JPH01281119A - Glass-ceramic-type filtration material and its manufacture - Google Patents
Glass-ceramic-type filtration material and its manufactureInfo
- Publication number
- JPH01281119A JPH01281119A JP11071688A JP11071688A JPH01281119A JP H01281119 A JPH01281119 A JP H01281119A JP 11071688 A JP11071688 A JP 11071688A JP 11071688 A JP11071688 A JP 11071688A JP H01281119 A JPH01281119 A JP H01281119A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- porous
- zirconia
- ceramic
- silica
- 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
- 239000000463 material Substances 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000001914 filtration Methods 0.000 title abstract description 8
- 239000000919 ceramic Substances 0.000 claims abstract description 35
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 239000005373 porous glass Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000010304 firing Methods 0.000 claims description 7
- 239000002241 glass-ceramic Substances 0.000 claims 2
- 239000000243 solution Substances 0.000 abstract description 19
- 239000007789 gas Substances 0.000 abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 5
- -1 Si(OCH3)4 Chemical class 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 17
- 239000011148 porous material Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000002131 composite material Substances 0.000 description 10
- 238000000926 separation method Methods 0.000 description 6
- 239000002344 surface layer Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 210000001179 synovial fluid Anatomy 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101100342332 Mus musculus Klf16 gene Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Filtering Materials (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、ガラス・セラミックス系濾過材およびその製
造方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a glass/ceramic filter medium and a method for manufacturing the same.
従来技術とその問題点
アルミニウムアルコキシドの溶液を多孔質セラミックス
上に付与し、乾燥により加水分解し、焼結して、多孔質
のアルミナ膜を形成させて、複層セラミックス系濾過材
を製造する方法は、公知である。しかしながら、この方
法により得られる濾過材においては、乾燥−焼結工程で
アルミナ膜にひび割れが生じるので、アルミニウムアル
コキシドの溶液塗布を１０回以上繰返し行う必要があり
、工程が煩瑣となるばかりではなく、濾過材としての透
過速度も、低下する欠点がある。Prior art and its problems A method of manufacturing multilayer ceramic filter media by applying a solution of aluminum alkoxide onto porous ceramics, drying it to hydrolyze it, and sintering it to form a porous alumina membrane. is publicly known. However, in the filter material obtained by this method, cracks occur in the alumina membrane during the drying and sintering process, so it is necessary to apply the aluminum alkoxide solution ten or more times, which not only makes the process cumbersome, but also It also has the disadvantage that the permeation rate as a filter medium decreases.
問題点を解消するための手段
本発明者は、上記の如きセラミックス系濾過材の問題点
に鑑みて種々研究を重ねた結果、多孔質シリカ−ジルコ
ニア系ガラス膜を多孔質セラミックス基村上に形成させ
る場合には、これらの問題点が大巾に軽減されることを
見出した。Means for Solving the Problems In view of the above-mentioned problems with ceramic filter media, the inventor of the present invention has conducted various studies, and as a result, formed a porous silica-zirconia glass membrane on a porous ceramic substrate. It has been found that these problems can be greatly alleviated in some cases.
すなわち、本発明は、下記のガラス・セラミックス系濾
過材及びその製造方法を提供するものである：
■多孔質セラミックス基材上にシリカージルコニア系多
孔質ガラス膜を備えたガラス・セラミック系濾過材。That is, the present invention provides the following glass/ceramic filtration material and its manufacturing method: ■Glass/ceramic filtration material provided with a silica-zirconia porous glass membrane on a porous ceramic base material. .
■多孔質セラミックス基材上にシリカ源およびジルコニ
ア源となるアルコキシドの混合溶液を付与し、乾燥し、
焼成することを特徴とするガラス・セラミックス系濾過
材の製造方法。■Apply a mixed solution of alkoxides that will become a silica source and a zirconia source onto a porous ceramic substrate, dry it,
A method for manufacturing a glass/ceramic filter material, which is characterized by firing.
