JPH05132309A - Compound oxide sol and its production - Google Patents
Compound oxide sol and its productionInfo
- Publication number
- JPH05132309A JPH05132309A JP4091650A JP9165092A JPH05132309A JP H05132309 A JPH05132309 A JP H05132309A JP 4091650 A JP4091650 A JP 4091650A JP 9165092 A JP9165092 A JP 9165092A JP H05132309 A JPH05132309 A JP H05132309A
- Authority
- JP
- Japan
- Prior art keywords
- sol
- particles
- aqueous solution
- silica
- specific surface
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、シリカと他の無機酸化
物とからなる複合酸化物ゾルおよびその製造法に関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite oxide sol composed of silica and other inorganic oxides and a method for producing the same.
【０００２】[0002]
【従来の技術】従来から、シリカとアルミナ、ジルコニ
ア等との複合酸化物ゾルは公知であり、種々の触媒原料
等として用いられている。これらのゾルに分散している
複合酸化物粒子は、いずれも粒子内部に殆ど細孔を持た
ない無孔質の粒子であり、その比表面積は小さく、微粒
子の平均粒径をDp（nm）で表した場合、比表面積Ｓ（m2
/g）の値は、３０００／Dp（nm）未満である。2. Description of the Related Art Conventionally, composite oxide sols of silica and alumina, zirconia, etc. have been known and used as various catalyst raw materials. The composite oxide particles dispersed in these sols are all non-porous particles having almost no pores inside the particles, their specific surface areas are small, and the average particle diameter of the particles is Dp (nm). When expressed, the specific surface area S (m 2
The value of / g) is less than 3000 / Dp (nm).
【０００３】また、例えば、特公昭５９−１７０４７号
公報には、触媒組成物の前駆体としての無定形アルミノ
シリケートゾルの製造法が開示されており、同公報記載
の製造法によれば、ヒールゾル溶液のｐＨを厳密に制御
して粒子成長を行い、３〜９０nmの無孔質のコロイド粒
子が分散したゾルを得、次いで、この無孔質粒子のゾル
を乾燥させ、多孔質の集塊粒子を構成することによっ
て、大きな比表面積の粉末を得ることに成功している。Further, for example, Japanese Examined Patent Publication No. 59-17047 discloses a method for producing an amorphous aluminosilicate sol as a precursor of a catalyst composition. According to the method described in the publication, heel sol is disclosed. Particle growth is performed by strictly controlling the pH of the solution to obtain a sol in which non-porous colloidal particles of 3 to 90 nm are dispersed, and then the sol of non-porous particles is dried to form porous agglomerated particles. By configuring the above, it has succeeded in obtaining a powder having a large specific surface area.
【０００４】[0004]
【発明の目的】しかしながら、上記製造方法で得られる
ゾルのコロイド粒子自体は無孔質であるから、その複合
酸化物ゾルの用途も制限されたものとならざるを得な
い。即ち、本発明は比表面積が大きく、多孔質の微粒子
が分散した新規な複合酸化物ゾル、およびその製造法を
提供することを目的とする。However, since the colloidal particles themselves of the sol obtained by the above-mentioned production method are non-porous, the use of the composite oxide sol must be limited. That is, an object of the present invention is to provide a novel complex oxide sol having a large specific surface area and porous fine particles dispersed therein, and a method for producing the same.
【０００５】[0005]
【発明の概要】本発明の複合酸化物ゾルは、シリカとシ
リカ以外の無機酸化物の１種または２種以上とからなる
複合酸化物の微粒子が分散したゾルであって、該微粒子
の平均粒径（Dp）と比表面積（Ｓ）が、不等式 Ｓ（m2/g）≧３０００／ Dp（nm） を満足するものである。また、本発明の複合酸化物ゾル
の製造法は、アルカリ金属、アンモニウムまたは有機塩
基の珪酸塩と、アルカリ可溶の無機化合物とを、ｐＨ１
０以上のアルカリ水溶液中に同時に添加し、この反応液
のｐＨを制御せずにコロイド粒子を生成させるものであ
る。SUMMARY OF THE INVENTION The complex oxide sol of the present invention is a sol in which fine particles of a complex oxide consisting of silica and one or more kinds of inorganic oxides other than silica are dispersed. The diameter (Dp) and the specific surface area (S) satisfy the inequality S (m 2 / g) ≧ 3000 / Dp (nm). In addition, in the method for producing the composite oxide sol of the present invention, a silicate of an alkali metal, ammonium or an organic base and an alkali-soluble inorganic compound are added at pH 1
It is added at the same time to an alkaline aqueous solution of 0 or more to generate colloidal particles without controlling the pH of the reaction solution.
