JPS63295484A - Heat-resistant inorganic porous composition and carrier for catalyst consisting of it - Google Patents
Heat-resistant inorganic porous composition and carrier for catalyst consisting of itInfo
- Publication number
- JPS63295484A JPS63295484A JP61310791A JP31079186A JPS63295484A JP S63295484 A JPS63295484 A JP S63295484A JP 61310791 A JP61310791 A JP 61310791A JP 31079186 A JP31079186 A JP 31079186A JP S63295484 A JPS63295484 A JP S63295484A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- surface area
- specific surface
- porous composition
- composition
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 238000010304 firing Methods 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 19
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052863 mullite Inorganic materials 0.000 abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 7
- 239000000377 silicon dioxide Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 229910052681 coesite Inorganic materials 0.000 abstract description 5
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 5
- 229910052682 stishovite Inorganic materials 0.000 abstract description 5
- 229910052905 tridymite Inorganic materials 0.000 abstract description 5
- 229910052593 corundum Inorganic materials 0.000 abstract description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract 2
- 239000006185 dispersion Substances 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 20
- 239000011148 porous material Substances 0.000 description 20
- 239000002244 precipitate Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 235000019353 potassium silicate Nutrition 0.000 description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 12
- 238000002485 combustion reaction Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 5
- 229910052878 cordierite Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000004438 BET method Methods 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 4
- -1 silicate compound Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 229940009827 aluminum acetate Drugs 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 241001365789 Oenanthe crocata Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
この発明は、新規耐熱性無機多孔組成物及びそれから成
る。高温下での使用に適した触媒担体に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention comprises a novel heat-resistant inorganic porous composition and a composition comprising the same. This invention relates to a catalyst carrier suitable for use at high temperatures.
［従来技術及びその欠点］
高温下て使用される触媒、例えばガスタービン、灯油及
びガス暖房器１石油及びガス給油器。[Prior Art and its Disadvantages] Catalysts used under high temperatures, such as gas turbines, kerosene and gas heaters 1 Oil and gas refuelers.
ｆｆｉ賀油燃油燃焼機器料電池用改質器燃焼触媒等の高
温燃焼触媒、スチームリフオーマ−触媒並びに臭気、廃
棄ガス浄化用触媒等の担体として、従来よりコージライ
ト（２１ｇＯ・２ＡｌｔＯｉ・５ＳｉＯ＊）及びムライ
ト（：ｌＡＩ＊０ｉ−２ＳｉＯ□）等が用いられている
が、これらは多孔性ではないので、これらの上に多孔性
物質をコーティングして使用している。多孔性物質とし
ては一般にアルミナが使用されている。このコーティン
グ剤の上に触媒活性金属を担持して触媒として使用する
。しかしながら、アルミナは高温下てその表面積が小さ
く、活性金属は使用中に分散状態が悪くなりすぐ失活す
る。Cordierite (21gO, 2AltOi, 5SiO*) has been used as a carrier for high-temperature combustion catalysts such as reformer combustion catalysts for fuel cells in oil combustion equipment, steam reformer catalysts, and odor and waste gas purification catalysts. and mullite (:lAI*0i-2SiO□), but since these are not porous, they are used by coating a porous substance on them. Alumina is generally used as the porous material. A catalytically active metal is supported on this coating agent and used as a catalyst. However, alumina has a small surface area at high temperatures, and active metals become poorly dispersed during use and are quickly deactivated.
また、ランタンベータアルミナ（ＬａｚＯｉ・１１Ａ１
２０：ｌ）やバリウムアルミナ（Ｂａ０・６ＡｌｔＯｚ
）が耐熱性か高いという報告があるが、いずれも高温焼
成後の比表面積か満足できる程度に大きくなく、かつ商
業的に使用するためにはコスト高になる。In addition, lanthanum beta alumina (LazOi・11A1
20:l) and barium alumina (Ba0.6AltOz
) have been reported to have high heat resistance, but the specific surface area after high-temperature firing is not sufficiently large, and the cost is too high for commercial use.
