JP2590433B2 - Manufacturing method of heat-resistant alumina carrier for catalytic combustion - Google Patents
Manufacturing method of heat-resistant alumina carrier for catalytic combustionInfo
- Publication number
- JP2590433B2 JP2590433B2 JP6079724A JP7972494A JP2590433B2 JP 2590433 B2 JP2590433 B2 JP 2590433B2 JP 6079724 A JP6079724 A JP 6079724A JP 7972494 A JP7972494 A JP 7972494A JP 2590433 B2 JP2590433 B2 JP 2590433B2
- Authority
- JP
- Japan
- Prior art keywords
- alumina
- catalytic combustion
- heat
- surface area
- alumina carrier
- 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 - Lifetime
Links
- 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
- 238000007084 catalytic combustion reaction Methods 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 11
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 11
- 239000004964 aerogel Substances 0.000 claims description 8
- 239000003002 pH adjusting agent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims 1
- 238000005245 sintering Methods 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 14
- 238000010304 firing Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 210000003739 neck Anatomy 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001935 peptisation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、触媒燃焼の触媒担体と
して利用することができ、高温でも安定に高表面積を維
持する触媒燃焼用耐熱性アルミナ担体の製造法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a heat-resistant alumina carrier for catalytic combustion which can be used as a catalytic carrier for catalytic combustion and maintains a high surface area stably even at high temperatures.
【０００２】[0002]
【従来の技術】窒素酸化物（ＮＯｘ）は、自動車排ガス
やボイラー排ガス等、燃料の燃焼によって発生し、酸性
雨等の原因となるものであるため、その排出抑制対策が
急がれている。上記窒素酸化物は、空気中の窒素が燃焼
による高熱で酸化されて生じるが、燃焼温度が１５００
℃以下になればその発生はほとんど０となる。一般に、
触媒燃焼（法）は火炎燃焼（法）に比べて種々の利点が
あることが知られているが、これは、火炎燃焼では燃焼
温度が２０００℃以上に達してしまうのに対し、触媒燃
焼では燃焼温度を１５００℃以下に抑えることができ、
窒素酸化物の発生が抑制され、エネルギーの利用効率も
高いためである。2. Description of the Related Art Nitrogen oxides (NOx) are generated by the combustion of fuel such as automobile exhaust gas and boiler exhaust gas and cause acid rain and the like. The nitrogen oxides are generated by oxidizing nitrogen in the air with high heat due to combustion.
When the temperature falls below ℃, the occurrence becomes almost zero. In general,
It is known that catalytic combustion (method) has various advantages as compared with flame combustion (method). The combustion temperature can be suppressed to 1500 ° C or less,
This is because generation of nitrogen oxides is suppressed and energy use efficiency is high.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、前記触
媒燃焼の作動温度の上限は窒素酸化物の発生抑制という
制限から１５００℃に抑えられるが、下限は少なくとも
１０００℃以上には達する。このような高温において
は、従来の触媒担体として用いられている材料では焼結
してしまい、その表面積を著しく減少させてしまうた
め、短期間で担体としての役目を果たさなくなってしま
う。即ち、このような触媒担体を触媒燃焼システムに使
用すると、次第に機能が低下してしまうため、一定期間
毎に頻繁に担体を交換する必要があった。したがって、
１０００℃以上の高温でも安定に高表面積を維持し、長
期間にわたって安定な運転を行うことができるような触
媒担体が嘱望されていた。However, the upper limit of the operating temperature for the catalytic combustion can be suppressed to 1500 ° C. due to the limitation of suppressing the generation of nitrogen oxides, but the lower limit reaches at least 1000 ° C. or more. At such a high temperature, the material used as a conventional catalyst carrier sinters, and its surface area is remarkably reduced, so that it does not serve as a carrier in a short time. That is, when such a catalyst carrier is used in a catalytic combustion system, its function gradually decreases, so that it is necessary to frequently replace the carrier at regular intervals. Therefore,
There has been a demand for a catalyst carrier that can stably maintain a high surface area even at a high temperature of 1000 ° C. or more and perform stable operation for a long period of time.
