JP2686291B2 - Method for producing catalyst carrier - Google Patents
Method for producing catalyst carrierInfo
- Publication number
- JP2686291B2 JP2686291B2 JP63258190A JP25819088A JP2686291B2 JP 2686291 B2 JP2686291 B2 JP 2686291B2 JP 63258190 A JP63258190 A JP 63258190A JP 25819088 A JP25819088 A JP 25819088A JP 2686291 B2 JP2686291 B2 JP 2686291B2
- Authority
- JP
- Japan
- Prior art keywords
- alumina
- catalyst carrier
- barium
- carrier
- catalyst
- 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 - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 62
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 claims description 52
- 229910052788 barium Inorganic materials 0.000 claims description 20
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 17
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- 229910015999 BaAl Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 238000005245 sintering Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 150000004703 alkoxides Chemical class 0.000 description 4
- 150000001553 barium compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 150000002604 lanthanum compounds Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical group 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 oxygen ions Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、アルミナを主成分とした自動車排ガス浄化
用触媒あるいは燃焼用触媒等に使用する触媒担体に係
り、特に高温において高い比表面積を維持する触媒担体
およびその製造方法に関するものである。Description: TECHNICAL FIELD The present invention relates to a catalyst carrier mainly used for an automobile exhaust gas purification catalyst or a combustion catalyst, etc., which has a high specific surface area at high temperature. And a method for producing the same.
従来、自動車排ガス浄化用触媒あるいは燃焼用触媒等
の担体に用いられているアルミナは、1000℃以上の高温
にさらされると、α−アルミナに転移し、これに伴って
比表面積は10m2/g以下にまで低下する。これによって、
担持した触媒成分がシンタリング等の変化を起こし、触
媒が劣化する（触媒の熱劣化）。したがって、熱劣化の
少ない触媒を得るためには、高温下でも高比表面積を維
持できる安定な触媒担体が必要である。Conventionally, alumina used as a carrier for automobile exhaust gas purification catalysts or combustion catalysts, etc., when exposed to a high temperature of 1000 ° C. or higher, is converted to α-alumina, and the specific surface area thereof is 10 m 2 / g. It drops to below. by this,
The carried catalyst component undergoes changes such as sintering, and the catalyst deteriorates (heat deterioration of the catalyst). Therefore, in order to obtain a catalyst with little thermal deterioration, a stable catalyst carrier capable of maintaining a high specific surface area even under high temperature is required.
従来、このようなアルミナ担体の熱的安定性を向上さ
せる方法としては、バリウム化合物を添加すること（特
開昭61−245844号、特開昭62−1454号、第56回触媒討論
会（Ａ）講演予稿収4N17、192（1985）等）、あるいは
ランタン化合物を添加すること（特開昭61−38627号
等）が提案されている。これらの方法は、バリウム化合
物あるいはランタン化合物を添加して焼成することによ
って、アルミナの一部または全部を耐熱性の高いβ−ア
ルミナに転化するものであり、これによって1200℃程度
の高温でも物性変化が小さく、比表面積が維持される担
体が得られるというものである。Conventionally, as a method for improving the thermal stability of such an alumina carrier, a barium compound has been added (JP-A 61-245844, JP-A 62-1454, and 56th catalyst discussion meeting (A). ) Proceedings of the lecture, 4N17, 192 (1985), etc.), or addition of lanthanum compounds (JP-A-61-38627, etc.) has been proposed. These methods are to convert a part or all of alumina into β-alumina having high heat resistance by adding a barium compound or a lanthanum compound and then firing, thereby changing the physical properties even at a high temperature of about 1200 ° C. Is small, and a carrier having a specific surface area maintained can be obtained.
しかしながら、上記従来技術においては、高温でも、
安定な担体が得られるものの、担体のもともとの比表面
積が20m2/gと小さいために高価な貴金属等の触媒活性成
分を高分散担持し難いという問題点があった。However, in the above conventional technique, even at high temperature,
Although a stable carrier can be obtained, the original specific surface area of the carrier is as small as 20 m 2 / g, so that there is a problem that it is difficult to highly disperse and carry a catalytically active component such as an expensive precious metal.