［発明か解決しようとする問題点］
この発明の目的は、高温下で長時間保持しても大きな比
表面積を保持できる耐熱性の多孔性組成物を提供するこ
とである。さらにこの発明の目的は、高温下て長時間保
持しても大きな比表面積を保持てきる耐熱性の多孔性組
成物から成る触媒担体を提供することである。[Problems to be Solved by the Invention] An object of the present invention is to provide a heat-resistant porous composition that can maintain a large specific surface area even when kept at high temperatures for a long time. A further object of the present invention is to provide a catalyst carrier made of a heat-resistant porous composition that maintains a large specific surface area even when kept at high temperatures for a long time.
［問題点を解決するための手段］
本願発明者らは、鋭意研究の結果、Ａ１．０３に一定範
囲のＳｉＯ□を加えることによって１０００℃ないし１
２００℃焼成後の比表面積を高く保持できることを見出
し、この発明を完成した。[Means for Solving the Problems] As a result of intensive research, the inventors of the present application found that by adding a certain range of SiO□ to A1.03, the
It was discovered that a high specific surface area could be maintained after firing at 200°C, and this invention was completed.
すなわち、この発明は、ＳｉＯ□とＡｌ２Ｏ：ｌとから
成り、ＳｉＯ□の含量か２ないし３０重量％てあり、空
気中て１２００℃て焼成した後の比表面積が２０ｍ２／
ｇ以上である耐熱性無機多孔組成物を提供する。That is, this invention consists of SiO□ and Al2O:l, the content of SiO□ is 2 to 30% by weight, and the specific surface area after firing at 1200°C in air is 20m2/
Provided is a heat-resistant inorganic porous composition having a molecular weight of at least 100 g.
さらにまた、この発明は、上記耐熱性無機多孔組成物か
ら成る触媒担体を提供する。Furthermore, the present invention provides a catalyst carrier comprising the heat-resistant inorganic porous composition.
［発明の効果］
この発明によると、高温下ての比表面積か大きな耐熱性
の多孔性の新規組成物か提供される。[Effects of the Invention] According to the present invention, a new heat-resistant porous composition with a large specific surface area at high temperatures is provided.
この発明の多孔性組成物を触媒の担体として用いると、
その多孔性の故に触媒金属を良く分散させた状態て担持
することかできるので、触媒ｆ彪か大きくなる。さらに
、高温下で長時間使用しても大きな比表面積を保持する
ので、触媒の良好な分散性を維持し、触媒面の低下を引
き起こさない。When the porous composition of this invention is used as a catalyst carrier,
Because of its porosity, the catalyst metal can be supported in a well-dispersed state, resulting in a large catalyst size. Furthermore, since it maintains a large specific surface area even when used for a long time at high temperatures, it maintains good dispersibility of the catalyst and does not cause deterioration of the catalyst surface.
［発明の詳細な説明］
上述したように、この発明の耐熱性多孔物質はＳｉＯ□
とＡ１．Ｏ□とから成り、ＳｉＯ□の全体に対する割合
は２ないし３０重量％、好ましくは２．５ないし２５重
量％である。[Detailed Description of the Invention] As mentioned above, the heat-resistant porous material of the present invention is SiO□
and A1. The proportion of SiO□ to the total is 2 to 30% by weight, preferably 2.5 to 25% by weight.
この発明の耐熱性多孔物質は、高温下での比表面積が非
常に大きなことを特徴とし、１２００℃で焼成した後の
比表面積か２０２■／ｇ以上、好ましくは５０ｍ２／ｇ
以上である。後述の実施例で明らかになるように、Ａｌ
５ｏ：＋単独の場合には１２００℃で焼成すると全てα
−ＡＩｓｏ：＋になるのに対し、この発明の耐熱性多孔
物質では、同温度で焼成するとムライト（３Ａ１□口□
−２３ｉＯ□）とθ−ＡｌｔＯｚとが存在しており、Ｓ
ｉＯ□がＡｌｔＯｉのα化を抑制して高表面積を維持す
ることがわかった。The heat-resistant porous material of the present invention is characterized by a very large specific surface area at high temperatures, and the specific surface area after firing at 1200°C is 202 cm/g or more, preferably 50 m2/g.
That's all. As will become clear in the examples below, Al
5o:+ When fired at 1200℃, all α
-AIso:+, whereas in the heat-resistant porous material of this invention, when fired at the same temperature, mullite (3A1□mouth□
-23iO□) and θ-AltOz exist, and S
It was found that iO□ suppresses gelatinization of AltOi and maintains a high surface area.
