JPH0143712B2 - - Google Patents
Info
- Publication number
- JPH0143712B2 JPH0143712B2 JP58227547A JP22754783A JPH0143712B2 JP H0143712 B2 JPH0143712 B2 JP H0143712B2 JP 58227547 A JP58227547 A JP 58227547A JP 22754783 A JP22754783 A JP 22754783A JP H0143712 B2 JPH0143712 B2 JP H0143712B2
- Authority
- JP
- Japan
- Prior art keywords
- alumina
- magnesia spinel
- porous
- powder
- pore
- 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
Landscapes
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、噴霧熱分解により得られる多孔質ア
ルミナ−マグネシアスピネル粉末を焼成すること
から成る多孔質アルミナ−マグネシアスピネル成
形体の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing a porous alumina-magnesia spinel molded body, which comprises firing porous alumina-magnesia spinel powder obtained by spray pyrolysis. .
従来の技術
高純度で高温まで化学的・物理的に安定な多孔
質セラミツクスは、触媒及びその担体、吸着剤、
分子ふるい、フイルター等として広く工業的に使
用されている。Conventional technology Porous ceramics, which are highly pure and chemically and physically stable even at high temperatures, are used for catalysts, their carriers, adsorbents, etc.
Widely used industrially as molecular sieves, filters, etc.
特に、触媒として石油化学の発達とともに研究
が進み、1970年以降環境問題、エネルギー対策と
関連し、ますます重要性が増している。代表的な
触媒としてよく知られているものにゼオライトが
あり、接触分解反応、改質反応に使用されてい
る。最近、生化学の分野で固定化酵素担体として
も、多孔質セラミツクスが注目を集めている。 In particular, research has progressed as a catalyst with the development of petrochemistry, and since the 1970s it has become increasingly important in connection with environmental issues and energy measures. Zeolite is a well-known typical catalyst and is used in catalytic cracking reactions and reforming reactions. Recently, porous ceramics have been attracting attention as immobilized enzyme carriers in the field of biochemistry.
従来、多孔質セラミツクスの製造方法は、ある
一定の粒度分布を有する無機粉末をバインダー等
で固めるか、場合によつては高温で焼成すること
により焼き固め、生じた空隙を利用し多孔体とし
ての機能を与えていたり、サブミクロンオーダー
での多孔体製造では、ガラスの分相作用により生
じた絡み合い構造を用いて多孔体を得ている。 Traditionally, porous ceramics have been produced by hardening inorganic powder with a certain particle size distribution with a binder, or in some cases by firing it at a high temperature, and then using the voids created to form a porous body. In order to provide functions or to produce porous bodies on the submicron order, porous bodies are obtained using the entangled structure created by the phase splitting effect of glass.
しかしながら、高温で焼き固める方法では、細
孔径分布のサブミクロンオーダーでの制御が困難
であり、オングストロームオーダーでの制御は不
可能であつた。またガラスの分相作用による多孔
体は、化学的侵食に対する安定性が低く、高温条
件下では多孔体としての能力が著しく低下してし
まい、使用限界温度が低いという欠点を有してい
る。 However, with the high-temperature baking method, it is difficult to control the pore size distribution on the submicron order, and it is impossible to control the pore size distribution on the angstrom order. Furthermore, porous materials produced by the phase-separating effect of glass have low stability against chemical attack, and their performance as porous materials is significantly reduced under high-temperature conditions, resulting in a low usable temperature limit.
発明が解決しようとする課題
本発明は、このような従来の欠点を克服し、純
度、細孔径、細孔径分布の制御、高温安定性など
の点で優れた多孔質アルミナ−マグネシアスピネ
ル成形体を簡単で効率的に製造しうる工業的製法
を提供することを目的としてなされたものであ
る。Problems to be Solved by the Invention The present invention overcomes these conventional drawbacks and provides a porous alumina-magnesia spinel molded body that is excellent in terms of purity, pore size, control of pore size distribution, high temperature stability, etc. This was done for the purpose of providing an industrial manufacturing method that is simple and efficient.