本発明において使用する多孔質セラミックス基材は、ア
ルミナ、ジルコニア、炭化ケイ素、炭素、チッ化ケイ素
などである。該基材の厚さ、細孔径、細孔容積などは、
特に限定されず、被濾過物、滑液の種類などに応じて、
適宜選択すれば良いが、通常厚さ１〜２ｍｎ＋程度、細
孔径０．１〜０．５μｍ程度、細孔容積０．３〜０．５
ｃｃ／ｇ程度である。Porous ceramic substrates used in the present invention include alumina, zirconia, silicon carbide, carbon, and silicon nitride. The thickness, pore diameter, pore volume, etc. of the base material are as follows:
There are no particular limitations, depending on the filtered material, type of synovial fluid, etc.
It may be selected as appropriate, but usually has a thickness of about 1 to 2 mm+, a pore diameter of about 0.1 to 0.5 μm, and a pore volume of 0.3 to 0.5.
It is about cc/g.
多孔質セラミックス基村上に形成されるシリカ−ジルコ
ニア系多孔質ガラス膜は、シリカ２０〜７０重量％とジ
ルコニア８０〜３０重量％の割合とすることが好ましい
。該ガラス膜の厚さ、細孔径、細孔容積なども、特に限
定されず、やはり被濾過物、滑液の種類などに応じて、
適宜選択すれば良いが、通常厚さ０．５〜１５μｍ程度
、細孔径２〜１１００ｎ程度、細孔容積０．０３〜０゜
３ ｃ ｃ ／ ｇ程度である。このようなセラミック
膜は、必要に応じて、複数層形成しても良い。The silica-zirconia based porous glass film formed on the porous ceramic substrate preferably has a ratio of 20 to 70% by weight of silica and 80 to 30% by weight of zirconia. The thickness, pore diameter, pore volume, etc. of the glass membrane are not particularly limited, and may vary depending on the substance to be filtered, the type of synovial fluid, etc.
Although it may be selected as appropriate, the thickness is usually about 0.5 to 15 μm, the pore diameter is about 2 to 1100 nm, and the pore volume is about 0.03 to 0.3 cc/g. A plurality of layers of such ceramic films may be formed as necessary.
本発明の複層セラミックス系濾過材は、以下のようにし
て、製造される。まず、シリカ源およびジルコニア源と
なるアルコキシドの混合溶液を調製する。シリカ源とな
るアルコキシドとしては、Ｓｉ （ＯＣＨ３）４、Ｓ
ｉ （ＯＣ２Ｈ５）４、Ｓ ｉ （ＯＣ３Ｈ７） ４
などが例示され、ジルコニア源となるアルコキシドとし
ては、
Ｚｒ （ＯＣ３Ｈ７）４ 、Ｚｒ （ＯＣ４Ｈ９）４、
Ｚ ｒ （ＯＣ５Ｈ１１） ４などが例示される。これ
らのアルコキシドを含有する溶液は、常法に従って、メ
タノール、エタノール、プロパツール、ブタノールなど
のアルコールと水との混合溶媒にアルコキシドを加える
ことにより、調製される。溶液の調製に際しては、必要
ならば、塩酸、硫酸、硝酸などを添加しても良い。次い
で、該溶液をセラミックス多孔質基材上に塗布するか、
該溶液にセラミックス多孔質基材上を浸漬するなどの任
意の手段により、基材上にアルコキシド溶液を付与した
後、室温〜１５０℃程度で乾燥し、３００〜８００℃程
度で焼成する。必要ならば、乾燥速度を制御するために
、乾燥工程中に湿度調整を行なっても良い。シリカ−ジ
ルコニアガラス膜の厚さおよび強度が不足する場合には
、溶液の付与、乾燥および焼成を複数回繰り返せば良い
。通常この繰返し操作は、５〜６回程度で十分である。The multilayer ceramic filter medium of the present invention is manufactured as follows. First, a mixed solution of alkoxides serving as a silica source and a zirconia source is prepared. Alkoxides serving as silica sources include Si (OCH3)4, S
i (OC2H5) 4, S i (OC3H7) 4
Examples include Zr (OC3H7)4, Zr (OC4H9)4,
Z r (OC5H11) 4 and the like are exemplified. Solutions containing these alkoxides are prepared by adding the alkoxides to a mixed solvent of alcohol, such as methanol, ethanol, propatool, butanol, and water, according to a conventional method. When preparing the solution, hydrochloric acid, sulfuric acid, nitric acid, etc. may be added if necessary. Next, apply the solution onto a ceramic porous substrate, or
After applying the alkoxide solution onto the substrate by any means such as dipping the porous ceramic substrate in the solution, it is dried at room temperature to about 150°C and fired at about 300 to 800°C. If desired, humidity adjustments may be made during the drying process to control the drying rate. If the thickness and strength of the silica-zirconia glass film are insufficient, applying the solution, drying and firing may be repeated multiple times. Usually, it is sufficient to repeat this operation about 5 to 6 times.