この発明の耐熱性多孔物質はアルミニウム水和物とケイ
酸化合物とを混合し、乾燥することによって製造するこ
とができる。アルミニウム水和物は、例えばアルミニウ
ム塩を水に溶解し、これにアンモニア水を加えてつくる
ことができる。アルミニウム塩としては硫酸アルミニウ
ム、塩化アルミニウム、硝酸アルミニウム及び酢酸アル
ミニウムが好ましく、水に溶解したときの濃度は０．０
５モルないし０．４モル、特に０．１３ないし０．１５
モルが好ましい、また、アンモニア水の濃度は特に重要
てはないか、例えば０．０５規定ないし２規定程度であ
る。アルミニウム塩溶液にアンモニア水を加えるとアル
ミニウム水和物か沈殿する。ケイ酸化合物としては水ガ
ラスが好ましい、水ガラスを１記アルミニウム永和物に
滴下する。水ガラスの添加量はＳｉｎｇの量が上記範囲
内になるように選択する。水ガラス添加後、混合物のｐ
Ｈを約７ないし８に調整するとこの発明の物質が沈殿す
る。The heat-resistant porous material of the present invention can be produced by mixing aluminum hydrate and a silicate compound and drying the mixture. Aluminum hydrate can be produced, for example, by dissolving aluminum salt in water and adding aqueous ammonia to the solution. As the aluminum salt, aluminum sulfate, aluminum chloride, aluminum nitrate, and aluminum acetate are preferable, and the concentration when dissolved in water is 0.0.
5 mol to 0.4 mol, especially 0.13 to 0.15
The concentration is preferably molar, and the concentration of aqueous ammonia is not particularly important, for example, about 0.05N to 2N. When aqueous ammonia is added to an aluminum salt solution, aluminum hydrate precipitates. Water glass is preferred as the silicic acid compound, and the water glass is added dropwise to the aluminum permanent product in step 1. The amount of water glass added is selected so that the amount of Sing falls within the above range. After adding water glass, p of the mixture
Adjusting H to about 7 to 8 precipitates the material of this invention.
この発明の物質を触媒担体として用いる場合には、上記
沈殿をろ過により採取し、これを適当な形態に成型する
。この発明の多孔物質は、従来の触媒担体と同様にして
ハニカム型、円柱型、球型やその他どのような形状にも
成型することがてきる。また、コージライトやムライト
のような非多孔性物質の表面にコーティングして触媒担
体として用いることもできる。When the substance of this invention is used as a catalyst carrier, the precipitate is collected by filtration and molded into a suitable form. The porous material of the present invention can be formed into any shape such as a honeycomb shape, a cylinder shape, a spherical shape, or any other shape in the same manner as conventional catalyst carriers. It can also be used as a catalyst carrier by coating the surface of a non-porous material such as cordierite or mullite.
この発明の触媒担体は、高温下での比表面積か大きいの
で、高温下で使用される触媒の担体に特に適している。Since the catalyst carrier of the present invention has a large specific surface area at high temperatures, it is particularly suitable as a carrier for catalysts used at high temperatures.
このような触媒の例としてガスタービン、灯油及びガス
暖房器、石油及びガス給油器、重質油燃焼機器、燃料電
池用改質層燃焼触媒等の高温燃焼触媒、スチームリフオ
ーマ−触媒並びに臭気、廃棄ガス外化用触媒等を挙げる
ことかてき、これらの触媒としては通常、金属触媒、特
に■属金属か用いられている。触媒担体上への金属触媒
のコーティングは従来と全く同様にして行なうことかて
きる。Examples of such catalysts include gas turbines, kerosene and gas heaters, oil and gas feeders, heavy oil combustion equipment, high temperature combustion catalysts such as reforming bed combustion catalysts for fuel cells, steam reformer catalysts, and odor, Catalysts for removing waste gas and the like are commonly used, and metal catalysts, particularly metals of group II, are usually used as these catalysts. Coating of the metal catalyst onto the catalyst carrier can be carried out in exactly the same manner as conventional methods.