上記した従来技術の課題は、アルミナを主成分とする
触媒担体の製造方法において、γ（ガンマ）−、θ（シ
ータ）−、δ（デルタ）−、η（イータ）−、χ（カ
イ）−、κ（カッパ）−アルミナの中から選ばれた１種
以上のアルミナに、予め調整した平均粒径が３μｍ以下
であるバリウム・β−アルミナ（BaAl12O19）および／
またはランタン・β−アルミナ（La2O3・11〜14Al2O3）
を、前記選ばれた１種以上のアルミナに対して２〜７モ
ル％添加することを特徴とする触媒担体の製造方法によ
り解決される。The above-mentioned problems of the prior art are, in the method for producing a catalyst carrier containing alumina as a main component, γ (gamma)-, θ (theta)-, δ (delta)-, η (eta)-, χ (chi)-. , Κ (kappa) -alumina, barium / β-alumina (BaAl 12 O 19 ) having a mean particle size of 3 μm or less, and //
Or lanthanum / β-alumina (La 2 O 3 / 11-14Al 2 O 3 )
Is added in an amount of 2 to 7 mol% with respect to the selected one or more types of alumina.
β−アルミナは、第２図に示すように、酸素イオンの
最密充填からなるスピネルブロックがBaやLaなどのカチ
オンを含む鏡映面によって隔てられた層状アルミネート
構造をとり、この構造のために耐熱性に優れているとさ
れている。確かに、アルミナ担体の一部あるいは全部を
β−アルミナに転化した担体は、耐熱性に優れている
が、このような担体は、比表面積が最大でも20m2/g程度
であり、貴金属等の触媒成分を高分散担持するには十分
ではない。これは、β−アルミナの結晶が層状構造であ
るために積層しやすく、高比表面積を得難い微細構造を
とるためであると考えられる。As shown in Fig. 2, β-alumina has a layered aluminate structure in which spinel blocks composed of the closest packing of oxygen ions are separated by a reflection surface containing cations such as Ba and La. It is said to have excellent heat resistance. Certainly, a carrier obtained by converting a part or all of the alumina carrier into β-alumina has excellent heat resistance, but such a carrier has a specific surface area of about 20 m 2 / g at the maximum, and the carrier such as precious metal It is not sufficient to support the catalyst component in a highly dispersed manner. It is considered that this is because the β-alumina crystal has a layered structure, so that the β-alumina crystals are easily laminated and have a fine structure that makes it difficult to obtain a high specific surface area.
そこで、本発明者らは鋭意研究した結果、β−アルミ
ナは、それ自身では高比表面積のアルミナ担体を実現す
るのが困難であるが、その高い耐熱性を生かして、焼結
抑制剤として他の比表面積の大きなアルミナ中に添加す
ることにより高耐熱性でかつ高比表面積の担体を実現で
きることを見い出した。Therefore, as a result of intensive studies by the present inventors, β-alumina is difficult to realize an alumina carrier having a high specific surface area by itself, but by utilizing its high heat resistance, it can be used as a sintering inhibitor other than that. It was found that a carrier with high heat resistance and high specific surface area can be realized by adding it to alumina having a large specific surface area.
