JP5003016B2 - Alumina porous body - Google Patents
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims description 27
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 53
- 239000002245 particle Substances 0.000 claims description 42
- 239000000843 powder Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 239000003513 alkali Substances 0.000 description 17
- 239000000919 ceramic Substances 0.000 description 17
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 13
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 150000002910 rare earth metals Chemical class 0.000 description 8
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 7
- 239000010419 fine particle Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 229920001353 Dextrin Polymers 0.000 description 3
- 239000004375 Dextrin Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 235000019425 dextrin Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910017414 LaAl Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Description
本発明は、セラミックフィルタ等に用いるアルミナ多孔体において、優れた耐アルカリ性能を有するアルミナ多孔体に関するものである。 The present invention relates to an alumina porous body having excellent alkali resistance in an alumina porous body used for a ceramic filter or the like.
アルミナ多孔体は、比較的粒径の大きなＡｌ２Ｏ３粒子を骨材とし、それらをSiO2を主体とするガラス成分からなる無機系の結合材にてＡｌ２Ｏ３粒子間を結合させ、目的に応じた細孔径を有するアルミナ多孔体を形成するものが良く利用されている。
特に、食品、医薬品、化成品等の生産において、原液中の不要物質の除去や原液中の所定物質の濃縮等のセラミックフィルタとして、アルミナ多孔体が用いられる。ここで、原液が強アルカリ性である場合や、気孔の目詰まり除去等にアルカリ溶液処理を行う場合などに、上記したＡｌ２Ｏ３粒子間を接合しているガラス成分の一部が溶出し、セラミックフィルタの強度を低下させることがあった。
Alumina porous body, a relatively having a large grain size Al 2 O 3 particles as aggregates, let them bond between Al 2 O 3 particles in binder inorganic made of glass component mainly comprising SiO2, object A material that forms an alumina porous body having a pore size corresponding to the above is often used.
In particular, in the production of foods, pharmaceuticals, chemical products, etc., a porous alumina body is used as a ceramic filter for removing unnecessary substances in a stock solution and concentrating a predetermined substance in the stock solution. Here, when the stock solution is strongly alkaline, or when an alkaline solution treatment is performed to remove clogging of pores, etc., a part of the glass component bonding between the Al 2 O 3 particles is eluted, The strength of the ceramic filter may be reduced.
また、アルミナ多孔体は、その用途として表面に水熱合成によりゼオライト膜を製膜し、分子ふるいとして利用される場合があるが、特許文献１に記載されているようにゼオライト膜製膜時の水熱処理の際にアルカリ性の薬剤により担体であるアルミナ多孔体が溶出し、この溶出分がゼオライト膜中に異物として混入され、ゼオライト膜の性状が不安定になってしまうという問題があった。 In addition, the alumina porous body may be used as a molecular sieve by forming a zeolite membrane on the surface by hydrothermal synthesis as its use, but as described in Patent Document 1, During the hydrothermal treatment, there was a problem that the alumina porous body as a carrier was eluted by an alkaline agent, and this eluted portion was mixed as a foreign substance in the zeolite membrane, resulting in unstable properties of the zeolite membrane.
従来、アルミナフィルタの耐アルカリ性を向上されるためには、例えば、特許文献２のようにＡｌ２Ｏ３粒子間を結合しているガラス成分の耐アルカリ性を向上させるために、Zr2OやMgOを特定量添加することがなされていた。
しかしながら、Ａｌ２Ｏ３粒子間を結合しているガラス成分の溶出にある程度の効果を有するものの、まだ、不十分であった。
本発明は、耐アルカリ性に優れた特性を有するアルミナ多孔体を提供することを目的とするものである。
However, although it has a certain effect on the elution of the glass component bonding between the Al 2 O 3 particles, it is still insufficient.
An object of this invention is to provide the alumina porous body which has the characteristic excellent in alkali resistance.