発明の効果
本発明による複層セラミックス系濾過材は、機械的強度
の大きな多孔質セラミックス基材上に分離性に優れたシ
リカ−ジルコニアガラス膜を備えており、透過速度が大
きいので、各種気体および液体の濾過用、分離用の濾過
材として有用である。Effects of the Invention The multilayer ceramic filtration medium of the present invention has a silica-zirconia glass membrane with excellent separation property on a porous ceramic base material with high mechanical strength, and has a high permeation rate, so it can absorb various gases and It is useful as a filter material for liquid filtration and separation.
また、その製造方法も、従来法に比して、簡便なもので
ある。Moreover, the manufacturing method thereof is also simpler than conventional methods.
実施例
以下実施例を示し、本発明の特徴とするところをより一
層明確にする。EXAMPLES Examples will be shown below to further clarify the features of the present invention.
実施例１
シリカ源としてのＳ ｉ （ＯＣ２Ｈ５） ４１３０
ｇ１ジル＝ｒ＝、ア源としてのＺｒ （ＯＣ３Ｈ７）
４８７ｇ、０．１５モル／１の塩酸水溶液１１ｇおよび
Ｃ２Ｈ５ＯＨ５２６ｇからなる混合溶液を調製した後、
表面層の平均細孔径が０．２μｍである多孔質アルミナ
管を該混合溶液に浸漬した。Example 1 S i (OC2H5) 4130 as a silica source
g1 Jill = r =, Zr as a source (OC3H7)
After preparing a mixed solution consisting of 487 g, 11 g of 0.15 mol/1 aqueous hydrochloric acid solution and 526 g of C2H5OH,
A porous alumina tube whose surface layer had an average pore diameter of 0.2 μm was immersed in the mixed solution.
次いで、これを温度９８°Ｃ１相対湿度９５％の恒温恒
湿器に入れ、６０分間保持した後、電気炉中３００℃で
１０分間焼成した。この様な溶液の付与、乾燥および焼
成をさらに４回繰返した。ただし、最終回の焼成は、５
００℃で２０分間行った。Next, this was placed in a constant temperature and humidity chamber at a temperature of 98° C. and a relative humidity of 95%, held for 60 minutes, and then baked at 300° C. for 10 minutes in an electric furnace. Application of the solution, drying, and baking were repeated four more times. However, the final firing is 5
The test was carried out at 00°C for 20 minutes.
かくして、多孔質アルミナ管の表面にＺｒ０２３０モル
９６Ｓｉ０２７０モル％のガラス膜を備えた複合多孔質
セラミックス管が得られた。ガラス膜の付着量は、０．
２０ｇ／ｄｒｒｆであった。In this way, a composite porous ceramic tube was obtained, which had a glass film of Zr0230 mol 96Si0270 mol % on the surface of the porous alumina tube. The adhesion amount of the glass film was 0.
It was 20g/drrf.