本発明になる触媒担体においては、第１図に示すよう
に、γ−、θ−、δ−アルミナ等の比較的粗い粒子の間
あるいは表面に、β−アルミナの微粒子が高分散あるい
は被覆しており、これによって上記の粗粒アルミナ粒子
が安定化されてシンタリングが抑制されており、一方微
粒のβ−アルミナも上記の粗粒アルミナ表面に高分散し
ているために安定化されてシンタリングし難い状態とな
っているものと考えられる。本発明になる触媒担体の製
造法では、微粒のβ−アルミナと上記の粗粒アルミナが
互いに安定化し合う状態を有効に生みだしている。β−
アルミナは粒径が小さいほど効果的であり、平均粒径が
３μｍ以下であれば有効である。また、その添加量には
適正値が存在し、添加量が少なければ、上記の粗粒アル
ミナの安定化効果が不十分となって耐熱性が得られな
い。反対にβ−アルミナの添加量が多い場合には、β−
アルミナ粒子が過剰となるために、β−アルミナ相同士
の結晶成長が起こり易くなって焼結抑制効果が発揮され
なくなり、比表面積が低下する。β−アルミナが上記粗
粒アルミナの粒子の間あるいは表面に高分散あるいは被
覆して、焼結抑制効果を発揮するのに適切なβ−アルミ
ナ添加量は、上記の粗粒アルミナに対して２〜７モル％
である。In the catalyst carrier according to the present invention, as shown in FIG. 1, β-alumina fine particles are highly dispersed or coated between or on the surface of relatively coarse particles such as γ-, θ-, and δ-alumina. By this, the above-mentioned coarse-grained alumina particles are stabilized and sintering is suppressed, while the fine-grained β-alumina is also stabilized because it is highly dispersed on the above-mentioned coarse-grained alumina surface. It is considered to be difficult to do. In the method for producing the catalyst carrier according to the present invention, a state in which the fine β-alumina and the coarse-grained alumina are mutually stabilized is effectively produced. β-
Alumina is more effective as the particle size is smaller, and is effective if the average particle size is 3 μm or less. In addition, there is an appropriate value for the addition amount, and if the addition amount is small, the stabilizing effect of the coarse-grained alumina becomes insufficient and heat resistance cannot be obtained. On the contrary, when the addition amount of β-alumina is large, β-alumina
Since the alumina particles are excessive, crystal growth between β-alumina phases is likely to occur, the effect of suppressing sintering is not exhibited, and the specific surface area decreases. An appropriate amount of β-alumina added so that β-alumina is highly dispersed or coated between particles of the above-mentioned coarse-grained alumina or on the surface thereof and exerts a sintering suppressing effect is 2 to the above-mentioned coarse-grained alumina. 7 mol%
It is.
本発明になる触媒担体の製造法においては、微粒のβ
−アルミナは予め調製し、それをγ−、θ−、δ−等の
アルミナに添加することでβ−アルミナの焼結抑制剤と
しての役割を有効に引き出している。従来の方法は、例
えば特開昭62−1454号にみられるように、アルミナ中に
バリウム化合物あるいはランタン化合物を適当量添加
し、焼成することによりβ−アルミナ相を形成させるも
のである。このような方法はβ−アルミナ相の高分散化
に対して一見有効であるように思われるが、この方法で
は実際には比表面積の小さなアルミナ担体しか得られな
い。これは、β−アルミナ相の生成が、アルミナ粒子と
バリウム化合物あるいはランタン化合物との固相反応に
よるものであるため、β−アルミナの均一な結晶成長が
実現しにくいことおよびβ−アルミナ相を成長させて担
体を十分に安定化させるためには高温焼成（1100℃以
上）することが必要であり、そのためにα−アルミナの
生成が避けられない等の理由によるものと考えられる。
本発明になる触媒担体の製造方法では、この従来法が有
していた欠点を解消することが可能であり、β−アルミ
ナの微粒子がγ−、θ−、δ−等のアルミナ粒子の間あ
るいは表面に高分散あるいは被覆した理想的な状態を実
現しているものと考えられる。In the method for producing the catalyst carrier according to the present invention, fine particles of β
-Alumina is prepared in advance, and by adding it to γ-, θ-, δ-, etc. alumina, the role of β-alumina as a sintering inhibitor is effectively brought out. A conventional method is to form a β-alumina phase by adding an appropriate amount of a barium compound or a lanthanum compound to alumina and calcining it, as disclosed in, for example, JP-A-62-1454. Although such a method seems to be effective for increasing the dispersion of the β-alumina phase, this method can only obtain an alumina carrier having a small specific surface area. This is because the β-alumina phase is generated by the solid-phase reaction between the alumina particles and the barium compound or lanthanum compound, so that it is difficult to achieve uniform crystal growth of β-alumina and the β-alumina phase is grown. In order to sufficiently stabilize the carrier, it is necessary to perform high-temperature calcination (1100 ° C. or higher), which is considered to be the reason why α-alumina is unavoidable.
In the method for producing a catalyst carrier according to the present invention, it is possible to eliminate the drawbacks of this conventional method, and the fine particles of β-alumina are between γ-, θ-, δ-, etc. alumina particles, or It is considered that the surface is highly dispersed or ideally realized.
