支持層にコートし、次に支持層
に堆積した薄膜を乾燥させ、次に熱処理によつて
増粘剤を除去して堆積薄膜の粒子の焼結を生起す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing elements for microfiltration, ultrafiltration or reverse osmosis. Typically, an alkoxide, an organometallic compound or a metal salt of an inorganic or organic acid is hydrolyzed to produce a sol of oxide or hydroxide particles of the corresponding chemical element, and a thickener is added to said sol. The resulting sol is coated on a support layer with pores coarser than those desired for the filtration element, the thin film deposited on the support layer is dried, and the thickener is removed by heat treatment. Removal causes sintering of the particles of the deposited film.
この種の方法は、フランス特許公開第2150390
号に提案されている。 This kind of method is described in French Patent Publication No. 2150390
proposed in No.
しかしながら、多孔性支持体に堆積によつて濾
過層を形成し得るゾルの製造は難しく、また微細
濾過、限外濾過及び逆浸透での使用に適する十分
に微細な粒子サイズを得ることも難しい。 However, it is difficult to produce sols that can be deposited onto porous supports to form filtration layers, and it is also difficult to obtain sufficiently fine particle sizes for use in microfiltration, ultrafiltration and reverse osmosis.
更に、支持層に堆積したゲル層の乾燥と焼成と
の過程でゲルの亀裂と崩壊の発生を阻止すること
も難しい。 Furthermore, it is difficult to prevent the gel from cracking and collapsing during the drying and baking process of the gel layer deposited on the support layer.
本発明の目的は、支持層にコーテイングによつ
て容易に堆積させることができ、ゲルの乾燥と焼
成との過程で粒子の阻粒化とゲルの亀裂及び崩壊
の発生とを阻止し得るような微細濾過、限外濾過
または逆浸透用エレメントの製造方法を提供する
ことである。本発明の目的はさらに、細孔直径が
極めて小さいこと、透過率が高いこと、厚みが薄
く均等であること、機械的耐久性が良く逆圧によ
る洗浄及び高い濾過圧力の使用ができること、化
学的耐性が良く微生物及び酸素の作用に強いこと
等の如き特性を有する微細濾過、限外濾過または
逆浸透用エレメントを提供することである。 The object of the present invention is to provide a coating material that can be easily deposited on a support layer by coating and that can prevent particles from becoming grain-restricted and cracking and collapsing of the gel during the gel drying and baking process. An object of the present invention is to provide a method for manufacturing an element for microfiltration, ultrafiltration, or reverse osmosis. Further objects of the present invention include extremely small pore diameters, high permeability, thin and uniform thickness, good mechanical durability and the ability to use back pressure cleaning and high filtration pressures, chemical It is an object of the present invention to provide an element for microfiltration, ultrafiltration or reverse osmosis which has characteristics such as good resistance and resistance to the action of microorganisms and oxygen.
本発明は、微細濾過、限外濾過または逆浸透用
エレメントの製造方法を提供し、該方法は、当該
エレメントに所望される細孔より大きな細孔を有
する支持層上に、増粘剤を加えた、アルコキシ
ド、有機金属化合物または無機もしくは有機の酸
の金属塩より得た混合物の薄層をコーテイングし
て堆積させ、堆積した層を熱処理して増粘剤を除
去し、該層の粒子を焼結することからなり、前記
アルコキシド、有機金属化合物または金属塩を最
初に無水有機溶媒中に溶解すること及びコーテイ
ングににより堆積された前記薄層を前記熱処理に
先立つて前記アルコキシド、有機金属化合物また
は金属塩を加水分解するのに十分な湿潤雰囲気下
で乾燥することを特徴とする。 The present invention provides a method of manufacturing an element for microfiltration, ultrafiltration or reverse osmosis, which method comprises adding a thickening agent onto a support layer having pores larger than the pores desired for the element. Alternatively, a thin layer of a mixture obtained from an alkoxide, an organometallic compound or a metal salt of an inorganic or organic acid is deposited as a coating, the deposited layer is heat treated to remove the thickening agent, and the particles of the layer are sintered. the thin layer deposited by first dissolving said alkoxide, organometallic compound or metal salt in an anhydrous organic solvent and coating said alkoxide, organometallic compound or metal prior to said heat treatment. Characterized by drying under a sufficiently humid atmosphere to hydrolyze the salt.
無水アルコール中の溶液を用いる場合には、増
粘剤はアセタール樹脂のような有機ポリマーであ
ることが好ましい。 When using solutions in absolute alcohol, the thickener is preferably an organic polymer such as an acetal resin.