【０００６】[0006]
【発明の具体的説明】本発明の複合酸化物は、シリカと
シリカ以外の無機酸化物とからなる複合酸化物であっ
て、それぞれの酸化物の混合物ではない。無機酸化物と
しては、周期表の３Ａ族、３Ｂ族、４Ａ族、４Ｂ族、５
Ａ族、５Ｂ族、６Ａ族の金属または非金属の元素の酸化
物を挙げることができ、具体的にはＡｌ2 Ｏ3 、Ｂ2 Ｏ
3 、ＴｉＯ2 、ＺｒＯ2 、ＳｎＯ2 、Ｃｅ2 Ｏ3 、Ｐ2
Ｏ5 、Ｓｂ2 Ｏ3 、ＭｏＯ3 、ＷＯ3 等がある。DETAILED DESCRIPTION OF THE INVENTION The composite oxide of the present invention is a composite oxide composed of silica and an inorganic oxide other than silica, and is not a mixture of the respective oxides. As the inorganic oxide, there are 3A group, 3B group, 4A group, 4B group and 5 of the periodic table.
Examples thereof include oxides of metal or non-metal elements of Group A, Group 5B and Group 6A, and specifically, Al 2 O 3 and B 2 O.
3 , TiO 2 , ZrO 2 , SnO 2 , Ce 2 O 3 , P 2
There are O 5 , Sb 2 O 3 , MoO 3 , WO 3 and the like.
【０００７】上記無機酸化物に対するシリカの複合割合
（モル比）は、０．５乃至２０の範囲が適当である。こ
の比が２０を越えると、後記する微粒子の比表面積が小
さくなり、一方、０．５未満では、微粒子の比表面積は
殆ど増加しなくなる。また、ゾルの安定性も劣ってく
る。The composite ratio (molar ratio) of silica to the above-mentioned inorganic oxide is suitably in the range of 0.5 to 20. If this ratio exceeds 20, the specific surface area of the fine particles to be described later becomes small, while if it is less than 0.5, the specific surface area of the fine particles hardly increases. Also, the stability of the sol becomes poor.
【０００８】本発明では、ゾル中に分散した複合酸化物
の微粒子の比表面積Ｓ（m2/g）が、大きいことが特徴で
あり、具体的には微粒子の平均粒径をDp（nm）で表した
場合、不等式 Ｓ（m2/g）≧３０００／ Dp（nm） を満足する微粒子が分散したゾルである。The present invention is characterized in that the specific surface area S (m 2 / g) of the fine particles of the composite oxide dispersed in the sol is large. Specifically, the average particle diameter of the fine particles is Dp (nm). In the case of, the sol is a dispersion of fine particles satisfying the inequality S (m 2 / g) ≧ 3000 / Dp (nm).
【０００９】次に、複合酸化物ゾルの製造法について説
明する。シリカの原料としては、アルカリ金属、アンモ
ニウムまたは有機塩基の珪酸塩を用いる。アルカリ金属
の珪酸塩としては、珪酸ナトリウム（水ガラス）や珪酸
カリウムが用いられる。有機塩基としては、テトラエチ
ルアンモニウム塩などの第４級アンモニウム塩、モノエ
タノールアミン、ジエタノールアミン、トリエタノール
アミンなどのアミン類を挙げることができ、アンモニウ
ムの珪酸塩または有機塩基の珪酸塩には、珪酸液にアン
モニア、第４級アンモニウム水酸化物、アミン化合物な
どを添加したアルカリ性溶液も含まれる。Next, a method for producing the composite oxide sol will be described. As a raw material of silica, a silicate of alkali metal, ammonium or organic base is used. As the alkali metal silicate, sodium silicate (water glass) or potassium silicate is used. Examples of the organic base include quaternary ammonium salts such as tetraethylammonium salt, amines such as monoethanolamine, diethanolamine and triethanolamine. For the ammonium silicate or the organic base silicate, a silicic acid solution is used. In addition, an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound or the like is also included.