［実施例及び比較例］
次にこの発明の実施例及び比較例を示し、この発明の効
果を具体的に説明する。[Examples and Comparative Examples] Next, Examples and Comparative Examples of the present invention will be shown to specifically explain the effects of the present invention.
イオン交換法により調製した脱イオン水を約３０℃に加
熱し、硫酸アルミニウム６３３ｇを０．１３〜０．１５
Ｍの濃度になるように溶解し、これに濃度ｌ規定のアン
モニア水を６０００ｍ１加え、アルミニウム水和物を沈
殿させた。Deionized water prepared by ion exchange method was heated to about 30°C, and 633g of aluminum sulfate was mixed with 0.13~0.15g of aluminum sulfate.
M was dissolved to a concentration of M, and 6000 ml of ammonia water with a specified concentration of 1 was added thereto to precipitate aluminum hydrate.
次に、ＳｉＯ２の含量が第１表に示す値になるように水
ガラス３号を滴下し、ｐＨを必要に応じて硝酸て７〜８
になるように調整して沈殿を生じさせた。Next, water glass No. 3 is added dropwise so that the SiO2 content becomes the value shown in Table 1, and the pH is adjusted to 7 to 8 with nitric acid as necessary.
The mixture was adjusted so that the precipitate was produced.
沈殿物をろ過洗浄して１２０℃で乾燥させ、１２００℃
て１５時間空気中て焼成した。The precipitate was filtered and washed, dried at 120°C, and heated at 1200°C.
and baked in air for 15 hours.
一方、比較のため、水ガラスを添加することなく上記操
作を行なった。On the other hand, for comparison, the above operation was performed without adding water glass.
得られた焼成物につきＮ２吸着によるＢＥＴ法で比表面
積を測定した。０定は得られた焼成物を１５０℃で１時
間真空乾燥して行なった。結果を第１表に示す。The specific surface area of the obtained fired product was measured by the BET method using N2 adsorption. Zero constant was carried out by vacuum drying the obtained baked product at 150° C. for 1 hour. The results are shown in Table 1.
第１表
実施例１ ２．５ ７０実施例２５８２
実施例３１０ ．８７
実施例４ ２５ ５８比較例１３５８
比較例２ ０ ５
また、実施例２及び３並びに比較例１の各焼成物及び焼
成前の組成物につき、上記ＢＥＴ法の結果より、その孔
径分布、孔の体積及び平均孔径な求めた。結果を第１図
から第６図に示す。Table 1 Example 1 2.5 70 Example 2582 Example 310. 87 Example 4 25 58 Comparative Example 1358 Comparative Example 2 0 5 In addition, from the results of the BET method described above, the pore size distribution and the pore size of each fired product and the composition before firing of Examples 2 and 3 and Comparative Example 1 were The volume and average pore diameter were determined. The results are shown in FIGS. 1 to 6.
また、上記各個の焼成物につきＸ線回折分析を行なった
。結果を第７図から第１２図に示す。In addition, X-ray diffraction analysis was conducted on each of the above-mentioned fired products. The results are shown in FIGS. 7 to 12.
このＸ線回折分析かられかった結晶構造をまとめると第
２表のようになる。The crystal structure determined from this X-ray diffraction analysis is summarized in Table 2.
第２表
結 晶 構 造
実施例１ １Ａ１２０：＋・２ＳｉＯｔ、θ・Ａｌ２
０ａ実施例２３＾１２０１・２ＳｉＯ，、θ・Ａ１□０
３実施例３ ３ Ａ Ｉ ２０３・２ＳｉＯｔ、
０・Ａ１．Ｏ。Table 2 Crystal structure Example 1 1A120: +・2SiOt, θ・Al2
0a Example 23^1201・2SiO,, θ・A1□0
3 Example 3 3 A I 203.2SiOt,
0・A1. O.