上記課題を解決するためになされた本発明は、Ａｌ２Ｏ３粒子間を結合することで構成されるアルミナ多孔体であって、前記Ａｌ２Ｏ３粒子間は、平均粒径１０〜５０μｍのＡｌ２Ｏ３粒子１００重量部に対して、１０〜３０重量部のＡｌ２Ｏ３微粒粉末と０．１〜１０重量部のＧｄ２Ｏ３またはＹ２Ｏ３との化合物（ＧｄＡｌＯ３またはＹ３Ａｌ５Ｏ１２）にて焼結により結合されていることを特徴とするアルミナ多孔体とした。
セラミックフィルタの強度低下の主たる要因となっていたＡｌ２Ｏ３粒子間のガラス成分を、主として、Ａｌ２Ｏ３と特定の希土類（Ln）酸化物との化合物（ＬｎｘＡｌｙ０ｚ）にかえて、Ａｌ２Ｏ３粒子間を結合させることにより、ガラス成分の溶出によるセラミックフィルタ強度低下を効果的に防止でき、アルカリ処理後においても優れた強度を維持することが可能となる。
The present invention has been made in order to solve the aforementioned problems is a porous alumina formed by coupling between Al 2 O 3 particles, between the Al 2 O 3 particles have an average particle diameter of 10~50μm against Al 2 O 3 particles 100 parts by weight, the compound of the Gd 2 O 3 or Y 2 O 3 of Al 2 O 3 fine powder and 0.1 to 10 parts by weight of 10 to 30 parts by weight (GdAlO 3 or Y 3 Al 5 O 12 ) to form a porous alumina body bonded by sintering.
The glass component between the Al 2 O 3 particles, which has been the main factor for reducing the strength of the ceramic filter, is mainly converted to a compound (Ln x Al y 0 z ) of Al 2 O 3 and a specific rare earth (Ln) oxide. Instead, by bonding the Al 2 O 3 particles, it is possible to effectively prevent the ceramic filter strength from being reduced due to elution of the glass component, and it is possible to maintain excellent strength even after the alkali treatment.
本発明の好ましい形態として、前記の希土類（Ｌｎ）酸化物は、Ｇｄ２Ｏ３、Ｌａ２Ｏ３、Ｙ２Ｏ３から選ばれた少なくとも１種類とすることが良い。 As a preferred embodiment of the present invention, the rare earth (Ln) oxide may be at least one selected from Gd 2 O 3 , La 2 O 3 , and Y 2 O 3 .
Ｇｄ２Ｏ３、Ｌａ２Ｏ３、Ｙ２Ｏ３は、ＧｄＡｌＯ３、ＬａＡｌ１１Ｏ１８やＹ３Ａl5Ｏ12等のＡｌ２Ｏ３と希土類酸化物の化合物を形成して、Ａｌ２Ｏ３粒子間の結合に寄与しており、また、アルカリ処理後、Ａｌ２Ｏ３粒子間のそれらの溶出は見られず、化合物組織を維持していることから、それらの化合物自体が耐アルカリ性に優れていると推測され、アルカリ処理後のセラミックフィルタの強度を維持することが可能となる。 Gd 2 O 3, La 2 O 3, Y 2 O 3 is to form a GdAlO 3, LaAl of 11 O 18 and Y 3 Al 5 O Al 2 O 3 and a rare earth oxide such as 12 compounds, Al 2 O These particles contribute to the bonding between the three particles, and after the alkali treatment, the elution between the Al 2 O 3 particles is not observed and the compound structure is maintained. It is presumed that the ceramic filter is excellent, and the strength of the ceramic filter after the alkali treatment can be maintained.
また、本発明の好ましい形態として、前記アルミナ多孔体において、ＳｉＯ２の含有率は、０．５重量％以下にすること良い。 As a preferred embodiment of the present invention, in the alumina porous body, the content of SiO 2 is preferably 0.5% by weight or less.
一般に、ＳｉＯ２はＡｌ２Ｏ３粒子間にガラス相として存在し、Ａｌ２Ｏ３の焼結助材あるいはＡｌ２Ｏ３粒子の結合材としての働きがあるが、本発明のＬｎｘＡｌｙ０ｚを含むアルミナ多孔体では、焼成過程で形成されるＬｎｘＡｌｙ０ｚが、優れた焼結助材や接合材の働きをするため、ＳｉＯ２等他の焼結助材や結合材の混合は不要である。一方、ＳｉＯ２は高アルカリ側で溶出して、アルミナ多孔体の強度を低下させるため、ＳｉＯ２は極力少ないことが望ましく、本発明のアルミナ多孔体では、ＳｉＯ２の含有率は０．５重量％以下、さらに好ましくは０．２重量％以下にする。 In general, SiO 2 is present as a glass phase between Al 2 O 3 particles, there is a function as a binding material of the sintering material or Al 2 O 3 particles of Al 2 O 3, Ln x Al y of the present invention In the alumina porous body containing 0 z , Ln x Al y 0 z formed in the firing process functions as an excellent sintering aid and bonding material, so other sintering aids and binders such as SiO 2 are used. Is not necessary. On the other hand, since SiO 2 elutes on the high alkali side and lowers the strength of the alumina porous body, it is desirable that SiO 2 is as small as possible. In the alumina porous body of the present invention, the content of SiO 2 is 0.5% by weight. % Or less, more preferably 0.2% by weight or less.