課題を解決するための手段
本発明者らは、上記の優れた特性を有する多孔
質アルミナ−マグネシアスピネル成形体の工業的
製法を開発するために種々研究を重ねた結果、所
定の金属塩含有溶液を所定温度以上で噴霧熱分解
して得た多孔質アルミナ−マグネシアスピネル粉
末を所定温度以上で焼成することにより、その目
的を達成しうることを見出し、この知見に基づい
て本発明を完成するに至つた。Means for Solving the Problems The present inventors have conducted various studies to develop an industrial manufacturing method for a porous alumina-magnesia spinel molded body having the above-mentioned excellent properties. It was discovered that the object could be achieved by firing porous alumina-magnesia spinel powder obtained by spray pyrolysis at a predetermined temperature or higher, and based on this knowledge, the present invention was completed. I've reached it.
すなわち、本発明は、それぞれAl2O3及びMgO
に換算し実質上等モルに相当する量のアルミニウ
ム塩とマグネシウム塩を含有する溶液を、800℃
以上に維持した酸化雰囲気中に噴霧状で導入して
熱分解させ、次いでこのようにして得たアルミナ
−マグネシアスピネル粉末を成形し、1000℃以上
の温度で焼成することを特徴とする多孔質アルミ
ナ−マグネシアスピネル成形体の製造方法を提供
するものである。 That is, the present invention provides Al 2 O 3 and MgO
A solution containing substantially equimolar amounts of aluminum salt and magnesium salt was heated at 800°C.
Porous alumina is produced by introducing the atomized alumina into an oxidizing atmosphere maintained as above to cause thermal decomposition, and then molding the thus obtained alumina-magnesia spinel powder and firing it at a temperature of 1000°C or higher. - A method for manufacturing a magnesia spinel molded body is provided.
本発明方法により得られる多孔質アルミナ−マ
グネシアスピネル成形体は、Ｘ線的にスピネル単
一相であるため、耐熱性に優れ、また高温におい
て使用しても変質することがなく、機械的強度に
おいても優れている。特に本発明方法では、上記
所定条件下での噴霧熱分解という特別なプロセス
を用いて粉末を合成しているために、化学的にア
ルミナ、マグネシア以外の不純物をppmオーダー
まで制御し、熱分解という熱履歴を経ているため
に、高温安定性が著しく優れている。また粉末粒
子自身が一次粒子の集合体から成る中空の粒子で
あり、集合粒子の細孔径分布など粒子の特性を制
御することが可能である。なお、「細孔径分布」
とは、窒素ガス吸着にて求められた分布を意味す
る。 The porous alumina-magnesia spinel molded body obtained by the method of the present invention has a spinel single phase according to X-rays, so it has excellent heat resistance, does not change in quality even when used at high temperatures, and has low mechanical strength. is also excellent. In particular, in the method of the present invention, since the powder is synthesized using a special process called spray pyrolysis under the above-mentioned predetermined conditions, impurities other than alumina and magnesia are chemically controlled to the ppm order, and pyrolysis is performed. Because it has gone through a thermal history, it has extremely high temperature stability. Furthermore, the powder particles themselves are hollow particles consisting of aggregates of primary particles, and it is possible to control the properties of the particles, such as the pore size distribution of the aggregate particles. In addition, "pore size distribution"
means the distribution determined by nitrogen gas adsorption.
本発明方法においては、先ず、それぞれAl2O3
及びMgOに換算し実質上等モルに相当する量の
アルミニウム塩とマグネシウム塩を含有する溶液
を、800℃以上に維持した酸化雰囲気中に噴霧状
で導入して熱分解させることにより、アルミナ−
マグネシアスピネル粉末を生成させる。 In the method of the present invention, first, each Al 2 O 3
A solution containing aluminum salt and magnesium salt in substantially equimolar amounts in terms of MgO and MgO is introduced in spray form into an oxidizing atmosphere maintained at 800°C or higher and thermally decomposed.