【００１０】また、無機酸化物の原料としては、アルカ
リ可溶の無機化合物を用い、前記した金属または非金属
のオキソ酸のアルカリ金属塩またはアルカリ土類金属
塩、アンモニウム塩、第４級アンモニウム塩を挙げるこ
とができ、より具体的には、アルミン酸ナトリウム、四
硼酸ナトリウム、炭酸ジルコニルアンモニウム、アンチ
モン酸カリウム、錫酸カリウム、アルミノ珪酸ナトリウ
ム、モリブデン酸ナトリウム、硝酸セリウムアンモニウ
ム、燐酸ナトリウムが適当である。As a raw material of the inorganic oxide, an alkali-soluble inorganic compound is used, and the alkali metal salt or alkaline earth metal salt, ammonium salt, or quaternary ammonium salt of the above-mentioned metal or nonmetal oxo acid is used. More specifically, sodium aluminate, sodium tetraborate, zirconyl ammonium carbonate, potassium antimonate, potassium stannate, sodium aluminosilicate, sodium molybdate, ammonium cerium nitrate, and sodium phosphate are more suitable. .
【００１１】複合酸化物ゾルを生成するには、予め、前
記化合物のアルカリ水溶液を個別に調製するか、また
は、混合水溶液を調製しておき、この水溶液を目的とす
る複合酸化物の複合割合に応じて、ｐＨ１０以上のアル
カリ水溶液中に撹拌しながら徐々に添加する。これらの
水溶液の添加と同時に同溶液のｐＨ値は変化するが、本
発明ではこのｐＨ値を所定の範囲に制御するような操作
は特に必要ない。水溶液は、最終的に、無機酸化物の種
類とその複合割合とによって定まるｐＨ値に落ち着く。
ｐＨを所定の範囲に制御するとき、例えば酸を添加する
ことがあるが、この場合、添加された酸により複合酸化
物の原料の金属の塩が生成し、このためゾルの安定性が
低下することがある。なお、このときの水溶液の添加速
度には格別の制限はない。In order to produce a complex oxide sol, an alkaline aqueous solution of the above compound is prepared individually or a mixed aqueous solution is prepared in advance, and this aqueous solution is adjusted to a complex ratio of the desired complex oxide. Correspondingly, it is gradually added to the alkaline aqueous solution having a pH of 10 or more while stirring. Although the pH value of the aqueous solution changes at the same time as the addition of these aqueous solutions, the present invention does not particularly require an operation for controlling the pH value within a predetermined range. The aqueous solution finally settles to a pH value determined by the type of inorganic oxide and its composite ratio.
When the pH is controlled within a predetermined range, for example, an acid may be added. In this case, the added acid forms a metal salt as a raw material of the composite oxide, which reduces the stability of the sol. Sometimes. There is no particular limitation on the addition rate of the aqueous solution at this time.
【００１２】シード粒子の分散液を出発原料として、本
発明の複合酸化物ゾルを製造することも可能である。こ
の場合には、シード粒子として、ＳｉＯ2 、Ａｌ
2 Ｏ3 、ＴｉＯ2 またはＺｒＯ2 等の無機酸化物または
これらの複合酸化物の微粒子が用いられ、通常、これら
のゾルを用いることができる。勿論、前記本発明の製造
法によって得られたゾルをシード粒子分散液としてもよ
い。It is also possible to produce the composite oxide sol of the present invention by using a dispersion liquid of seed particles as a starting material. In this case, as seed particles, SiO 2 , Al
Fine particles of an inorganic oxide such as 2 O 3 , TiO 2 or ZrO 2 or a composite oxide thereof are used, and normally, a sol of these can be used. Of course, the sol obtained by the production method of the present invention may be used as the seed particle dispersion liquid.
【００１３】このｐＨ１０以上に調整したシード粒子分
散液中に前記化合物の水溶液を、上記したアルカリ水溶
液中に添加する方法と同様にして、撹拌しながら添加す
る。この場合も、分散液のｐＨ制御は行わず成り行きに
任せる。このように、シード粒子を核として複合酸化物
粒子を成長させると、成長粒子の粒径コントロールが容
易であり、粒度の揃ったものを得ることができる。An aqueous solution of the above compound is added to the seed particle dispersion liquid adjusted to pH 10 or above with stirring in the same manner as the above-mentioned method of adding to the alkaline aqueous solution. In this case as well, the pH of the dispersion liquid is not controlled and left as it is. In this way, when the composite oxide particles are grown with the seed particles as the nuclei, it is easy to control the particle size of the grown particles and it is possible to obtain particles having a uniform particle size.