本発明は、Ａｌ２Ｏ３粒子間を耐アルカリ性に優れたＡｌ２Ｏ３と希土類（Ln）酸化物との化合物（ＬｎｘＡｌｙ０ｚ）にて結合することで、アルカリ処理後においても優れた強度を有するセラミックフィルタを提供できる。 In the present invention, Al 2 O 3 particles are bonded with a compound of Al 2 O 3 and rare earth (Ln) oxide (Ln x Al y 0 z ) excellent in alkali resistance so that even after alkali treatment. A ceramic filter having excellent strength can be provided.
以下の本発明を更に詳細に説明する。
図１は、本発明のアルミナ多孔体の構造を説明する模式図である。
図１は、円筒状のセラミックフィルタ１断面の一部を示しており、骨材としてのＡｌ２Ｏ３粒子２間を結合材３にて結合し、それらの界面に孔４を形成しているものである。
Ａｌ２Ｏ３粒子としては、要求される細孔径に合わせて適宜選択されるものであるが、平均粒径１０μｍ〜５０μｍを利用することで、細孔径３μｍ〜１６μｍのセラミックフィルタを得ることができる。また、このセラミックフィルタを支持体として、その表層の平均粒径１μｍ以下のＡｌ２Ｏ３粒子を被覆して細孔径０．３μｍ以下の複層のセラミックフィルタを構成しても良い。
The following present invention will be described in more detail.
FIG. 1 is a schematic diagram illustrating the structure of the alumina porous body of the present invention.
FIG. 1 shows a part of a cross section of a cylindrical ceramic filter 1, in which Al 2 O 3 particles 2 as aggregates are bonded together by a bonding material 3, and a hole 4 is formed at the interface between them. Is.
The Al 2 O 3 particles are appropriately selected according to the required pore diameter, but a ceramic filter having a pore diameter of 3 μm to 16 μm can be obtained by using an average particle diameter of 10 μm to 50 μm. . Alternatively, a multilayer ceramic filter having a pore diameter of 0.3 μm or less may be formed by coating Al 2 O 3 particles having an average particle diameter of 1 μm or less on the surface layer using this ceramic filter as a support.
また、結合材については、Ａｌ２Ｏ３と希土類酸化物を利用するが、Ａｌ２Ｏ３については、上記骨材粒子の一部を利用することも可能である。耐アルカリ性では、Ａｌ２Ｏ３微粒子の添加は無い方が、好ましく、その際のＡｌ２Ｏ３骨材粒径としては、小さい方が好ましい。なお、Ａｌ２Ｏ３微粒子を利用することで、成形後の成形体を焼成する際の保形成を保つためには、効果的であるので、ある程度の微粒子の存在はあった方が好ましい。この場合、Ａｌ２Ｏ３微粒粉末と希土類酸化物粉末の混合比は、反応生成物のＬｎｘＡｌｙ０ｚから、Ｌｎ：Ａｌが原子量比でｘ：ｙと等しい、もしくは、ｘ：ｙよりＡｌが多くなるように計算して混合するのが良い。ｘ：ｙよりＡｌ２Ｏ３微粒粉末が少ない場合には、未反応の希土類酸化物が残存し、反って耐食性を落とす原因になることもある。希土類酸化物は、Ａｌ２Ｏ３と反応し、ＬｎｘＡｌｙ０ｚの化合物を形成するものであれば、利用可能であるが、特に、Ｇｄ２Ｏ３、Ｌａ２Ｏ３、Ｙ２Ｏ３が好適に利用できる。また、これらの酸化物は、複数種を利用しても良い。粒径としては、平均粒径１０μｍ以下が望ましい。 As for the binder, it utilizes a Al 2 O 3 and a rare earth oxide, for Al 2 O 3, it is possible to use a part of the aggregate particles. In terms of alkali resistance, it is preferable that no Al 2 O 3 fine particles are added, and the smaller the Al 2 O 3 aggregate particle size, the better. It should be noted that the use of Al 2 O 3 fine particles is effective in maintaining the retention during firing of the molded body after molding, and therefore it is preferable that a certain amount of fine particles exist. In this case, the mixing ratio of the Al 2 O 3 fine particle powder and the rare earth oxide powder is such that Ln: Al is equal to x: y in terms of atomic weight ratio from Ln x Al y 0 z of the reaction product, or from x: y It is good to calculate and mix so that Al may increase. When the Al 2 O 3 fine powder is less than x: y, unreacted rare earth oxide remains, which may cause the corrosion resistance to deteriorate. The rare earth oxide can be used as long as it reacts with Al 2 O 3 to form a compound of Ln x Al y 0 z , and in particular, Gd 2 O 3 , La 2 O 3 , Y 2 O 3 can be suitably used. Moreover, you may utilize multiple types of these oxides. As the particle size, an average particle size of 10 μm or less is desirable.