実施例４ ３Ａ１２０．・２ＳｉＯ２、θ・Ａ１ｇＯ
ｉ比較例１ ３ＡＩ２（ｈ・２ＳｉＯ，、θ・ＡＩＪ
＊比較例２ α・Ａ１．（ｈExample 4 3A120.・2SiO2, θ・A1gO
i Comparative Example 1 3AI2(h・2SiO,, θ・AIJ
*Comparative example 2 α・A1. (h
第１図、第３図及び第５図は、実施例２、実施例３及び
比較例１の組ｒ＆物の焼成前の孔径分布をそれぞれ示す
図。
第２図、第４図及び第６図は、実施例２、実施例３及び
比較例１の組成物の焼成後の孔径分布をそれぞれ示す図
、
第７図から第１２図は、実施例１から実施例４並びに比
較例１及び２の組成物のＸ線回折図をそれぞれ示す。
特許出願人 東亜燃料工業株式会社
４、′？許出願人代理人 弁理士 各州 英次部＝’Ｔ
’−ｋｉｔ ネ山 正 書 （方式）昭和６２年８月
４日
特、ＰＩ庁長官 小川邦夫殿
１ 用件の表示
昭和６１年特許願第３１０７９１号
２ 発明の名称
耐熱性無機多孔組成物及びそれから成る触媒担体３ 補
正をする者
＝３件との関係 特許出願人
４ 代理人
５ 補正指令の日付 昭和６２年３月３１日６
補正の対象
ｌシ・′ｌヱ芋
７ 補正の内容
８ 添付書類の目録
手続補正書（［１釦
昭和６３年８月４日
１ ！３件の表示
昭和６１年特許願第３１０７９１号
２ 発明の名称
耐熱性無機多孔性組成物及びそれから成る触媒担体４
代理人
６ 補正の対象
７ 補正の内容
明 細 書
１１発明の名称
耐熱性無機多孔性組成物及びそれから成る触媒担体
２、特許請求の範囲
ｆｌｌ ５ｉｎｓとＡｌ２Ｏ３とから成り、５ｉｎｓの
含量が２重１％ないし３０重量％であり、空気中で１０
００℃なｌｒｔ Ｌ １２００℃で焼成して られ、
・にθアルミナ びムライトを し、比表面積が
２０ｍ”７ｇ以上である耐熱性無機多孔性組成物。
（２１ＳｉＯ□の含量が２．５重量％ないし２５重量％
である特許請求の範囲第１項記載の組成物。
（３１ＳｉＯ□とＡ１２０ｍとから成り、Ｓｔｏｗの含
量が２重量％ないし３０重量％であり、空気中で１００
０℃なｕｌ Ｌ １２００℃で焼成して られ、
・にθアルミナ びムライトを し、比表面積が２０
ｍ”７ｇ以上である耐熱性無機多孔性組成物から成る触
媒担体。
４）燃 虫 である、−・ の ２記ＪＢ１
鮪ＪＪＬ体よ
３、発明の詳細な説明
［産業上の利用分野］
この発明は、新規耐熱性無機多孔性組成物及びそれから
成る、高温下での使用に適した触媒担体に関する。
［従来技術及びその欠点］
高温下で使用される触媒、例えばガスタービン、灯油及
びガス暖房器、石油及びガス給油器、重質油燃焼機器、
燃料電池用改質器燃焼触媒等の高温燃焼触媒、スチーム
リフオーマ−触媒並びに臭気、廃棄ガス浄化用触媒等の
担体として、従来よりコージライト（２Ｍｇ０・２Ａｌ
ｚＯｓ・５ＳｉＯ＊）及びムライト（３Ａｌ＊０ｓ−２
ＳｉＯｓ１等が用いられているが、これらは多孔性では
ないので、これらの上に多孔性物質をコーティングして
使用している。多孔性物質としては一般にアルミナが使
用されている。このコーティング剤の上に触媒活性金属
を担持して触媒として使用する。しかしながら、アルミ
ナは高温下でその表面積が小さく、活性金属は使用中に
分散状態が悪くなりすぐ失活する。
また、ランタンベータアルミナ（Ｌａ＊Ｏｓ・１１Ａ１
．ｏ、ｌやバリウムアルミナ［ＢａＯ・６ＡｌｉＯｓ）
が耐熱性が高いという報告があるが、いずれも高温焼成
後の比表面積が満足できる程度に大きくなく、かつ商業
的に使用するためにはコスト高になる。
［発明が解決しようとする問題点］
この発明の目的は、高温下で長時間保持しても大きな比
表面積を保持できる耐熱性の多孔性組成物を提供するこ
とである。さらにこの発明の目的は、高温下で長時間保
持しても大きな比表面積を保持できる耐熱性の多孔性組
成物から成る触媒担体を提供することである。
［問題点を解決するための手段］
本願発明者らは、鋭意研究の結果、Ａｌ＊Ｏｓに一定範
囲の５ｉＯａを加えることによって得られるシリカアル
ミナ組成物をさらに１０００℃ないし１２００℃で焼成
することにより得られる特定の結晶構造を有する組成物
が高温条件下での使用において比表面積を高く保持でき
ることを見出し、この発明を完成した。