【００１４】上記したシリカ原料および無機酸化物原料
はアルカリ側で高い溶解度をもっている。しかしなが
ら、この溶解度の大きいｐＨ領域で両者を混合すると、
珪酸イオンおよびアルミン酸イオンなどのオキソ酸イオ
ンの溶解度が低下し、これらの複合物が析出してコロイ
ド粒子に成長したり、あるいは、シード粒子上に析出し
て粒子成長が起こる。従って、コロイド粒子の析出、成
長に際して、従来法のようなｐＨ制御は不要となる。ま
た、このようにして得られたゾルのコロイド粒子は従来
法によるコロイド粒子と異なり、大きな比表面積をもっ
ており、従って、多孔質となる。The above-mentioned silica raw material and inorganic oxide raw material have high solubility on the alkaline side. However, if both are mixed in the pH range where the solubility is high,
The solubilities of oxo acid ions such as silicate ions and aluminate ions decrease, and these composites precipitate and grow into colloidal particles, or precipitate on seed particles to cause particle growth. Therefore, when the colloidal particles are deposited and grown, it is not necessary to control pH as in the conventional method. In addition, the colloidal particles of the sol thus obtained have a large specific surface area, unlike the colloidal particles obtained by the conventional method, and are therefore porous.
【００１５】上記の微粒子が分散したゾルを濃縮する場
合には、予め分散液中のアルカリ金属イオン、アルカリ
土類金属イオンおよびアンモニウムイオン等の一部を除
去した後に濃縮したほうが、複合酸化物微粒子が分散し
た安定な濃縮ゾルが得られる。除去方法としては、限外
濾過等の公知の方法を採用する。In the case of concentrating the sol in which the above-mentioned fine particles are dispersed, it is better to remove some of the alkali metal ions, alkaline earth metal ions, ammonium ions and the like in the dispersion liquid in advance and then concentrate the mixture. A stable concentrated sol in which is dispersed is obtained. As a removal method, a known method such as ultrafiltration is adopted.
【００１６】[0016]
〔実施例１〕平均粒径５nm、ＳｉＯ2 濃度２０重量％の
シリカゾル２０ｇと純水３８０ｇの混合物を８０℃に加
温した。この反応母液のｐＨは１０．５であり、同母液
にＳｉＯ2 として１．５重量％の珪酸ナトリウム水溶液
１８００ｇとＡｌ2 Ｏ3 として０．５重量％のアルミン
酸ナトリウム水溶液１８００ｇとを同時に添加した。添
加速度は５ml／分であり、その間、反応液の温度を８０
℃に保持した。反応液のｐＨは添加直後、１２．５に上
昇し、その後、殆ど変化しなかった。添加終了後、反応
液を室温まで冷却し、ＳｉＯ2 ・Ａｌ2 Ｏ3 複合酸化物
ゾルを得た。Example 1 A mixture of 20 g of silica sol having an average particle size of 5 nm and a SiO 2 concentration of 20% by weight and 380 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor was 10.5, and 1800 g of 1.5 wt% sodium silicate aqueous solution as SiO 2 and 1800 g of 0.5 wt% sodium aluminate aqueous solution as Al 2 O 3 were simultaneously added to the mother liquor. . The addition rate was 5 ml / min, during which the temperature of the reaction solution was 80
Hold at 0 ° C. Immediately after the addition, the pH of the reaction solution rose to 12.5, and thereafter hardly changed. After the addition was completed, the reaction solution was cooled to room temperature to obtain a SiO 2 · Al 2 O 3 composite oxide sol.
【００１７】この複合酸化物ゾル中に分散したコロイド
粒子の比表面積と平均粒径を表１に示す。なお、比表面
積はタイトレーション法〔Analytical Chemistry Vol.2
8,No.12(1956) 〕に基づいて測定し、平均粒径は動的光
散乱法により測定した。Table 1 shows the specific surface area and average particle diameter of the colloidal particles dispersed in this composite oxide sol. The specific surface area is determined by the titration method [Analytical Chemistry Vol.
8, No. 12 (1956)], and the average particle size was measured by the dynamic light scattering method.