なお、例えば、円筒状セラミックフィルタは、数十、数百本をモジュールとして組み付けることから、ハンドリング、組み付けする際の負荷などを考慮して、数％程度のガラス分を添加して、初期のセラミックフィルタ強度を向上させるようにしても良い。この場合でも主たるＡｌ２Ｏ３粒子間の結合は、Ａｌ２Ｏ３と希土類酸化物との化合物によって結合されているので、アルカリ処理後に前記ガラス分が溶出した場合でも問題ない。
次に、製造方法について、以下の説明する。
骨材としての純度９９.５％以上のＡｌ２Ｏ３粒子１００重量部に対して、純度９９％以上Ａｌ２Ｏ３微粒粉末を０〜３０重量部と、少なくとも１種類の希土類酸化物粉末を０．１〜１０重量部と水、デキストリン等の成形助材を適宜添加混合し、その後、混合物を押出し成形機など用途の応じた成形手段を用いて成形する。成形体は、大気中で、焼成温度１６００℃〜１７００℃程度で焼成する。
For example, since a cylindrical ceramic filter is assembled from several tens or hundreds as a module, an amount of glass of about several percent is added in consideration of handling and loading when assembling. The filter strength may be improved. Even in this case, since the bonds between the main Al 2 O 3 particles are bonded by a compound of Al 2 O 3 and a rare earth oxide, there is no problem even when the glass component is eluted after the alkali treatment.
Next, the manufacturing method will be described below.
With respect to 100 parts by weight of Al 2 O 3 particles having a purity of 99.5% or more as aggregate, 0 to 30 parts by weight of Al 2 O 3 fine particles having a purity of 99% or more and at least one kind of rare earth oxide powder 0.1 to 10 parts by weight and a molding aid such as water and dextrin are appropriately added and mixed, and then the mixture is molded using a molding means suitable for the application such as an extrusion molding machine. The molded body is fired in the air at a firing temperature of about 1600 ° C to 1700 ° C.
得られたアルミナ多孔体の組織を確認するために、Ｘ線回折装置（XRD）、走査電子顕微鏡（SEM）、エネルギー分散型蛍光X線分析装置（EDX）にて分析した。
例えば、希土類酸化物として、Ｇｄ２Ｏ３、Ｌａ２Ｏ３を添加した際の結果を例に説明する。
図２は、XRDの結果を示す。Ｇｄ２Ｏ３、Ｌａ２Ｏ３共にＧｄ２Ｏ３、Ｌａ２Ｏ３の残存ピークは見られず、また、共にＡｌ２Ｏ３と反応し、Ｇｄ２Ｏ３添加については ＧdＡlＯ3 が生成、また、Ｌa２Ｏ３ 添加については ＬaＡl11Ｏ18が生成することが分かった。
図３は、Ｇｄ２Ｏ３添加について、（ａ）図は、SEM像、（ｂ）図は、EDXのAl分布像、（ｃ）図は、EDXのGd分布像を示す。また、図４は、Lａ２Ｏ３添加については （ａ）図は、SEM像、（ｂ）図は、EDXのAl分布像、（ｃ）図は、EDXのＬａ分布像を示す。 図３では、Ｇｄ元素が、Ａｌ２Ｏ３粒子を包み込み込むように存在し、また、図４では、La元素が、Ａｌ２Ｏ３粒子を包み込み込むように存在し、それらが結合材として、Ａｌ２Ｏ３粒子間を結合していることがわかった。
In order to confirm the structure of the obtained porous alumina body, the structure was analyzed with an X-ray diffractometer (XRD), a scanning electron microscope (SEM), and an energy dispersive X-ray fluorescence analyzer (EDX).