実施例２
シリカ源としてのＳ ｉ（ＯＣ２Ｈ５） Ａ ８０ ｇ
ｓジルコニア源としてのＺ ｒ （ＯＣ３Ｈｖ ）
４１２５ｇ、０．１５モル／１の塩酸水溶液７ｇおよび
Ｃ２Ｈ５０Ｈ４４８ｇからなる混合溶液を調製した後、
表面層の平均細孔径が０．２μｍである多孔質アルミナ
管を該混合溶液に浸漬した。Example 2 80 g of Si(OC2H5) A as silica source
Zr (OC3Hv) as a zirconia source
After preparing a mixed solution consisting of 4125 g, 7 g of 0.15 mol/1 hydrochloric acid aqueous solution and 448 g of C2H50H,
A porous alumina tube whose surface layer had an average pore diameter of 0.2 μm was immersed in the mixed solution.
次いで、これを温度１００℃、相対湿度１００％の恒温
恒湿器に入れ、１２０分間保持した後、電気炉中３００
℃で１０分間焼成した。この様な溶液の付与、乾燥およ
び焼成をさらに４回繰返した。Next, this was placed in a constant temperature and humidity chamber at a temperature of 100°C and a relative humidity of 100%, held for 120 minutes, and then heated at 300°C in an electric furnace.
It was baked at ℃ for 10 minutes. Application of the solution, drying, and baking were repeated four more times.
ただし、最終回の焼成は、５００℃で２０分間行った。However, the final firing was performed at 500° C. for 20 minutes.
かくして、多孔質アルミナ管の表面にＺｒ０２５０モル
％−８ｉ０２５０モル％のガラス膜を備えた複合多孔質
セラミックス管が得られた。ガラス膜の付着量は、０．
２５ｇ／ｄｒ＆であった。In this way, a composite porous ceramic tube having a glass film containing 250 mol% of Zr0250 mol% and 250 mol% of 8i0 on the surface of a porous alumina tube was obtained. The adhesion amount of the glass film was 0.
It was 25g/dr&.
実施例３
シリカ源としてのＳ ｉ （ＯＣ２Ｈ５） ４１６１
ｇ１ジルコニア源としてのＺ ｒ （ＯＣ３Ｈ７） ４
６３ｇ、０．１５モル／１の塩酸水溶液１４ｇおよびＣ
２Ｈ６ＯＨ５７４ｇからなる混合溶液を調製した後、表
面層の平均細孔径が０．２μｍである多孔質アルミナ管
を該混合溶液に浸漬した。Example 3 S i (OC2H5) 4161 as a silica source
g1 Z r (OC3H7) 4 as a zirconia source
63 g, 14 g of 0.15 mol/1 aqueous hydrochloric acid solution and C
After preparing a mixed solution consisting of 574 g of 2H6OH, a porous alumina tube whose surface layer had an average pore diameter of 0.2 μm was immersed in the mixed solution.
次−いで、これを温度１２０℃の恒温器に入れ、１０分
間保持した後、電気炉中３００℃で１０分間焼成した。Next, this was placed in a constant temperature oven at a temperature of 120°C, held for 10 minutes, and then fired at 300°C for 10 minutes in an electric furnace.
この様な溶液の付与、乾燥および焼成をさらに４回繰返
した。ただし、最終回の焼成は、５００℃で２０分間行
った。Application of the solution, drying, and baking were repeated four more times. However, the final firing was performed at 500° C. for 20 minutes.
かくして、多孔質アルミナ管の表面にＺｒ０２２０モル
％−３ｉＯ２８０モル％のガラス膜を備えた複合多孔質
セラミックス管が得られた。ガラス膜の付着量は、０．
１８ｇ／ｄｒｒｉ’であった。In this way, a composite porous ceramic tube having a glass film of 20 mol % Zr02-80 mol % Zr02 on the surface of the porous alumina tube was obtained. The amount of glass film attached is 0.
It was 18g/drri'.
実施例４
シリカ源としてのＳ ｉ （ＯＣ２Ｈ５） ４４２ｇ
５ジルコニア源としてのＺｒ （ＯＣ３Ｈ７） ４１５
４ｇ、０．１５モル／１の塩酸水溶液４ｇおよびＣ２Ｈ
５０Ｈ３９０ｇからなる混合溶液を調製した後、表面層
の平均細孔径が０．２μｍである多孔質アルミナ管を該
混合溶液に浸漬した。Example 4 442 g of S i (OC2H5) as a silica source
5 Zr (OC3H7) as a zirconia source 415
4g, 4g of 0.15 mol/1 aqueous hydrochloric acid solution and C2H
After preparing a mixed solution consisting of 390 g of 50H, a porous alumina tube whose surface layer had an average pore diameter of 0.2 μm was immersed in the mixed solution.