【００１８】〔実施例２〕実施例１のアルミン酸ナトリ
ウム水溶液の代わりに、Ｂ2 Ｏ3 として０．５重量％の
四硼酸ナトリウム水溶液１８００ｇを用いた以外は実施
例１と同様にして、ＳｉＯ2 ・Ｂ2Ｏ3 複合酸化物ゾル
を得た。Example 2 The procedure of Example 1 was repeated except that 1800 g of a 0.5 wt% sodium tetraborate aqueous solution as B 2 O 3 was used instead of the sodium aluminate aqueous solution of Example 1. A 2 · B 2 O 3 composite oxide sol was obtained.
【００１９】〔実施例３〕実施例１のアルミン酸ナトリ
ウム水溶液の代わりに、ＺｒＯ2 として０．５重量％の
炭酸ジルコニルアンモニウム水溶液１８００ｇを用いた
以外は実施例１と同様にして、ＳｉＯ2 ・ＺｒＯ2 複合
酸化物ゾルを得た。[0019] Instead of an aqueous sodium aluminate solution in Example 3 Example 1, except for using as the ZrO 2 of 0.5 wt% ammonium zirconyl carbonate solution 1800g in the same manner as in Example 1, SiO 2 · A ZrO 2 composite oxide sol was obtained.
【００２０】〔実施例４〕実施例１のアルミン酸ナトリ
ウム水溶液の代わりに、ＳｎＯ2 として０．５重量％の
錫酸カリウム水溶液１８００ｇを用いた以外は実施例１
と同様にして、ＳｉＯ2 ・ＳｎＯ2 複合酸化物ゾルを得
た。Example 4 Example 1 was repeated except that 1800 g of a 0.5 wt% potassium stannate aqueous solution as SnO 2 was used in place of the sodium aluminate aqueous solution of Example 1.
A SiO 2 · SnO 2 composite oxide sol was obtained in the same manner as in.
【００２１】〔実施例５〕実施例１で用いたものと同じ
反応母液を８０℃に加温した後、これにＳｉＯ2 として
２．３重量％の珪酸ナトリウム水溶液１２００ｇ、Ａｌ
2 Ｏ3 として０．４重量％のアルミン酸ナトリウム水溶
液１２００ｇおよびＢ2 Ｏ3 として１．０重量％の四硼
酸ナトリウム水溶液１２００ｇを、添加速度５ml／分で
同時に注加して、ＳｉＯ2 ・Ａｌ2 Ｏ3 ・Ｂ2Ｏ3 複合
酸化物ゾルを得た。Example 5 The same reaction mother liquor as that used in Example 1 was heated to 80 ° C., and then 1200 g of a 2.3 wt% sodium silicate aqueous solution as SiO 2 and Al were added.
The 2 O 3 as a 0.4 wt% aqueous solution of sodium aluminate 1200g and B 2 O 3 as a 1.0 wt.% Of sodium tetraborate aqueous 1200g, and poured simultaneously at an addition rate 5 ml / min, SiO 2 · Al A 2 O 3 .B 2 O 3 composite oxide sol was obtained.
【００２２】〔実施例６〕８０℃に加温した０．１重量
％の水酸化ナトリウム水溶液（ｐＨ１２．５）４００ｇ
中に、ＳｉＯ2 として０．５重量％の珪酸ナトリウム水
溶液１８００ｇとＡｌ2 Ｏ3 として１．４重量％のアル
ミン酸ナトリウム水溶液１８００ｇとを同時に添加し
た。添加速度は５ml／分であり、その間、反応液の温度
を８０℃に保持した。反応液のｐＨは僅かに変化し、添
加終了時には１２．４となった。添加終了後、反応液を
室温まで冷却し、ＳｉＯ2 ・Ａｌ2 Ｏ3 複合酸化物ゾル
を得た。Example 6 400 g of 0.1 wt% sodium hydroxide aqueous solution (pH 12.5) heated to 80 ° C.
Then, 1800 g of a 0.5 wt% sodium silicate aqueous solution as SiO 2 and 1800 g of a 1.4 wt% sodium aluminate aqueous solution as Al 2 O 3 were simultaneously added. The addition rate was 5 ml / min, during which the temperature of the reaction solution was maintained at 80 ° C. The pH of the reaction solution changed slightly and reached 12.4 at the end of the addition. After the addition was completed, the reaction solution was cooled to room temperature to obtain a SiO 2 · Al 2 O 3 composite oxide sol.