For example, the results when Gd 2 O 3 and La 2 O 3 are added as rare earth oxides will be described as an example.
FIG. 2 shows the results of XRD. The residual peaks of Gd 2 O 3 and La 2 O 3 are not observed for both Gd 2 O 3 and La 2 O 3 , and both react with Al 2 O 3, and Gd2O 3 is produced when Gd 2 O 3 is added, In addition, it was found that LaAl 11 O 18 was formed when La 2 O 3 was added.
FIG. 3 shows Gd 2 O 3 addition. FIG. 3A shows an SEM image, FIG. 3B shows an EDX Al distribution image, and FIG. 3C shows an EDX Gd distribution image. FIG. 4 shows La 2 O 3 addition. FIG. 4A shows an SEM image, FIG. 4B shows an EDX Al distribution image, and FIG. 4C shows an EDX La distribution image. In FIG. 3, the Gd element is present so as to encapsulate the Al 2 O 3 particles, and in FIG. 4, the La element is present so as to encapsulate the Al 2 O 3 particles, and they are used as a binder. It was found that Al 2 O 3 particles were bonded.
本発明の実施例を以下に説明する。
（実施例）
平均粒径が約２０μｍのＡｌ２Ｏ３粗粒粉末に、平均粒径が約０．６μｍのＡｌ２Ｏ３微粒粉末、及び、表１及び表２に示すように各種希土類酸化物粉末等を混合し、さらに、成形助材として、粉末１００重量部に対し、１重量部のデキストリンと３重量部の水を添加混合し、成形圧力２０ｋＰａで、６ｍｍ×６ｍｍ×５０ｍｍの棒状サンプルを圧縮成形し、大気中で１６５０℃、２時間焼成し、実施例１〜２４を作製した。
また、平均粒径が約３５μｍのＡｌ２Ｏ３粗粒粉末を用いた以外は、上記実施例と同様にしたものを実施例２５とした。
ただし、希土類酸化物としてＬａ２Ｏ３のみを用いた実施例２、５、７および９、並びにＡｌ ２ Ｏ ３ 微粒粉末の比率「なし」の実施例１３から１７および２５は、本発明に対応しない参考例である。
Examples of the present invention will be described below.
(Example)
Al 2 O 3 coarse particles having an average particle size of about 20 μm, Al 2 O 3 fine particles having an average particle size of about 0.6 μm, and various rare earth oxide powders as shown in Tables 1 and 2 Furthermore, as a forming aid, 1 part by weight dextrin and 3 parts by weight of water are added to and mixed with 100 parts by weight of the powder, and a 6 mm × 6 mm × 50 mm rod-shaped sample is compression-molded at a molding pressure of 20 kPa. Then, it was baked at 1650 ° C. for 2 hours in the air to produce Examples 1 to 24.
In addition, Example 25 was made the same as the above example except that Al 2 O 3 coarse powder having an average particle diameter of about 35 μm was used.
However, Examples 2, 5, 7 and 9 using only La 2 O 3 as the rare earth oxide, and Examples 13 to 17 and 25 of “None” of the Al 2 O 3 fine powder correspond to the present invention. Not a reference example.
（比較例）
平均粒径が約２０μｍのＡｌ２Ｏ３粉末に、平均粒径が約０．６μｍのＡｌ２Ｏ３粉末、粘土（０．４重量部）、ジルコニア（２重量部）と粉末１００重量部に対し、１重量部のデキストリンと３重量部の水を添加混合し、成形圧力２０ｋＰａで、６ｍｍ×６ｍｍ×５０ｍｍの棒状サンプルを圧縮成形し、大気中で１６５０℃、２時間焼成し、比較例１として、アルミナ多孔体を作製した。
また、表１に示すように希土類酸化物粉末を添加しないものを同様の方法にて、比較例２、３を作製した。
(Comparative example)
The Al 2 O 3 powder having an average particle size of about 20 [mu] m, Al 2 O 3 powder having an average particle size of about 0.6 .mu.m, clay (0.4 parts by weight), and the powder 100 parts by weight of zirconia (2 parts by weight) On the other hand, 1 part by weight of dextrin and 3 parts by weight of water were added and mixed, a 6 mm × 6 mm × 50 mm rod-shaped sample was compression-molded at a molding pressure of 20 kPa, and calcined in the atmosphere at 1650 ° C. for 2 hours. As a result, an alumina porous body was produced.