【０００４】[0004]
【課題を解決するための手段】本発明は上記に鑑み提案
されたもので、通常触媒担体として広く用いられている
アルミナの耐熱性を改善し、１０００℃以上の高温でも
安定に高表面積を維持する触媒担体を提供することを目
的とし、ベーマイトゾルをゲル化させたアルミナエアロ
ゲルを乾燥し、焼成して得られた触媒燃焼用耐熱性アル
ミナ担体が、上記の特性を有することを見出したもので
ある。DISCLOSURE OF THE INVENTION The present invention has been proposed in view of the above, and improves the heat resistance of alumina, which is generally widely used as a catalyst carrier, and stably maintains a high surface area even at a high temperature of 1000 ° C. or higher. The purpose of the present invention is to provide a catalyst carrier, which is obtained by drying alumina aerogel obtained by gelling a boehmite sol, and obtaining a heat-resistant alumina carrier for catalytic combustion obtained by firing, having the above-described properties. is there.
【０００５】アルミナは５００℃程度で加熱した場合に
はγ相であるが、高温で熱処理するとδ相、θ相と転移
し、１１５０℃以上の加熱で最終的にα相に転移し、相
転移に著しい粒成長が伴うので表面積が激減する。した
がって、相転移をできるだけ高温まで抑えることで表面
積の減少を抑制できる。[0005] Alumina is in the γ phase when heated at about 500 ° C, but changes to the δ phase and the θ phase when heat-treated at a high temperature, and finally changes to the α phase when heated at 1150 ° C or more, and the phase transition occurs. The surface area is drastically reduced due to significant grain growth. Therefore, a decrease in surface area can be suppressed by suppressing the phase transition to as high a temperature as possible.
【０００６】また、相転移に伴う粒成長を抑制すること
で、相転移後の表面積の減少を抑制することができる。Further, by suppressing the grain growth accompanying the phase transition, it is possible to suppress a decrease in the surface area after the phase transition.
【０００７】アルミナ粒子と粒子のネック部分には格子
欠陥や転移が多数存在するため、α相生成の際の核生成
サイトになりやすいと考えられている。また、粒成長の
際にネックは原子の拡散経路となる。拡散経路を極力少
なくすることで粒成長も抑制されると考えられる。した
がって、ネックの数を減少させれば核生成或いは粒成長
が抑制される筈である。ネックの数を減少させること
は、単位体積中に存在するアルミナ粒子の数を減少させ
ることで実現できる。このことは、即ちアルミナのかさ
密度を低減することである。[0007] Since a large number of lattice defects and dislocations exist in the alumina particles and in the neck portions of the particles, it is considered that they are likely to be nucleation sites during α phase generation. In addition, the neck becomes a diffusion path of atoms during grain growth. It is considered that grain growth is suppressed by minimizing the diffusion path. Thus, reducing the number of necks should suppress nucleation or grain growth. Reducing the number of necks can be achieved by reducing the number of alumina particles present in a unit volume. This means reducing the bulk density of the alumina.
【０００８】そのような物質としてエアロゲルがある。
エアロゲルとすることでかさ密度を０．１ｇ／ｃｍ3 以
下と著しく低下させることが可能となり、上述のように
ネックの数を低減させることができる。このように本発
明は、アルミナエアロゲルを用いることにより、粒生成
や粒成長が抑制され、即ち表面積の減少が抑制されるア
ルミナ担体を得るものである。An example of such a substance is aerogel.
By using an airgel, the bulk density can be significantly reduced to 0.1 g / cm 3 or less, and the number of necks can be reduced as described above. As described above, the present invention is to obtain an alumina carrier in which grain generation and grain growth are suppressed, that is, a decrease in surface area is suppressed by using alumina aerogel.
【０００９】上記アルミナエアロゲルとしては、一般に
アルコキシドを用いて合成した非晶質ゲルも知られてい
るが、本発明ではベーマイトゾルを原料として用いたア
ルミナエアロゲルを使用する。このベーマイトゾルはＡ
ｌＯＯＨという化学式で表される繊維状のアルミニウム
の水酸化物であり、アルミナゾルとして市販され、工業
的に大量生産され、安価であるから、経済的な利点が大
きい。As the alumina aerogel, an amorphous gel synthesized using an alkoxide is generally known, but in the present invention, an alumina aerogel using a boehmite sol as a raw material is used. This boehmite sol is A
It is a fibrous aluminum hydroxide represented by the chemical formula IOOH, which is commercially available as alumina sol, industrially mass-produced, and inexpensive, and thus has great economic advantages.