【００２３】〔実施例７〕実施例６の珪酸ナトリウム水
溶液の濃度を３．０重量％に変え、アルミン酸ナトリウ
ム水溶液の濃度を０．３重量％に変えた以外は実施例６
と同様にして、ＳｉＯ2 ・Ａｌ2 Ｏ3 複合酸化物ゾルを
得た。[Example 7] Example 6 was repeated except that the concentration of the sodium silicate aqueous solution was changed to 3.0% by weight and the concentration of the sodium aluminate aqueous solution was changed to 0.3% by weight.
In the same manner as described above, a SiO 2 · Al 2 O 3 composite oxide sol was obtained.
【００２４】〔実施例８〕珪酸ナトリウム水溶液を陽イ
オン交換樹脂で処理して得られた珪酸液（ＳｉＯ2 濃度
１．５重量％）にテトラエチルアンモニウムハイドロオ
キサイドを、ＳｉＯ2 ／（Ｃ2 Ｈ5)4 ＮＯＨモル比１０
の割合で添加したアルカリ水溶液を調製した。実施例１
で用いたものと同じ反応母液に上記アルカリ水溶液１８
００ｇと、Ａｌ2 Ｏ3 として０．５重量％のアルミン酸
ナトリウム水溶液１８００ｇを同時に添加して、ＳｉＯ
2 ・Ａｌ2 Ｏ3複合酸化物ゾルを得た。添加時の条件は
実施例１と同様である。Example 8 Tetraethylammonium hydroxide was added to a silicic acid solution (SiO 2 concentration: 1.5% by weight) obtained by treating an aqueous solution of sodium silicate with a cation exchange resin, and SiO 2 / (C 2 H 5 ) 4 NOH molar ratio 10
The alkaline aqueous solution added in the ratio of was prepared. Example 1
In the same reaction mother liquor as that used in
00 g and 1800 g of 0.5 wt% sodium aluminate aqueous solution as Al 2 O 3 were added at the same time to obtain SiO 2
A 2 · Al 2 O 3 composite oxide sol was obtained. The conditions at the time of addition are the same as in Example 1.
【００２５】〔実施例９〕テトラエチルアンモニウムハ
イドロオキサイドの代りにアンモニアを用い、ＳｉＯ2
／ＮＨ3 モル比２とした以外は実施例８と同様にしてＳ
ｉＯ2 ・Ａｌ2 Ｏ3 複合酸化物ゾルを得た。Example 9 Ammonia was used instead of tetraethylammonium hydroxide, and SiO 2
S / S in the same manner as in Example 8 except that the NH 3 molar ratio was changed to 2.
An iO 2 · Al 2 O 3 composite oxide sol was obtained.
【００２６】[0026]
【表１】 反応液ｐＨ 複合割合 コロイド粒子 初期 終期 （モル比） 比表面積(S) 平均粒径(Dp) S×Dp 実施例１ 10.5 12.5 5.1 1100(m2/g) 20(nm) 22000 実施例２ 10.5 12.1 3.5 1500 15 22500 実施例３ 10.5 12.0 6.2 1000 21 21000 実施例４ 10.5 12.4 7.5 1050 40 42000 実施例５ 10.5 12.3 2.0 1200 18 21600 実施例６ 12.5 12.4 0.6 1150 52 59800 実施例７ 12.5 12.0 18.0 500 10 5000 実施例８ 10.5 12.3 5.1 1200 12 14400 実施例９ 10.5 12.1 5.1 950 10 9500[Table 1] Reaction solution pH composite ratio Colloidal particles Initial stage (molar ratio) Specific surface area (S ) Average particle size (Dp) S × Dp Example 1 10.5 12.5 5.1 1100 (m 2 / g) 20 (nm) 22000 Example 2 10.5 12.1 3.5 1500 15 22500 Example 3 10.5 12.0 6.2 1000 21 21000 Example 4 10.5 12.4 7.5 1050 40 42000 Example 5 10.5 12.3 2.0 1200 18 21600 Example 6 12.5 12.4 0.6 1150 52 59800 Example 7 12.5 12.0 18.0 500 10 5000 Example 8 10.5 12.3 5.1 1200 12 14400 Example 9 10.5 12.1 5.1 950 10 9500
【００２７】[0027]
【発明の効果】本発明に係る複合酸化物ゾルは、分散微
粒子の比表面積が大きく、微粒子の内部に多数の細孔を
有している。従って、触媒としての用途以外にも、以下
のような種々の用途に適用することができる。INDUSTRIAL APPLICABILITY The complex oxide sol according to the present invention has a large specific surface area of dispersed fine particles and has a large number of fine pores inside the fine particles. Therefore, in addition to the use as a catalyst, it can be applied to various uses such as the following.