Generates magnesia spinel powder.
このアルミニウム塩としては、例えば硝酸アル
ミニウムなどが好ましく、またマグネシウム塩と
しては、例えば硝酸マグネシウムなどが好まし
い。 The aluminum salt is preferably, for example, aluminum nitrate, and the magnesium salt is, for example, preferably magnesium nitrate.
得られたアルミナ−マグネシアスピネル粉末は
約100m2／ｇの比表面積を有し、非常に活性であ
る。 The alumina-magnesia spinel powder obtained has a specific surface area of about 100 m 2 /g and is very active.
次いでこのようにして得たアルミナ−マグネシ
アスピネル粉末を成形し、1000℃以上の温度で焼
成する。この際、該粉末を目的とする細孔径分布
を有するように加圧成形し、酸化雰囲気中で焼成
するのが好ましい。 The alumina-magnesia spinel powder thus obtained is then molded and fired at a temperature of 1000°C or higher. At this time, it is preferable that the powder is pressure-molded to have a desired pore size distribution and then fired in an oxidizing atmosphere.
細孔径分布を制御する方法は、通常、上記スピ
ネル粉末の生成条件及び生成粉末の成形圧力、焼
成温度、焼成時間等を変化させることによつて行
われる。 The pore size distribution is usually controlled by changing the conditions for producing the spinel powder, the compacting pressure of the produced powder, the firing temperature, the firing time, etc.
また、本発明方法により得られる成形体の形状
及び構造は任意のものでよく、実施例に示すよう
な円柱状に限られず、例えば球状体、ハニカム構
造体などでもよい。 Furthermore, the shape and structure of the molded body obtained by the method of the present invention may be arbitrary, and is not limited to the cylindrical shape shown in the examples, but may be, for example, a spherical body, a honeycomb structure, etc.
発明の効果
本発明方法によれば、純度、細孔径、細孔径分
布の制御、高温安定性などの点で優れた多孔質ア
ルミナ−マグネシアスピネル成形体を簡単で効率
よく工業的に製造しうるという顕著な効果を奏す
る。Effects of the Invention According to the method of the present invention, porous alumina-magnesia spinel molded bodies that are excellent in terms of purity, pore diameter, control of pore diameter distribution, high temperature stability, etc. can be easily and efficiently industrially produced. It has a remarkable effect.
実施例
次に実施例によつて本発明をさらに詳細に説明
する。EXAMPLES Next, the present invention will be explained in more detail with reference to Examples.
実施例
硝酸アルミニウムと硝酸マグネシウムを１：１
のモル比でスピネル組成0.5モル／になるよう
に水／メタノール（体積比１：１）溶媒に溶解し
た溶液を、酸化雰囲気中800℃で噴霧熱分解を行
い、得られたアルミナ−マグネシアスピネル粉末
を円柱状に300、500、800Kg／cm2の圧力で成形し、
1300℃で１時間焼成し、多孔質セラミツクスを得
た。得られた多孔体について、その気孔半径ｒに
対する細孔容積ΔV／Δlog ｒを水銀圧入法によ
り測定した。その結果を第１図に、横軸を対数目
盛で気孔半径ｒ(A)、縦軸を等分目盛で細孔容積
ΔV／Δlog ｒ（cm3／ｇ・Ａ）として示した。な
お、細孔容積とは、気孔半径ｒにおいてΔlog ｒ
＝0.45の幅の範囲に存在する細孔容積を示す。第
１図より明らかなように、細孔容積の分布は成形
圧により変化し、狭い範囲において細孔が分布し
ていることが分る。Example Aluminum nitrate and magnesium nitrate 1:1
Alumina-magnesia spinel powder was obtained by spray pyrolysis of a solution dissolved in a water/methanol (volume ratio 1:1) solvent at 800°C in an oxidizing atmosphere so that the spinel composition was 0.5 mol/molar ratio. is formed into a cylindrical shape at a pressure of 300, 500, 800Kg/ cm2 ,
It was fired at 1300°C for 1 hour to obtain porous ceramics. For the obtained porous body, the pore volume ΔV/Δlog r relative to the pore radius r was measured by mercury intrusion method. The results are shown in FIG. 1, where the horizontal axis is plotted as pore radius r(A) on a logarithmic scale, and the vertical axis is plotted as pore volume ΔV/Δlog r(cm 3 /g·A) on equal division scale. Note that the pore volume is Δlog r at the pore radius r
It shows the pore volume existing in the width range of =0.45. As is clear from FIG. 1, it can be seen that the pore volume distribution changes depending on the molding pressure, and the pores are distributed in a narrow range.