【００１０】尤もベーマイトゾルをそのまま用いると、
ベーマイト粒子の分散が不十分であるため、酸を加えて
解膠する必要がある。解膠により分散状態が良好な透明
ゾルが得られる。解膠に用いる酸は、強酸であれば特に
その種類を特定するものではないが、焼成後に不純物が
残らない硝酸が好ましい。また、その酸の量は、ベーマ
イト（固形分）の０．０５〜０．２モル倍が好ましい。
より好ましくは０．１モル倍である。[0010] If boehmite sol is used as it is,
Since the dispersion of boehmite particles is insufficient, it is necessary to peptize by adding an acid. A transparent sol with a good dispersion state is obtained by peptization. The acid used for deflocculation is not particularly limited as long as it is a strong acid, but nitric acid, which does not leave any impurities after firing, is preferable. The amount of the acid is preferably 0.05 to 0.2 mol times the boehmite (solid content).
More preferably, it is 0.1 mole times.
【００１１】上記の透明ゾルをゲル化させるためには、
ｐＨを上昇させ、ベーマイト粒子の表面電位を低下させ
る必要がある。ところが、アンモニア水等の塩基を直接
添加すると、添加された部分のみ沈澱を生成し、ゲルを
得ることができないため不適当である。そこで鋭意研究
の結果、ゲルのｐＨを均一に上昇させる必要があること
が明らかになった。その具体的な方法としては、加水分
解により塩基を生成するｐＨ調整剤を予め添加し、添加
後にこのｐＨ調整剤が加水分解して透明ゾルのｐＨを徐
々に均一に上昇させるようにする。そのようなｐＨ調整
剤として尿素、ホルムアミドなどがあげられる。また、
このｐＨ調整剤の添加量は、解膠に用いた酸の０．５〜
２モル倍が好ましい。In order to gel the above transparent sol,
It is necessary to raise the pH and lower the surface potential of the boehmite particles. However, when a base such as aqueous ammonia is directly added, it is not suitable because a precipitate is formed only in the added portion and a gel cannot be obtained. Then, as a result of earnest study, it became clear that it was necessary to raise the pH of the gel uniformly. As a specific method, a pH adjuster that generates a base by hydrolysis is added in advance, and after the addition, the pH adjuster is hydrolyzed to gradually and uniformly raise the pH of the transparent sol. Examples of such a pH adjuster include urea and formamide. Also,
The addition amount of this pH adjuster is 0.5 to 0.5 of the acid used for peptization.
2 mole times is preferred.
【００１２】そして、上記のようにして得られたゲルを
臨界乾燥に使用する溶媒中に浸漬し、ゲル細孔中に存在
する水を所定の溶媒に置換する。置換後、その溶媒の超
臨界条件で乾燥させる。尚、上記溶媒としては水との親
和性も考えて一般的にメタノール、エタノール、プロパ
ノール等の低級アルコールが使用される。Then, the gel obtained as described above is immersed in a solvent used for critical drying, and the water present in the gel pores is replaced with a predetermined solvent. After the replacement, the solvent is dried under supercritical conditions. In addition, lower alcohols such as methanol, ethanol, and propanol are generally used as the solvent in consideration of affinity with water.
【００１３】最後に、乾燥したアルミナエアロゲルを１
１００〜１５００℃で焼成した後、触媒担体としての用
に供する。尚、触媒燃焼の燃焼温度は１５００℃以下で
あるため、上記焼成温度を１５００℃を越える温度にす
る必要はない。また、焼成温度が低すぎると強度が低く
なるので、１１００℃以上の高温で焼成する必要があ
る。Finally, dry alumina aerogel was added to 1
After calcining at 100 to 1500 ° C., it is used as a catalyst carrier. Since the combustion temperature of the catalytic combustion is 1500 ° C. or lower, it is not necessary to set the firing temperature to a temperature exceeding 1500 ° C. Also, if the firing temperature is too low, the strength will be low, so it is necessary to fire at a high temperature of 1100 ° C. or higher.