【００２８】（１）バインダー力が大きいので、種々の
耐火物用のバインダーとして用いれば、高強度の成形体
を得ることができ、例えば、精密鋳造用ロストワックス
法のバインダーとして用いれば、強度に優れた型を得る
ことができる。また、セラミックスシート等の無機繊維
のバインダーとして用いれば、引張強度の優れた無機繊
維が得られる。 （２）陽イオン吸着能力が大きいので、排水中のアンモ
ニウムイオンおよび重金属イオンを吸着除去するための
吸着剤や、高分子電解質の固定化剤、または、合成洗剤
に配合されるビルダーとして利用できる。(1) Since it has a large binder strength, it can be used as a binder for various refractory materials to obtain a high-strength molded article. For example, if it is used as a binder in the lost wax method for precision casting, it will have high strength. An excellent mold can be obtained. When it is used as a binder for inorganic fibers such as ceramic sheets, inorganic fibers having excellent tensile strength can be obtained. (2) Since it has a large ability to adsorb cations, it can be used as an adsorbent for adsorbing and removing ammonium ions and heavy metal ions in waste water, a fixing agent for polymer electrolytes, or a builder compounded in synthetic detergents.
【００２９】（３）特に、高アルカリ側で安定であるこ
とから、セメント配合剤や土壌硬化剤としても用いるこ
とができ、土壌硬化剤として用いた場合には、配合量に
よって硬化剤のゲル化速度を調整することが可能にな
る。 （４）更に、多孔質であることから、低屈折率用のフィ
ラーとしたり、コロイド粒子の細孔中に染料や顔料を固
定して色素材料としての利用も可能である。 （５）その他、清酒、ビールの製造過程で使用されるオ
リ下げ剤、クロマトグラフ充填剤、各種プラスチックや
ゴムの充填剤、滑り性向上剤、化粧品配合剤、潤滑剤、
増粘剤、食料品の鮮度保持剤等に有用である。(3) In particular, since it is stable on the high alkaline side, it can be used also as a cement compounding agent or a soil hardening agent. When it is used as a soil hardening agent, the hardening agent gels depending on the blending amount. It becomes possible to adjust the speed. (4) Furthermore, since it is porous, it can be used as a filler for a low refractive index, or can be used as a coloring material by fixing a dye or pigment in the pores of colloid particles. (5) In addition, a depressant used in the manufacturing process of sake and beer, a chromatographic filler, a filler for various plastics and rubbers, a slipperiness improver, a cosmetic compounding agent, a lubricant,
It is useful as a thickener and a freshness-keeping agent for foods.
【００３０】本発明に係る複合酸化物ゾルの製造法は、
反応液のｐＨコントロールを不要とするものであるか
ら、コロイド粒子を生成させる操作が容易で、製造プロ
セスを簡略化することができる。The method for producing the complex oxide sol according to the present invention is as follows:
Since it is not necessary to control the pH of the reaction solution, the operation of generating colloidal particles is easy and the manufacturing process can be simplified.
Claims (3)
または２種以上とからなる複合酸化物の微粒子が分散し
たゾルであって、該微粒子の平均粒径（Dp）と比表面積
（Ｓ）が、不等式 Ｓ（m2/g）≧３０００／ Dp（nm） を満足することを特徴とする複合酸化物ゾル。1. A sol in which fine particles of a composite oxide comprising silica and one or more kinds of inorganic oxides other than silica are dispersed, wherein the average particle diameter (Dp) and the specific surface area (S ) Satisfies the inequality S (m 2 / g) ≧ 3000 / Dp (nm).
塩基の珪酸塩と、アルカリ可溶の無機化合物とを、ｐＨ
１０以上のアルカリ水溶液中に同時に添加し、この反応
液のｐＨを制御せずにコロイド粒子を生成させることを
特徴とする複合酸化物ゾルの製造法。2. A silicate of an alkali metal, ammonium or an organic base, and an alkali-soluble inorganic compound are mixed in a pH range.