次いで、これを温度９８℃、相対湿度９５％の恒温恒湿
器に入れ、１２０分間保持した後、電気炉中３００℃で
１０分間焼成した。この様な溶液の付与、乾燥および焼
成をさらに４回繰返した。ただし、最終回の焼成は、５
００℃で２０分間行った。Next, this was placed in a constant temperature and humidity chamber at a temperature of 98° C. and a relative humidity of 95%, held for 120 minutes, and then baked at 300° C. for 10 minutes in an electric furnace. Application of the solution, drying, and baking were repeated four more times. However, the final firing is 5
The test was carried out at 00°C for 20 minutes.
かくして、多孔質アルミナ管の表面にＺｒ０２７０モル
％−８１０２３０モル％のガラス膜を備えた複合多孔質
セラミックス管が得られた。ガラス膜の付着量は、０．
３０ｇ／ｄｒｎ”であった。In this way, a composite porous ceramic tube having a glass film containing Zr0270 mol% to 810230 mol% on the surface of the porous alumina tube was obtained. The amount of glass film attached is 0.
30 g/drn".
実験例１
実施例３の方法で得たＺｒ０２７０モル％−３ｉ０２３
０モル％のガラス膜を備えた複合多孔質セラミックス管
を使用して、Ｎ２５０モル％−Ｎ２５０モル％の混合ガ
スの分離を行った。Experimental Example 1 Zr0270 mol%-3i023 obtained by the method of Example 3
A composite porous ceramic tube with a 0 mol% glass membrane was used to perform the separation of a N250 mol%-N250 mol% gas mixture.
第１図に得られた結果を曲線Ａとして示す。The results obtained are shown as curve A in FIG.
なお、第１図には、多孔質アルミナのみからなる管を使
用して同様の混合ガスの分離を行った場合の結果を曲線
Ｂとして併せて示す。Note that FIG. 1 also shows, as curve B, the results when a similar mixed gas was separated using a tube made only of porous alumina.
第１図に示す結果から明らかな様に、本発明の複合多孔
質セラミックス管の分離比は、多孔質アルミナ管のそれ
と実質的に変わらない。As is clear from the results shown in FIG. 1, the separation ratio of the composite porous ceramic tube of the present invention is not substantially different from that of the porous alumina tube.
しかるに、Ｈ２の透過係数は、本発明の複合多孔質セラ
ミックス管の場合には、３６０Ｘ１０’（ｍ３／ば・Ｐ
−５ｅｃ）であったのに対し、多孔質アルミナ管の
場合には、僅か１８Ｘ１０’（ｍ３／ゴ・Ｐ−８ｅＣ）
に過ぎなかった。However, in the case of the composite porous ceramic tube of the present invention, the permeability coefficient of H2 is 360X10' (m3/ba・P
-5ec), whereas in the case of porous alumina tube, it was only 18X10' (m3/go・P-8eC)
It was nothing more than
実験例２
実施例１の方法に準じて、下記第１表に示す割合（モル
％）のジルコニアとシリカとからなるガラス膜を多孔質
セラミックス管上に形成した。次いで、該ガラス膜を１
００℃の蒸留水１０１００Ｏに浸漬し、４８時間還流し
て、液中のＺｒとＳｔの濃度を測定したところ、Ｚｒは
、検出されず、Ｓｉの溶出量は、第１表に示す通りであ
った。Experimental Example 2 According to the method of Example 1, a glass film consisting of zirconia and silica in the proportions (mol %) shown in Table 1 below was formed on a porous ceramic tube. Then, the glass film was
The sample was immersed in 10,100 O of distilled water at 00°C, refluxed for 48 hours, and the concentrations of Zr and St in the liquid were measured. Zr was not detected, and the amount of Si eluted was as shown in Table 1. Ta.