すなわち、この発明は、 ＳｉＯｘとＡｌ１０ｍとから
成り、５ｉｎｓの含量が２重量％ないし３０重量％であ
り、空気中で１０００℃ないし１２００℃で焼成して得
られ、実質的にθアルミナ及びムライトを含有し、比表
面積が２０ｍ”７ｇ以上である耐熱性無機多孔性組成物
を提供する。
さらにまた、この発明は、上記耐熱性無機多孔性組成物
から成る触媒担体を提供する。
［発明の効果］
この発明によると、高温下での比表面積が大きな耐熱性
の多孔性の新規組成物が提供される。
この発明の多孔性組成物を触媒の担体として用いると、
その多孔性の故に触媒金属を良く分散させた状態で担持
することができるので、触媒能が大きくなる。さらに、
高温下で長時間使用しても大きな比表面積を保持するの
で、触媒の良好な分散性を維持し、触媒能の低下を引き
起こさない。
［発明の詳細な説明］
上述したように、この発明の耐熱性多孔性組成物の第１
の特徴は５ｉｎｓとＡｌ２Ｏ３とから成り、ＳｉＯ２の
全体に対する割合が２重量％ないし３０重量％、好まし
くは２．５重量％ないし２５重量％であるということに
ある。
この発明の耐熱性無機多孔性組成物の第２の特徴は、１
０００℃ないし１２００℃の高温燃焼により得られ、実
質的にθアルミナとムライトを含有する特定の組成物で
あるということにある。これは、下記実施例に示すよう
に、１１回折分析により把握することができる。
この発明の耐熱性無機多孔性組成物は、高温下での比表
面積が非常に大きなことを特徴とし。
１０００℃ないし１２００℃で焼成した後の比表面積が
２０■”／ｇ以上、好ましくは５０ｍ”／ｇ以上、さら
に好ましくは７０ ｍ”／ｇ以上である。後述の実施例
で明らかになるように、Ａ１．Ｏ，単独の場合には１２
００℃で焼成するとＡｌｌ０Ｉは全てα−Ａｌｔｏｓに
なるのに対し、この発明の耐熱性無機多孔性組成物では
、同温度で焼成するとムライト（３ＡＩＪｓ−２ＳｉＯ
ｍｌとθ−Ａｌ＊Ｏｓとが存在しており、ＳｉＯ□がＡ
ｌ＊０＊のα化を抑制して高表面積を維持することがわ
かった。
この発明の耐熱性無機多孔性組成物中のＳｉＯヨの含量
が上記の範囲外、すなわち、２重量％未溝の場合はＡ１
．０．の焼結とα−ＡＩＪｓの生成を抑制し得るムライ
トが生成せず、従って、後述の実施例においても明らか
な如く高温下での使用により比表面積の激減をもたらす
、一方、Ｓｉｎｇの含量が３０重量％を超える場合は、
はぼ全量に近いＡＩｔｏｓがムライトに転化し、高比表
面積のθ−ＡＩＪｓの含量は少なくなり、当該組成物の
比表面積を低下させる。
次に、この発明の耐熱性無機多孔性組成物の結晶構造に
ついて説明すると、当該組成物は、実施例の第７図ない
し第１０図に示すＸ線回折図形を示し、Ｘ線回折図形中
、格子面間隔３．３９人。
２．２１人はムライト（３ＡｌＩＯ，−２３ｉＯ，）の
存在を示し、格子面間隔２．８４Ａ、２．７３人はθ−
Ａ１．０．を示す、この発明の組成物の高温焼成物には
α−ＡＩ−Ｏｓが含有されていないことが顕著な特徴で
あるが、これは、上記Ｘ線回折図形には比較例２で示さ
れるα−Ａｌｔｏ、の全でのピークが現われていないこ
とからも明らかである。また、θ−Ａｌｔｏｓの基準ピ
ーク（ｄ ＝ ２．７３人、２θ＝３２．８’ ）に対
しムライトの基準ピーク（ｄ −３，３９人、２θ＝２
６、２７°）の高さの比が０．１〜５の範囲のもの特に
４以下のものがこの発明の目的を達成する上で顕著な効
果を発揮することが確認されている。
この発明の耐熱性無機多孔性組成物はアルミニウム水和
物とケイ酸化合物とを混合し、乾燥することによって製
造することができる。アルミニウム水和物は、例えばア
ルミニウム塩を水に溶解し、これにアンモニア水を加え
てつくることができる。アルミニウム塩としては硫酸ア
ルミニウム、塩化アルミニウム、硝酸アルミニウム及び
酢酸アルミニウムが好ましく、水に溶解したときの濃度
は０．０５モルないし０．４モル、特に０．１３モルな
いし０．１５モルが好ましい、また、アンモニア水の濃
度は特に重要ではないが、例えば０．０５規定ないし２
規定程度である。アルミニウム塩溶液にアンモニア水を
加えるとアルミニウム水和物が沈殿する。ケイ酸化合物
としては水ガラスが好ましい。
水ガラスを上記アルミニウム水和物に滴下する。
水ガラスの添加量は５ＬＯＷの量が上記範囲内になるよ