A method for producing a complex oxide sol, which comprises simultaneously adding to 10 or more aqueous alkali solutions to produce colloidal particles without controlling the pH of the reaction solution.
散液中に、アルカリ金属、アンモニウムまたは有機塩基
の珪酸塩と、アルカリ可溶の無機化合物とを同時に添加
し、この分散液のｐＨを制御せずにシード粒子を核とし
て複合酸化物の粒子成長を行わせることを特徴とする複
合酸化物ゾルの製造法。3. The pH of the dispersion liquid is controlled by simultaneously adding an alkali metal, ammonium or organic base silicate and an alkali-soluble inorganic compound to a dispersion liquid of pH 10 or more in which seed particles are dispersed. A method for producing a complex oxide sol, characterized in that the complex oxide particles are grown without using seed particles as nuclei.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09165092A JP3729205B2 (en) | 1991-03-23 | 1992-03-17 | Composite oxide sol and process for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3-83578 | 1991-03-23 | ||
| JP8357891 | 1991-03-23 | ||
| JP09165092A JP3729205B2 (en) | 1991-03-23 | 1992-03-17 | Composite oxide sol and process for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05132309A true JPH05132309A (en) | 1993-05-28 |
| JP3729205B2 JP3729205B2 (en) | 2005-12-21 |
Family
ID=26424617
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09165092A Expired - Lifetime JP3729205B2 (en) | 1991-03-23 | 1992-03-17 | Composite oxide sol and process for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3729205B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0859404A (en) * | 1994-08-26 | 1996-03-05 | Catalysts & Chem Ind Co Ltd | Antimicrobial inorganic oxide particle |
| JPH0867505A (en) * | 1994-08-26 | 1996-03-12 | Catalysts & Chem Ind Co Ltd | Inorganic oxide particle |
| JPH0920888A (en) * | 1995-07-06 | 1997-01-21 | Nissan Chem Ind Ltd | Injection agent for ground |
| JPH10237362A (en) * | 1997-02-26 | 1998-09-08 | Catalysts & Chem Ind Co Ltd | Electrodeposition coating material and electrodeposition coating |
| WO2004006873A1 (en) | 2002-07-11 | 2004-01-22 | Catalysts & Chmicals Industries Co.,Ltd. | Cosmetic |
| JP2006247460A (en) * | 2005-03-08 | 2006-09-21 | Catalysts & Chem Ind Co Ltd | Manufacturing method of adsorbent |
| WO2011155536A1 (en) | 2010-06-09 | 2011-12-15 | 日揮触媒化成株式会社 | Support for protein immobilization, immobilized protein and method for producing same |
| JP2013508256A (en) * | 2010-04-27 | 2013-03-07 | 広東省生態環境与土壌研究所 | Foliar composite silicon fertilizer used to reduce heavy metal and nitrate content in vegetables and its preparation method |
-
1992
- 1992-03-17 JP JP09165092A patent/JP3729205B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0859404A (en) * | 1994-08-26 | 1996-03-05 | Catalysts & Chem Ind Co Ltd | Antimicrobial inorganic oxide particle |
| JPH0867505A (en) * | 1994-08-26 | 1996-03-12 | Catalysts & Chem Ind Co Ltd | Inorganic oxide particle |
| JPH0920888A (en) * | 1995-07-06 | 1997-01-21 | Nissan Chem Ind Ltd | Injection agent for ground |
| JPH10237362A (en) * | 1997-02-26 | 1998-09-08 | Catalysts & Chem Ind Co Ltd | Electrodeposition coating material and electrodeposition coating |
| WO2004006873A1 (en) | 2002-07-11 | 2004-01-22 | Catalysts & Chmicals Industries Co.,Ltd. | Cosmetic |
| JP2006247460A (en) * | 2005-03-08 | 2006-09-21 | Catalysts & Chem Ind Co Ltd | Manufacturing method of adsorbent |
| JP2013508256A (en) * | 2010-04-27 | 2013-03-07 | 広東省生態環境与土壌研究所 | Foliar composite silicon fertilizer used to reduce heavy metal and nitrate content in vegetables and its preparation method |
| WO2011155536A1 (en) | 2010-06-09 | 2011-12-15 | 日揮触媒化成株式会社 | Support for protein immobilization, immobilized protein and method for producing same |
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| Publication number | Publication date |
|---|---|
| JP3729205B2 (en) | 2005-12-21 |
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