本発明になる触媒担体を製造するにあたって、使用す
るβ−アルミナは、アルコキシド法で得られたものが好
ましい。あるいはアルミナ源としてベーマイトゲルを用
いて得られたβ−アルミナも比較的良い特性を与える。
また、これらβ−アルミナは1250℃以下の熱処理で得ら
れたものが微粒であるので好ましい。また、このβ−ア
ルミナは、1150℃以上で焼成した時にβ−アルミナに転
化しうる前駆体であっても同等の効果を与える。In producing the catalyst carrier according to the present invention, β-alumina used is preferably one obtained by the alkoxide method. Alternatively, β-alumina obtained by using boehmite gel as an alumina source also gives relatively good properties.
Further, these β-aluminas are fine particles obtained by the heat treatment at 1250 ° C. or less, which is preferable. Further, even if this β-alumina is a precursor that can be converted into β-alumina when fired at 1150 ° C. or higher, the same effect is obtained.
本発明になる触媒担体の主成分であるβ−アルミナ以
外のアルミナ相は、γ−、θ−、δ−、η−、χ−、κ
−アルミナの中から選ばれた１種以上のものであればい
ずれでも有効であるが、この中でもθ、η−あるいはχ
−アルミナが好ましい。また、単独系よりもθ−とη−
あるいはχ−が混合した複合系の方が好ましい結果を与
える。また、添加するβ−アルミナについても、バリウ
ム・β−アルミナあるいはランタン・β−アルミナの単
独系でも有効であるが、これらを複合するとより好まし
い結果を与える。Alumina phases other than β-alumina, which is the main component of the catalyst carrier according to the present invention, are γ-, θ-, δ-, η-, χ-, κ.
-Any one or more selected from alumina is effective, and among these, θ, η- or χ
-Alumina is preferred. In addition, θ- and η-
Alternatively, a composite system in which χ − is mixed gives a preferable result. Further, as the β-alumina to be added, barium / β-alumina or lanthanum / β-alumina alone is also effective, but a combination of these gives more preferable results.
また、本発明になる触媒担体の製造方法において、主
成分のアルミナ相に微粒のβ−アルミナを添加した後
は、β−アルミナの分散性を高めるために湿式で十分混
合あるいは混練するのが好ましい。β−アルミナを予め
水に分散、膨潤させた後添加する方法も有効である。In addition, in the method for producing a catalyst carrier according to the present invention, it is preferable that, after adding fine particles of β-alumina to the main component alumina phase, sufficiently mixed or kneaded by a wet method in order to enhance the dispersibility of β-alumina. . A method of adding β-alumina after dispersing and swelling it in water is also effective.
主成分のアルミナ相にβ−アルミナを添加し、湿式で
混合あるいは混練した後は、担体を安定化させるために
700〜1250℃で焼成するとより好ましい結果を与える。In order to stabilize the carrier after adding β-alumina to the main component alumina phase and mixing or kneading it in a wet manner
Baking at 700-1250 ° C gives more favorable results.
以下、本発明を具体的実施例を用いて詳細に説明す
る。Hereinafter, the present invention will be described in detail with reference to specific examples.
実施例１ ベーマイトゲルを大気中で1100℃、２時間熱処理して
θ−アルミナを得た。この粉末100gにアルコキシド法で
調製した平均粒径が1.8μｍのバリウム・β−アルミナ
（BaAl12O19）を、θ−アルミナのアルミナ分に対して
４モル％となるように添加し、これに水200mlを加えて
乳鉢で混練し、スラリを得た。このスラリを110℃で24
時間乾燥し、さらに1150℃で２時間焼成して（1150℃ま
で２時間で昇温）触媒担体を得た。Example 1 Boehmite gel was heat-treated in the air at 1100 ° C. for 2 hours to obtain θ-alumina. The average particle size of 1.8μm barium · beta-alumina prepared by the alkoxide method to the powder 100g (BaAl 12 O 19), it was added in an amount of 4 mol% based on the alumina content of the θ- alumina, to 200 ml of water was added and kneaded in a mortar to obtain a slurry. 24 hours at 110 ℃ this slurry
After drying for 1 hour, it was further calcined at 1150 ° C. for 2 hours (heating to 1150 ° C. in 2 hours) to obtain a catalyst carrier.