第１図は、本発明方法の実施例で得られた成形
体の気孔半径ｒと細孔容積ΔV／Δlog ｒとの関
係線図である。
FIG. 1 is a diagram showing the relationship between the pore radius r and the pore volume ΔV/Δlog r of a molded body obtained in an example of the method of the present invention.
Claims (1)
ルに相当する量のアルミニウム塩とマグネシウム
塩を含有する溶液を、800℃以上に維持した酸化
雰囲気中に噴霧状で導入して熱分解させ、次いで
このようにして得たアルミナ−マグネシアスピネ
ル粉末を成形し、1000℃以上の温度で焼成するこ
とを特徴とする多孔質アルミナ−マグネシアスピ
ネル成形体の製造方法。1 A solution containing substantially equimolar amounts of aluminum salt and magnesium salt in terms of Al 2 O 3 and MgO, respectively, was introduced in atomized form into an oxidizing atmosphere maintained at 800°C or higher to cause thermal decomposition. A method for producing a porous alumina-magnesia spinel molded body, which comprises: then molding the alumina-magnesia spinel powder thus obtained and firing it at a temperature of 1000°C or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58227547A JPS60122779A (en) | 1983-12-01 | 1983-12-01 | Manufacture of ceramic porous body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58227547A JPS60122779A (en) | 1983-12-01 | 1983-12-01 | Manufacture of ceramic porous body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60122779A JPS60122779A (en) | 1985-07-01 |
| JPH0143712B2 true JPH0143712B2 (en) | 1989-09-22 |
Family
ID=16862605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58227547A Granted JPS60122779A (en) | 1983-12-01 | 1983-12-01 | Manufacture of ceramic porous body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60122779A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5707910A (en) * | 1995-03-28 | 1998-01-13 | Taimei Kagaku Kogyo Kabushiki Kaisha | Alumina-magnesia oxide, method of making the same, and fine pulverulent body of the same |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6004525A (en) * | 1997-10-06 | 1999-12-21 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Hollow oxide particle and process for producing the same |
| JP5446060B2 (en) * | 2006-06-09 | 2014-03-19 | 戸田工業株式会社 | Porous material for honeycomb, porous material mixture, suspension for supporting honeycomb, catalyst body, and method for producing mixed reaction gas using the catalyst body |
| JP5730115B2 (en) * | 2011-04-26 | 2015-06-03 | コバレントマテリアル株式会社 | Porous ceramics and manufacturing method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5319560A (en) * | 1976-08-05 | 1978-02-22 | Nippon Electric Co | Method of producing multilayer circuit substrate |
-
1983
- 1983-12-01 JP JP58227547A patent/JPS60122779A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5707910A (en) * | 1995-03-28 | 1998-01-13 | Taimei Kagaku Kogyo Kabushiki Kaisha | Alumina-magnesia oxide, method of making the same, and fine pulverulent body of the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60122779A (en) | 1985-07-01 |
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