本発明の方法により、特に粒子がアルミニウ
ム、チタン、ジルコニウムもしくはケイ素または
それらの混合物の水酸化物または酸化物から成る
ような、微細濾過、限外濾過または逆浸透用エレ
メントを製造し得る。 By the method of the invention it is possible to produce elements for microfiltration, ultrafiltration or reverse osmosis, in particular in which the particles consist of hydroxides or oxides of aluminum, titanium, zirconium or silicon or mixtures thereof.
以下に実施例として、本発明による膜の製造方
法を示す。 The method for manufacturing a membrane according to the present invention will be shown below as an example.
実施例
チタンのエトキシド、プロポキシドまたはイソ
プロポキシド、またはジルコニウムのエトキシ
ド、プロポキシドまたはイソプロポキシド、ある
いはまた四塩化チタンまたは四塩化ジルコニウム
といつたアルコキシドを出発物質とする。Examples Starting materials are ethoxide, propoxide or isopropoxide of titanium, or ethoxide, propoxide or isopropoxide of zirconium, or alternatively alkoxides such as titanium tetrachloride or zirconium tetrachloride.
これをエタノール、プロパノール、イソプロパ
ノールまたはグリコールといつた無水有機溶媒中
に溶かす。 This is dissolved in an anhydrous organic solvent such as ethanol, propanol, isopropanol or glycol.
これをアルコキシドと同じ溶媒中に増粘剤ポリ
マー（たとえばシヤウイニガン［Shawinigan］
社が“ブトバール（Butvar）”の商品名で市販し
ているもの、あるいはローヌプーラン［Rhone
Poulenc］社が“ロビナール（Rhovinal）”の商
品名で市販しているもののようなアセタール樹
脂）を溶かしたゲルと混合する。 This is added to a thickening polymer (e.g. Shawinigan) in the same solvent as the alkoxide.
sold under the trade name “Butvar” by the company, or Rhone Poulenc.
Acetal resin (such as that sold under the trade name ``Rhovinal'' by Poulenc) is mixed with a dissolved gel.
この混合物の膜を、限外濾過膜を形成したいと
所望する多孔性セラミツクの表面上に堆積させる
が、その方法は該混合物を多孔性管につめ、１〜
数分間接触させた後にこの管を空けるという手順
による。 A membrane of this mixture is deposited onto the surface of the porous ceramic in which it is desired to form an ultrafiltration membrane, by packing the mixture into a porous tube and
The procedure involves emptying the tube after several minutes of contact.
次に膜を湿潤雰囲気中で乾燥させる。出発溶媒
によつて空気中の湿気が膜中に侵入することがで
き、次の反応のうちのいずれかに従つてアルコキ
シドの加水分解が生じる。 The membrane is then dried in a humid atmosphere. The starting solvent allows atmospheric moisture to enter the membrane and hydrolysis of the alkoxide occurs according to one of the following reactions.
Ti（OC2H5）4＋4H2O
→Ti（OH）4＋4C2H5OH
Zr（OC3H8）4＋4H2O
→Zr（OH）4＋4C3H8OH
TiCl4＋2H2O→TiO2＋4HCl
増粘剤の存在によつて、加水分解に際して形成
される水酸化物の結晶の成長を防ぐことができ
る。 Ti(OC 2 H 5 ) 4 +4H 2 O →Ti(OH) 4 +4C 2 H 5 OH Zr(OC 3 H 8 ) 4 +4H 2 O →Zr(OH) 4 +4C 3 H 8 OH TiCl 4 +2H 2 O→ The presence of the TiO 2 +4HCl thickener makes it possible to prevent the growth of hydroxide crystals formed during hydrolysis.
そして、有機化合物の燃焼による除去と二酸化
チタンまたは二酸化ジルコニウムへの水酸化物の
完全な分解を達成するように、数100℃から1000
℃に至る温度で焼成を行う。所望の細孔直径が達
成されたときに焼成を停止する。 and from several 100°C to 1000°C to achieve combustion removal of organic compounds and complete decomposition of hydroxide into titanium dioxide or zirconium dioxide.
Firing is carried out at temperatures up to ℃. Firing is stopped when the desired pore diameter is achieved.
酸化チタンまたは酸化ジルコニウムをベースと
する限外濾過エレメントは、ガンマアルミニウム
をベースとするエレメントに比べてより優れた化
学的耐性を提供する。 Ultrafiltration elements based on titanium oxide or zirconium oxide offer better chemical resistance compared to elements based on gamma aluminum.