うに選択する。水ガラス添加後、混合物のｐＨを約７な
いし８に調整するとシリカアルミナの沈殿が生成する０
次いでこの沈殿を１０００℃ないし１２００℃で焼成す
ることによりこの発明の耐熱性無機多孔性組成物が得ら
れる。
この発明の組成物を触媒担体として用いる場合には、上
記沈殿をろ過により採取し、これを適当な形態に成型す
る。この発明の多孔性組成物は、従来の触媒担体と同様
にしてハニカム型１円柱型、球型やその他どのような形
状にも成型することができる。また、コージライトやム
ライトのような非多孔性物質の表面にコーティングして
触媒担体として用いることもできる。すなわち、従来法
に従い、例えばろ過により採取した沈殿を乾燥し、必要
に応じて粉砕して得られる粉末に水分を添加、調湿混合
する。又は沈殿を混合してもよい、この混合物を押出し
成型器により例えば押出し成型体、ハニカム、粒状等の
形状のものを得、これを空気中で焼成することができる
。また、従来法に従い、ムライト、シリカアルミナ、コ
ージライトハニカム等の支持体にウォッシュコートする
場合は、例λば、上記の扮東と酸（酢酸、硝酸、塩酸等
）又は塩基（水酸化アンモニウム等）を混合したもの及
び／又はそれにヒドロゲルを添加したものを使用した溶
液に上記支持体を浸漬する。余剰の付着物は不活性ガス
（窒素ガス等）でパージした後乾燥及び焼成を行なう。
この発明の触媒担体は、高温下での比表面積が大きいの
で、高温下で使用される触媒の担体に特に適している。
このような触媒の例としてガスタービン、灯油及びガス
暖房器、石油及びガス給油器１重質油燃焼機器、燃料電
池用改質器燃焼触媒等の高温燃焼触媒、スチームリフオ
ーマ−触媒並びに臭気、廃棄ガス浄化用触媒等を挙げる
ことができ、これらの触媒としては通常、金属触媒、特
に■属金属が用いられている。触媒担体上への金属触媒
のコーティングは従来と全（同様にして行なうことがで
きる。
〔実施例及び比較例］
次にこの発明の実施例及び比較例を示し、この発明の効
果を具体的に説明する。
イオン交換法により調製した脱イオン水を約３０℃に加
熱し、硫酸アルミニウム６３３ｇを０．１３〜０．１５
Ｍの濃度になるように溶解し、これに濃度ｌ規定のアン
モニア水を６０００ｍ１加え、アルミニウム水和物を沈
殿させた。
次に、５１０ｍの含量が第１表に示す値になるように水
ガラス３号を滴下し、ｐＨを必要に応じて硝酸で７〜８
になるように調整して沈殿を生じさせた。
沈殿物をろ過洗浄して１２０℃で乾燥させ、１２００℃
で１５時間空気中で焼成した。
一方、比較のため、水ガラスを添加することなく上記操
作を行なった。
得られた焼成物につきＮ８吸着によるＢＥＴ法で比表面
積を測定した。測定は得られた焼成物を１５０℃で１時
間真空乾燥して行なった。結果を第１表に示す。
第１表
実施例１ ２．５ Ｔ。
実施例２５８２
実施例３ １０ ８７実施例４
２５ ５８比較例１３５８
比較例２ ０ ５
また、実施例２及び３並びに比較例１の各焼成物及び焼
成前の組成物につき、上記ＢＥＴ法の結果より、その孔
径分布、孔の体積及び平均孔径を求めた。結果を第１図
から第６図に示す。
また、上記各個の焼成物につきＸ線回折分析を行なった
。結果を第７図から第１２図に示す。
このＸ線回折分析かられかった結晶構造をまとめると第
２表のようになる。
第２表
騙■１
実施例１ ３Ａｌ＊Ｏｓ’２５１０ｇ、θ・ＡＩＪｓ
実施例２ ３ＡｌｍＯｍ・２ｓｉＯ＊、θ・Ａ１．Ｏ
。
実施例３ ３ＡｌｓＯｓ・２ＳｉＯ＊、θ’ Ａｌｔ
ｏｎ実施例４ ３Ａｌ−Ｏｓ・２ＳｉＯ＊、θ・Ａ１
．０゜比較例１ ３ＡｌｓＯｓ・２５１０ｍ、θ・＾
１ｉｄｓ比較例２ α・ＡＩＪｎ
４、図面の簡単な説明
第１図、第３図及び第５図は、実施例２．実施例３及び
比較例１の組成物の焼成前の孔径分布をそれぞれ示す図
。
第２図、第４図及び第６図は、実施例２、実施例３及び
比較例１の組成物の焼成後の孔径分布をそれぞれ示す図
、
第７図から第１２図は、実施例１から実施例４並びに比