第１表
Ｓｔ
（ｐｐｍ）
Ｚｒ０１０： Ｓ ｉ０２９０ ６７、０５Ｚ ｒ０３
０： Ｓ ｔ ０２ Ｔｏ ２７．０５Ｚ ｒ０５０
： Ｓ ｉ ０２５０ ７．６５Ｚ ｒ０７０： Ｓ
ｉ ０２３０ ２．９３実験例３
実施例２の方法に準じて得たＺｒ０２５０モル％−８ｉ
０２５０モル％のガラス膜を備えた複合多孔質セラミッ
クス管を各種の条件で熱処理した後、実験例１と同様に
して、Ｎ２５０モル％−Ｎ２５０モル％の混合ガスの分
離を行った。Table 1 St (ppm) Zr010: S i0290 67, 05Z r03
0: S t 02 To 27.05Z r050
: S i 0250 7.65Z r070: S
i 0230 2.93 Experimental Example 3 Zr0250 mol%-8i obtained according to the method of Example 2
After heat treating a composite porous ceramic tube equipped with a glass membrane of 0.250 mol% under various conditions, a mixed gas of 250 mol% of N250 mol% of N2 was separated in the same manner as in Experimental Example 1.
第２図に得られた結果を曲線Ｃ−Ｅとして示す。The results obtained are shown in FIG. 2 as curve C-E.
第２図には、多孔質アルミナのみからなる管を使用して
同様の混合ガスの分離を行った場合の結果を曲線Ｆとし
て併せて示す。FIG. 2 also shows, as curve F, the results when a similar mixed gas was separated using a tube made only of porous alumina.
なお、各曲線と熱処理条件との関係およびそれぞれの処
理後のＮ２の透過係数は、以下の通りである。The relationship between each curve and the heat treatment conditions and the N2 permeability coefficient after each treatment are as follows.
曲線Ｃ・・・５００℃×１時間、透過係数＝４２０ Ｘ
ｌ ０−” （ｒ＝３／ｒｒｒ ・Ｐ ・ｓｅｅ ）
曲線Ｄ・・・５００℃×５時間、透過係数＝４８９Ｘ１
０−９（ｍ３／ｒｒＩｔ−Ｐ −８ｅＣ）曲線Ｅ・・・
５００℃×２１時間、透過係数＝４９２Ｘ １０’ （
ｒｎ３／ｒｒｒ・Ｐ −５ｅｃ ）曲線Ｆ・・・熱処
理なし。透過係数＝２８２Ｘ１０’ （ｍ３／ｒｄ−Ｐ
−５ｅｅ ）第２図に示す結果から明らかな様に、
本発明の複合多孔質セラミックス管の分離比は、多孔質
アルミナ管のそれと実質的に変わらない。Curve C...500°C x 1 hour, transmission coefficient = 420
l 0-” (r=3/rrr・P・see)
Curve D...500°C x 5 hours, transmission coefficient = 489X1
0-9 (m3/rrIt-P -8eC) curve E...
500℃ x 21 hours, permeability coefficient = 492X 10' (
rn3/rrr・P −5ec) Curve F: No heat treatment. Transmission coefficient = 282X10' (m3/rd-P
-5ee) As is clear from the results shown in Figure 2,
The separation ratio of the composite porous ceramic tube of the present invention is not substantially different from that of a porous alumina tube.
しかるに、Ｎ２の透過速度は、むしろ向上している。However, the N2 permeation rate is rather improved.
このような事実から、本発明による複層セラミックス系
濾過材は、５００℃で十分な耐熱性を備えていることが
明らかである。From these facts, it is clear that the multilayer ceramic filter medium according to the present invention has sufficient heat resistance at 500°C.