Further, as shown in Table 1, Comparative Examples 2 and 3 were prepared by the same method except that the rare earth oxide powder was not added.
（耐アルカリ試験及び強度試験）
焼成後の各実施例及び各比較例のアルミナ多孔体を、ＮａＯＨ１２％の９０℃加熱溶液に５時間浸漬させた後、曲げ強度をＪＩＳ Ｒ１６０１に基づいて測定した。結果を表１に示す。
(Alkali resistance test and strength test)
The alumina porous bodies of each Example and each Comparative Example after firing were immersed in a 90% heated solution of NaOH 12% for 5 hours, and then the bending strength was measured based on JIS R1601. The results are shown in Table 1.
従来のＺｒＯ２を添加しているものや希土類酸化物粉末を混合しない比較例１〜３では、曲げ強度が１０ＭＰａ前後であるのに対し、希土類酸化物粉末を混合した実施例１〜１１は、１重量部の混合でも、曲げ強度が３０前後〜４０ＭＰａでほぼ３倍以上になっていることが分かる。同実施例１〜１１は、骨材のＡｌ２Ｏ３粒子間に、Ａｌ２Ｏ３と希土類（Ｌｎ）酸化物との化合物（ＬｎｘＡｌｙ０ｚ）が介在することが、ＸＲＤやＥＰＭＡ等の分析で確認することができる。すなわち、耐アルカリ性に優れ、また、Ａｌ２Ｏ３との濡れ性の良いＬｎｘＡｌｙ０ｚを、骨材のＡｌ２Ｏ３粒子間に形成させることによって、耐アルカリ試験後の強度を向上させることができる。 In Comparative Examples 1 to 3 in which the conventional ZrO 2 is added and the rare earth oxide powder is not mixed, the bending strength is around 10 MPa, while the examples 1 to 11 in which the rare earth oxide powder is mixed are It can be seen that even with 1 part by weight of the mixture, the bending strength is about 3 times or more at around 30 to 40 MPa. In Examples 1 to 11, it is XRD or EPMA that the compound of Al 2 O 3 and rare earth (Ln) oxide (Ln x Al y 0 z ) is interposed between the Al 2 O 3 particles of the aggregate. It can be confirmed by analysis. That is, excellent in alkali resistance, also, a wettable Ln x Al y 0 z and Al 2 O 3, by forming between Al 2 O 3 particles of the aggregate, improved strength after the alkali resistance test Can be made.
また、初期強度とアルカリ処理後の強度の割合を強度保持率で見た際にも、従来に比べ高い保持率を有し、このことは、強度劣化をもたらす成分の溶出が少ないことを意味し、溶出された成分の種々の影響を低減できるものとなる。例えば、分子ふるいとしてのゼオライト膜の担体として好適に利用できる。 In addition, when the ratio between the initial strength and the strength after alkali treatment is viewed as the strength retention rate, it has a higher retention rate than before, which means that there is less elution of components that cause strength deterioration. Thus, various effects of the eluted components can be reduced. For example, it can be suitably used as a support for a zeolite membrane as a molecular sieve.
また、Ｇｄ２Ｏ３とＹ２Ｏ３との複合添加系では、耐アルカリ強度を保ちつつ、初期強度からの強度劣化が無いので、微量のＹ２Ｏ３の微粒添加は望ましい。また、Ｙ２Ｏ３の添加は、表面の色合いをより均一に保つ効果があり外観性を向上できる。 In addition, in the combined addition system of Gd 2 O 3 and Y 2 O 3 , since there is no strength deterioration from the initial strength while maintaining the alkali resistance strength, it is desirable to add a minute amount of fine particles of Y 2 O 3 . Further, the addition of Y 2 O 3 has an effect of keeping the surface color more uniform and can improve the appearance.
また、通常、セラミックフィルターの気孔率は、圧力損失の関係上、３０％程度もしくはそれ以上であることが望ましい。気孔率が３０％前後のセラミックフィルターは、通気性や通液性においても問題ない範囲である。 In general, the porosity of the ceramic filter is desirably about 30% or more in terms of pressure loss. A ceramic filter having a porosity of around 30% is in a range where there is no problem in air permeability and liquid permeability.
１…セラミックフィルタ（アルミナ多孔体）
２…Ａｌ２Ｏ３
３…結合材
４…孔
1 ... Ceramic filter (alumina porous body)
2 ... Al 2 O 3
3 ... Binder 4 ... Hole
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