実施例２ 実施例１において、バリウム・β−アルミナの添加量
をθ−アルミナに対して2.5モル％となるように添加
し、あとは同様にして触媒担体を得た。Example 2 A catalyst carrier was obtained in the same manner as in Example 1, except that barium.β-alumina was added in an amount of 2.5 mol% with respect to θ-alumina.
実施例３ バイアライトを大気中で750℃、２時間熱処理してη
−アルミナを得た。この粉末100gにアルコキシド法で調
製した平均粒径が2.7μｍのバリウム・β−アルミナ
を、η−アルミナのアルミナ分に対して６モル％となる
ように添加し、これに水200mlを加えて乳鉢で混練し、
スラリを得た。このスラリを110℃で24時間乾燥し、さ
らに1150℃で２時間焼成して（1150℃まで２時間で昇
温）触媒担体を得た。Example 3 Vialite was heat-treated in the atmosphere at 750 ° C. for 2 hours to obtain η.
-Alumina was obtained. Barium .beta.-alumina having an average particle size of 2.7 .mu.m prepared by the alkoxide method was added to 100 g of this powder so as to be 6 mol% with respect to the alumina content of .eta.-alumina, and 200 ml of water was added to this and the mortar was added. Knead with
Got a slurry. The slurry was dried at 110 ° C. for 24 hours and then calcined at 1150 ° C. for 2 hours (heating to 1150 ° C. in 2 hours) to obtain a catalyst carrier.
実施例４ 実施例１において、バリウム・β−アルミナをアルコ
キシド法で調製した平均粒径が2.1μｍのランタン・β
−アルミナに代えて、同様にして触媒担体を得た。Example 4 In Example 1, lanthanum / β having an average particle size of 2.1 μm prepared by alkoxide method of barium / β-alumina
-In place of alumina, a catalyst carrier was obtained in the same manner.
実施例５ 実施例４において、θ−アルミナを、大気中でギブサ
イトを750℃で２時間焼成して得たχ−アルミナに代え
て、同様にして触媒担体を得た。Example 5 A catalyst carrier was obtained in the same manner as in Example 4, except that θ-alumina was replaced with χ-alumina obtained by calcining gibbsite at 750 ° C. for 2 hours in the air.
実施例６ 実施例１、３および５でそれぞれ用いた、θ−、η
−、χ−アルミナの1:1:1混合物100gに、実施例１と４
でそれぞれ用いたバリウム・β−アルミナとランタン・
β−アルミナを各２モル％ずつ添加し、他は実施例１と
同様にして触媒担体を得た。Example 6 θ−, η used in Examples 1, 3 and 5, respectively.
Examples 1 and 4 in 100 g of a 1: 1: 1 mixture of-, χ-alumina.
Barium .beta.-alumina and lanthanum.
β-alumina was added in an amount of 2 mol% each, and a catalyst carrier was obtained in the same manner as in Example 1.
比較例１ γ−アルミナ100gに水酸化バリウム（Ba（OH）２）5.
2g添加し、さらに水200mlを加えて乳鉢で混合し、スラ
リを得た。このスラリを110℃で24時間乾燥した後、115
0℃で２時間焼成（1150℃までの昇温時間は２時間）し
て触媒担体を得た。Comparative Example 1 Barium hydroxide (Ba (OH) 2 ) 5.
2 g was added, and 200 ml of water was further added and mixed in a mortar to obtain a slurry. After drying this slurry at 110 ° C for 24 hours, 115
The catalyst carrier was obtained by firing at 0 ° C. for 2 hours (heating time up to 1150 ° C. for 2 hours).
比較例２ 実施例１において、バリウム・β−アルミナの添加量
を、θ−アルミナのアルミナ分に対して１モル％となる
ように添加し、他は同様にして触媒担体を得た。Comparative Example 2 A catalyst carrier was obtained in the same manner as in Example 1, except that the addition amount of barium / β-alumina was 1 mol% with respect to the alumina content of θ-alumina.
比較例３ 実施例１において、バリウム・β−アルミナの添加量
を、θ−アルミナのアルミナ分に対して８モル％となる
ように添加し、他は同様にして触媒担体を得た。Comparative Example 3 A catalyst carrier was obtained in the same manner as in Example 1, except that the addition amount of barium.β-alumina was 8 mol% with respect to the alumina content of θ-alumina.