【００１４】[0014]
【実施例】ベーマイトゾル９０ｍｌ（固形分としてベー
マイト０．１モル含有）に硝酸を０．０１モル添加して
解膠し、透明ゾルを得た。これに尿素０．５ｇを加えて
密閉容器中で８０℃に保つと、６時間程度でゲル化し
た。ゲル化後、直ちにエタノールに浸漬し、ゲル細孔中
に存在する水をエタノールに置換した。置換後、オート
クレーブ中で３００℃、８０気圧の条件で、エタノール
超臨界乾燥を行った。乾燥後、１１００〜１４００℃で
５時間焼成した。EXAMPLES A transparent sol was obtained by adding 0.01 mol of nitric acid to 90 ml of boehmite sol (containing 0.1 mol of boehmite as a solid content) to peptize. When 0.5 g of urea was added to this and kept at 80 ° C. in a closed container, it gelled in about 6 hours. Immediately after the gelation, the gel was immersed in ethanol to replace the water present in the gel pores with ethanol. After the replacement, ethanol supercritical drying was performed in an autoclave at 300 ° C. and 80 atm. After drying, firing was performed at 1100 to 1400 ° C for 5 hours.
【００１５】上記ゲルは、１２００℃で焼成した後もθ
相からなり、通常のアルミナ粉体が１２００℃で焼成し
た後には完全にα相に転移してしまうのに比べ、良好な
相転移抑制効果を有することが認められた。その結果、
本発明によるアルミナ担体は、図１に示すように１２０
０℃で焼成した後も９０ｍ2 ／ｇという高い比表面積を
示した。１３００℃で焼成した後はα層へ転移するが、
１４００℃で焼成した後も１０ｍ2 ／ｇ以上という高い
比表面積を示した。通常のアルミナは１４００℃で焼成
した後には１〜２ｍ2 ／ｇ程度に比表面積が減少するの
で、上記の値はこのような高温ではかなり大きな相違で
あり、低かさ密度化による粒成長抑制効果が現れたもの
と考えられる。The above gel can be maintained at θ even after firing at 1200 ° C.
It was confirmed that the alumina powder had a good phase transition suppressing effect as compared with the case where normal alumina powder was completely converted to the α phase after firing at 1200 ° C. as a result,
The alumina support according to the present invention has a size of 120 as shown in FIG.
Even after firing at 0 ° C., it showed a high specific surface area of 90 m 2 / g. After firing at 1300 ° C, it changes to α layer,
Even after firing at 1400 ° C., it exhibited a high specific surface area of 10 m 2 / g or more. Since the specific surface area of ordinary alumina decreases to about 1 to 2 m 2 / g after firing at 1400 ° C., the above value is a considerable difference at such a high temperature, and the effect of suppressing the grain growth due to the low bulk density is obtained. Is considered to have appeared.
【００１６】以上本発明を実施例に基づいて説明した
が、本発明は前記した実施例に限定されるものではな
く、特許請求の範囲に記載した構成を変更しない限りど
のようにでも実施することができる。Although the present invention has been described based on the embodiments, the present invention is not limited to the above-described embodiments, and may be implemented in any manner unless the configuration described in the claims is changed. Can be.
【００１７】[0017]
【発明の効果】以上説明したように、本発明は、触媒燃
焼の触媒担体として利用することができ、高温でも高表
面積を安定して維持するアルミナ担体を容易に製造する
ことができる。As described above, the present invention can be used as a catalyst carrier for catalytic combustion, and can easily produce an alumina carrier stably maintaining a high surface area even at a high temperature.
【００１８】また、本発明により得られたアルミナ担体
は、上述のように高温でも高表面積を安定して維持する
ものであるから、触媒燃焼システムに適用した場合には
頻繁に交換する必要がなく、触媒劣化による機能低下を
防止し、長期にわたって安定した運転を維持させること
ができる。Since the alumina support obtained by the present invention maintains a high surface area stably even at a high temperature as described above, it does not need to be replaced frequently when applied to a catalytic combustion system. Further, it is possible to prevent the function from being deteriorated due to the deterioration of the catalyst, and to maintain a stable operation for a long time.
【００１９】さらに、本発明はベーマイトゾルを原料と
して用いるものであるから、経済的な利点が大きいもの
となる。Further, since the present invention uses boehmite sol as a raw material, it has a great economic advantage.