第１図および第２図は、本発明の複合多孔質セラミック
ス管のＮ２−Ｎ２混合ガスのＮ２分離比を多孔質アルミ
ナ管のそれと対比して示すグラフである。
（以上）
第１図
差 ｒＬ（ａｔｍ）
第２図
０ ０．５ ｆ、ｏ １．５ ２
０ ２５ ３．０差 圧（ａｔｍ）1 and 2 are graphs showing the N2 separation ratio of the N2-N2 mixed gas of the composite porous ceramic tube of the present invention in comparison with that of the porous alumina tube. (more than) 1st figure difference rL (atm) 2nd figure 0 0.5 f, o 1.5 2
0 25 3.0 differential pressure (atm)
Claims (2)
系多孔質ガラス膜を備えたガラス・セラミック系濾過材
。(1) A glass-ceramic filter material comprising a silica-zirconia porous glass membrane on a porous ceramic substrate.
コニア源となるアルコキシドの混合溶液を付与し、乾燥
し、焼成することを特徴とするガラス・セラミックス系
濾過材の製造方法。(2) A method for manufacturing a glass-ceramic filter material, which comprises applying a mixed solution of alkoxides serving as a silica source and a zirconia source onto a porous ceramic substrate, drying and firing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11071688A JPH01281119A (en) | 1988-05-06 | 1988-05-06 | Glass-ceramic-type filtration material and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11071688A JPH01281119A (en) | 1988-05-06 | 1988-05-06 | Glass-ceramic-type filtration material and its manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01281119A true JPH01281119A (en) | 1989-11-13 |
| JPH0582B2 JPH0582B2 (en) | 1993-01-05 |
Family
ID=14542669
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11071688A Granted JPH01281119A (en) | 1988-05-06 | 1988-05-06 | Glass-ceramic-type filtration material and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01281119A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5139540A (en) * | 1991-07-24 | 1992-08-18 | Texaco Inc. | Membrane separation of gases |
| US5160352A (en) * | 1991-09-06 | 1992-11-03 | Texaco Inc. | Method of forming membranes useful for separation of gases |
| US5183482A (en) * | 1991-06-19 | 1993-02-02 | Texaco Inc. | Separation by membrane techniques |
| CN1058908C (en) * | 1997-06-20 | 2000-11-29 | 清华大学 | Method for prepn. of ultra filtering silica membrane used for seawater desalination |
| US6372020B2 (en) * | 1999-08-26 | 2002-04-16 | Jae-Jin Hong | Oxygen enriching membrane |
| JP2002292261A (en) * | 2001-03-30 | 2002-10-08 | Kyocera Corp | Inorganic porous body for gas separation filter, gas separation filter and method for producing the same |
| WO2007112340A3 (en) * | 2006-03-27 | 2007-12-21 | 3M Innovative Properties Co | Glass ceramic self-supporting film and process for its production |
| JP2016055272A (en) * | 2014-09-11 | 2016-04-21 | 株式会社ノリタケカンパニーリミテド | One-end sealed type cylindrical ceramic |
-
1988
- 1988-05-06 JP JP11071688A patent/JPH01281119A/en active Granted
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5183482A (en) * | 1991-06-19 | 1993-02-02 | Texaco Inc. | Separation by membrane techniques |
| US5139540A (en) * | 1991-07-24 | 1992-08-18 | Texaco Inc. | Membrane separation of gases |
| US5160352A (en) * | 1991-09-06 | 1992-11-03 | Texaco Inc. | Method of forming membranes useful for separation of gases |
| CN1058908C (en) * | 1997-06-20 | 2000-11-29 | 清华大学 | Method for prepn. of ultra filtering silica membrane used for seawater desalination |
| US6372020B2 (en) * | 1999-08-26 | 2002-04-16 | Jae-Jin Hong | Oxygen enriching membrane |
| JP2002292261A (en) * | 2001-03-30 | 2002-10-08 | Kyocera Corp | Inorganic porous body for gas separation filter, gas separation filter and method for producing the same |
| WO2007112340A3 (en) * | 2006-03-27 | 2007-12-21 | 3M Innovative Properties Co | Glass ceramic self-supporting film and process for its production |
| JP2016055272A (en) * | 2014-09-11 | 2016-04-21 | 株式会社ノリタケカンパニーリミテド | One-end sealed type cylindrical ceramic |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0582B2 (en) | 1993-01-05 |
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