比較例４、５、６ 実施例１において、添加するバリウム・β−アルミナ
として、平均粒径がそれぞれ4.4μｍ、6.9μｍ、11.0μ
ｍのものを用い、他は同様にして触媒担体を得た。Comparative Examples 4, 5 and 6 In Example 1, as barium .beta.-alumina to be added, average particle diameters are 4.4 .mu.m, 6.9 .mu.m and 11.0 .mu.m, respectively.
A catalyst carrier was obtained in the same manner as the above, except that m.
実施例１〜６、および比較例１〜６の担体について、
担体を得たときとそれを1200℃で４時間熱処理したとき
の比表面積（BET表面積）を測定した結果を第１表に示
す。Regarding the carriers of Examples 1 to 6 and Comparative Examples 1 to 6,
Table 1 shows the results of measuring the specific surface area (BET surface area) when the carrier was obtained and when it was heat-treated at 1200 ° C. for 4 hours.
本発明になる触媒担体は従来（比較例１）のものに比
較して著しく高い比表面積を有しており、しかも1200℃
で熱処理しても比表面積の低下度が小さく、高耐熱性を
兼ね備えていることが分かる。また、実施例６のように
母体となるアルミナあるいは、添加するβ−アルミナを
数種類複合化させるとさらに効果が大きい。 The catalyst carrier according to the present invention has a remarkably high specific surface area as compared with the conventional carrier (Comparative Example 1) and has a temperature of 1200 ° C.
It can be seen that even when heat-treated, the specific surface area is reduced to a small extent, and it has high heat resistance. In addition, as in Example 6, when a plurality of types of alumina as a base material or β-alumina to be added is compounded, the effect is further enhanced.
第３図には、バリウム・β−アルミナの添加量に対す
る1200℃熱処理後の担体の比表面積の関係を示した。図
から、バリウム・β−アルミナの添加量が２〜７モル％
の範囲で効果の高いことが分かる。FIG. 3 shows the relationship of the specific surface area of the carrier after heat treatment at 1200 ° C. with respect to the amount of barium / β-alumina added. From the figure, the amount of barium / β-alumina added is 2 to 7 mol%.
It can be seen that the effect is high in the range of.
第４図には、添加するバリウム・β−アルミナの平均
粒径に対する1200℃熱処理後の担体の比表面積の関係を
示した。平均粒径が３μｍ以下で効果の著しいことが分
かる。FIG. 4 shows the relationship between the average particle size of barium / β-alumina to be added and the specific surface area of the carrier after heat treatment at 1200 ° C. It can be seen that the effect is remarkable when the average particle size is 3 μm or less.
第５図には、実施例１および実施例４で得た担体の12
00℃、４時間熱処理後のＸ線回折図を示した。図には、
θ−アルミナの明確なピークが認められるのみであり、
バリウム・β−アルミナのピークやα−アルミナのピー
クは全く認められない。本発明になる触媒担体では、母
体となるアルミナ粒子の間あるいは表面にβ−アルミナ
の微細粒子が高分散あるいは被覆しており、これが焼結
抑制剤となって高耐熱性が実現しているものと思われ
る。FIG. 5 shows 12 of the carriers obtained in Examples 1 and 4.
The X-ray diffraction pattern after heat treatment at 00 ° C. for 4 hours is shown. In the figure,
Only a clear peak of θ-alumina is observed,
No peaks of barium / β-alumina and α-alumina are observed. In the catalyst carrier according to the present invention, fine particles of β-alumina are highly dispersed or coated between or on the surface of the alumina particles as a base material, and this serves as a sintering inhibitor to realize high heat resistance. I think that the.
本発明になる触媒担体は、1200℃で４時間処理しても
55〜75m2/g程度の高比表面積を維持することができるの
で、高温下でも触媒成分を高分散担持して活性低下の少
ない触媒を実現することが可能となる。The catalyst carrier according to the present invention can be treated at 1200 ° C. for 4 hours.
Since it is possible to maintain a high specific surface area of about 55 to 75 m 2 / g, it becomes possible to realize a catalyst in which the catalyst component is highly dispersed and supported even at a high temperature and whose activity is less deteriorated.