Claims (1)
トの製造方法であつて、当該エレメントに所望さ
れる細孔より大きな細孔を有する支持層上に、増
粘剤を加えた、アルコキシド、有機金属化合物ま
たは無機もしくは有機の酸の金属塩より得た混合
物の薄層をコーテイングして堆積させ、堆積した
層を熱処理して増粘剤を除去し、該層の粒子を焼
結することからなり、前記アルコキシド、有機金
属化合物または金属塩を最初に無水有機溶媒中に
溶解すること及びコーテイングにより堆積された
前記薄層を前記熱処理に先立つて前記アルコキシ
ド、有機金属化合物または金属塩を加水分解する
のに十分な湿潤雰囲気下で乾燥することを特徴と
する前記方法。 ２ 増粘剤がアセタール樹脂であり、溶媒が無水
アルコールであることを特徴とする特許請求の範
囲第１項に記載の方法。 ３ 酸化物または水酸化物粒子の化学元素がアル
ミニウム、チタン、ジルコニウムまたはケイ素で
あること、またはこれら元素の化合物の混合物を
出発材料とすることを特徴とする特許請求の範囲
第１項または第２項に記載の方法。[Claims] 1. A method for producing an element for microfiltration, ultrafiltration, or reverse osmosis, which comprises adding a thickener to a support layer having pores larger than those desired for the element. , alkoxides, organometallic compounds or metal salts of inorganic or organic acids are coated and deposited, the deposited layer is heat treated to remove the thickening agent and the particles of the layer are sintered. the alkoxide, organometallic compound or metal salt is first dissolved in an anhydrous organic solvent and the thin layer deposited by coating is coated with the alkoxide, organometallic compound or metal salt prior to the heat treatment. A method as described above, characterized in that the drying is carried out under a humid atmosphere sufficient to effect hydrolysis. 2. The method according to claim 1, wherein the thickener is an acetal resin and the solvent is anhydrous alcohol. 3. Claims 1 or 2, characterized in that the chemical element of the oxide or hydroxide particles is aluminum, titanium, zirconium, or silicon, or that the starting material is a mixture of compounds of these elements. The method described in section.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8314212 | 1983-09-06 | ||
| FR8314212 | 1983-09-06 | ||
| FR8318648 | 1983-11-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63116709A JPS63116709A (en) | 1988-05-21 |
| JPH0334970B2 true JPH0334970B2 (en) | 1991-05-24 |
Family
ID=9292012
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18722584A Granted JPS6071007A (en) | 1983-09-06 | 1984-09-06 | Production of fine filtration, ultrafiltration or reverse osmosis element |
| JP25816887A Granted JPS63116709A (en) | 1983-09-06 | 1987-10-13 | Manufacture of element for fine filtration, ultrafiltration or reverse osmosis |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18722584A Granted JPS6071007A (en) | 1983-09-06 | 1984-09-06 | Production of fine filtration, ultrafiltration or reverse osmosis element |
Country Status (1)
| Country | Link |
|---|---|
| JP (2) | JPS6071007A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8609248D0 (en) * | 1986-04-16 | 1986-05-21 | Alcan Int Ltd | Composite membranes |
| JP4968990B2 (en) * | 2001-06-29 | 2012-07-04 | 京セラ株式会社 | Manufacturing method of inorganic separation membrane |
| JP5033670B2 (en) * | 2008-02-14 | 2012-09-26 | 日本碍子株式会社 | Manufacturing method of ceramic filter |
| JP4960286B2 (en) * | 2008-03-21 | 2012-06-27 | 日本碍子株式会社 | Method for producing nanofiltration membrane |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE787964A (en) * | 1971-08-24 | 1973-02-26 | Montedison Spa | PROCESS FOR PREPARING POROUS COMPOSITE MEMBRANES OR BARRIERS FOR GAS DIFFUSION SYSTEMS |
| US3941719A (en) * | 1972-08-17 | 1976-03-02 | Owens-Illinois, Inc. | Transparent activated nonparticulate alumina and method of preparing same |
| JPS5425520A (en) * | 1977-07-27 | 1979-02-26 | Kankyo Kaihatsu Kk | Method of connecting sewer and so on |
| JPS5959224A (en) * | 1982-09-28 | 1984-04-05 | Mitsubishi Heavy Ind Ltd | Preparation of porous diaphragm |
| JPS5992001A (en) * | 1982-11-18 | 1984-05-28 | Mitsubishi Heavy Ind Ltd | Preparation of porous diaphragm |
| NL8303079A (en) * | 1983-09-05 | 1985-04-01 | Stichting Energie | PROCESS FOR THE PREPARATION OF CRACK-FREE SEMI-PERMEABLE INORGANIC MEMBRANES. |
-
1984
- 1984-09-06 JP JP18722584A patent/JPS6071007A/en active Granted
-
1987
- 1987-10-13 JP JP25816887A patent/JPS63116709A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6071007A (en) | 1985-04-22 |
| JPS6336808B2 (en) | 1988-07-21 |
| JPS63116709A (en) | 1988-05-21 |
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