【図１】本発明によるアルミナ担体と通常のアルミナと
の高温焼成後の表面積を示し、焼成温度に対する比表面
積の変化を示すグラフである。FIG. 1 is a graph showing the surface area of an alumina carrier according to the present invention and ordinary alumina after firing at a high temperature, and showing the change in specific surface area with respect to the firing temperature.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭63−17220（ＪＰ，Ａ) 特開 平５−7780（ＪＰ，Ａ) 特開 平３−257060（ＪＰ，Ａ) 特開 平５−309268（ＪＰ，Ａ) ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-17220 (JP, A) JP-A-5-7780 (JP, A) JP-A-3-257060 (JP, A) 309268 (JP, A)
Claims (2)
Ｈを均一に上昇させ、ゲル化させたアルミナエアロゲル
を、有機溶媒の超臨界状態を利用して乾燥した後、焼成
することを特徴とする触媒燃焼用耐熱性アルミナ担体の
製造法。1. A method for preparing boehmite sol by using a pH adjuster.
A method for producing a heat-resistant alumina carrier for catalytic combustion, comprising drying a gelled alumina aerogel using a supercritical state of an organic solvent, and baking the gelled alumina aerogel.
５００℃とする請求項１に記載の触媒燃焼用耐熱性アル
ミナ担体の製造法。2. The sintering temperature of the dried gel is from 1100 to 1
The method for producing a heat-resistant alumina carrier for catalytic combustion according to claim 1, wherein the temperature is 500 ° C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6079724A JP2590433B2 (en) | 1994-03-24 | 1994-03-24 | Manufacturing method of heat-resistant alumina carrier for catalytic combustion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6079724A JP2590433B2 (en) | 1994-03-24 | 1994-03-24 | Manufacturing method of heat-resistant alumina carrier for catalytic combustion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07256100A JPH07256100A (en) | 1995-10-09 |
| JP2590433B2 true JP2590433B2 (en) | 1997-03-12 |
Family
ID=13698154
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|---|---|---|---|
| JP6079724A Expired - Lifetime JP2590433B2 (en) | 1994-03-24 | 1994-03-24 | Manufacturing method of heat-resistant alumina carrier for catalytic combustion |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100337024B1 (en) * | 1999-07-02 | 2002-05-17 | 손재익 | Manufacturing Method of high surface area alumina for high temperature catalytic combustion using surfactant |
| JP2001187773A (en) * | 2000-01-06 | 2001-07-10 | Mitsubishi Chemicals Corp | Acrylonitrile composition |
| KR100439854B1 (en) * | 2002-03-13 | 2004-07-12 | 한국과학기술연구원 | Aerogel type Platinum-Ruthenium-Carbon Catalyst, Method to Manufacture the said Catalyst and Direct Methanol Fuel Cell comprising the said Catalyst |
| JPWO2010013428A1 (en) * | 2008-07-28 | 2012-01-05 | サトーリサーチ株式会社 | Method for producing polyinorganic monobasic aluminum hydrate and / or aqueous alumina sol, and polyinorganic monobasic aluminum hydrate and / or aqueous alumina sol obtained by the production method |
| WO2014091665A1 (en) | 2012-12-11 | 2014-06-19 | ニチアス株式会社 | Insulation material and method of manufacturing same |
| JP5833152B2 (en) * | 2014-01-31 | 2015-12-16 | ニチアス株式会社 | Insulating material and manufacturing method thereof |
| CN108602055A (en) | 2016-02-01 | 2018-09-28 | 日挥触媒化成株式会社 | The hydrotreating catalyst of hydrocarbon ils, its manufacturing method and hydrogenation treatment method |
| CN108585798B (en) * | 2018-05-09 | 2022-02-18 | 安徽弘徽科技有限公司 | Nano porous alumina aerogel ceramic pellet and preparation method thereof |
| CN110467207B (en) * | 2019-09-02 | 2021-11-09 | 哈尔滨工业大学 | Preparation method of boehmite nanorod aerogel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH075298B2 (en) * | 1986-07-07 | 1995-01-25 | 三菱化学株式会社 | Manufacturing method of micro spherical alumina |
| JPH03257060A (en) * | 1990-03-07 | 1991-11-15 | Mitsubishi Kasei Corp | Production of silica modified alumina |
| JPH0747129B2 (en) * | 1991-07-02 | 1995-05-24 | 株式会社コロイドリサーチ | Method for producing porous gel supporting catalytic metal compound |
| JPH05309268A (en) * | 1992-05-12 | 1993-11-22 | Nippon Oil Co Ltd | Hydrocarbon combustion catalyst |
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1994
- 1994-03-24 JP JP6079724A patent/JP2590433B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JPH07256100A (en) | 1995-10-09 |
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