第１図は本発明になる触媒担体の微細構造図、第２図は
バリウムおよびランタン・β−アルミナの構造を示す模
式図、第３図はバリウム・β−アルミナの添加量と1200
℃で４時間の熱処理後の担体の比表面との関係図、第４
図は添加したバリウム・β−アルミナの平均粒径と1200
℃で４時間の熱処理後の担体の比表面積との関係図、第
５図は実施例１および４で得られた触媒担体の1200℃で
４時間熱処理後のＸ線回折図である。FIG. 1 is a fine structure diagram of a catalyst carrier according to the present invention, FIG. 2 is a schematic diagram showing the structures of barium and lanthanum .beta.-alumina, and FIG. 3 is an addition amount of barium .beta.-alumina and 1200.
Relationship diagram with specific surface of carrier after heat treatment at 4 ° C for 4 hours,
The figure shows the average particle size of the added barium β-alumina and 1200
FIG. 5 is a diagram showing the relationship with the specific surface area of the carrier after heat treatment at 4 ° C. for 4 hours, and FIG. 5 is an X-ray diffraction pattern of the catalyst carriers obtained in Examples 1 and 4 after heat treatment at 1200 ° C. for 4 hours.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 吉田 直美 広島県呉市宝町３番36号 バブコック日 立株式会社呉研究所内 (72)発明者 新田 昌弘 広島県呉市宝町３番36号 バブコック日 立株式会社呉研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Naomi Yoshida, No. 36 Takara-cho, Kure City, Hiroshima Prefecture Babcock Day Kure Institute Co., Ltd. (72) Masahiro Nitta No. 36, Takara-cho, Kure City, Hiroshima Prefecture Babcock Day Standing Kure Research Institute
Claims (2)
法において、γ（ガンマ）−、θ（シータ）−、δ（デ
ルタ）−、η（イータ）−、χ（カイ）−、κ（カッ
パ）−アルミナの中から選ばれた１種以上のアルミナ
に、予め調整した平均粒径が３μｍ以下であるバリウム
・β−アルミナ（BaAl12O19）および／またはランタン
・β−アルミナ（La2O3・11〜14Al2O3）を、前記選ばれ
た１種以上のアルミナに対して２〜７モル％添加するこ
とを特徴とする触媒担体の製造方法。1. A method for producing a catalyst carrier containing alumina as a main component, wherein γ (gamma)-, θ (theta)-, δ (delta)-, η (eta)-, χ (chi)-, κ ( Kappa) -alumina selected from barium / β-alumina (BaAl 12 O 19 ) and / or lanthanum / β-alumina (La 2 ) having an average particle size of 3 μm or less. O 3 · 11~14Al 2 a O 3), process for preparing a catalyst carrier which comprises adding 2 to 7 mol% relative to one or more of alumina the chosen.
おいて、前記選ばれた１種以上のアルミナに、バリウム
・β−アルミナおよび／またはランタン・β−アルミナ
を添加したのち、700〜1250℃で焼成することを特徴と
する触媒担体の製造方法。2. The method for producing a catalyst carrier according to claim 1, wherein barium .beta.-alumina and / or lanthanum .beta.-alumina is added to the selected one or more kinds of alumina, and then 700- A method for producing a catalyst carrier, which comprises calcination at 1250 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63258190A JP2686291B2 (en) | 1988-10-13 | 1988-10-13 | Method for producing catalyst carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63258190A JP2686291B2 (en) | 1988-10-13 | 1988-10-13 | Method for producing catalyst carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02107331A JPH02107331A (en) | 1990-04-19 |
| JP2686291B2 true JP2686291B2 (en) | 1997-12-08 |
Family
ID=17316767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63258190A Expired - Fee Related JP2686291B2 (en) | 1988-10-13 | 1988-10-13 | Method for producing catalyst carrier |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2686291B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3492431B1 (en) | 2016-07-29 | 2023-11-22 | Sumitomo Chemical Company Limited | Alumina and method for producing automotive catalyst using same |
-
1988
- 1988-10-13 JP JP63258190A patent/JP2686291B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02107331A (en) | 1990-04-19 |
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