較例１及び２の組成物のｘ１１回折図をそれぞれ示す。FIG. 1, FIG. 3, and FIG. 5 are diagrams showing the pore size distributions of the assemblies of Example 2, Example 3, and Comparative Example 1 before firing, respectively. Figures 2, 4 and 6 are diagrams showing the pore size distributions of the compositions of Example 2, Example 3 and Comparative Example 1 after firing, respectively. Figures 7 to 12 are diagrams showing the pore size distribution of the compositions of Example 1 2 shows the X-ray diffraction patterns of the compositions of Example 4 and Comparative Examples 1 and 2, respectively. Patent applicant: Toa Fuel Industry Co., Ltd. 4,'? Patent applicant agent Patent attorney Each state English department='T
'-kit Masashi Neyama (Method) August 4, 1985 Director-General of the Special and PI Agency Mr. Kunio Ogawa 1 Indication of matter 1985 Patent Application No. 310791 2 Name of the invention Heat-resistant inorganic porous compositions and the like Catalyst carrier consisting of 3 Person making the amendment = Relationship with the 3 cases Patent applicant 4 Agent 5 Date of amendment order March 31, 1988 6
Target of correction
7 Contents of amendment 8 Written amendment to catalog procedure for attached documents ([1 button August 4, 1988 1 ! Showing 3 items 1985 Patent Application No. 310791 2 Name of invention Heat resistance Inorganic porous composition and catalyst carrier 4 made of it
Agent 6 Subject of amendment 7 Description of the amendment Document 11 Name of the invention Heat-resistant inorganic porous composition and catalyst carrier made of the same 2, Claims fll Consisting of 5ins and Al2O3, the content of 5ins is double 1 % to 30% by weight and 10% by weight in air.
00℃ lrt L is fired at 1200℃,
・A heat-resistant inorganic porous composition made of θ alumina and mullite and having a specific surface area of 20m"7g or more. (The content of 21SiO□ is 2.5% to 25% by weight.
The composition according to claim 1. (It is composed of 31SiO□ and A120m, the Stow content is 2% to 30% by weight, and the
0℃ul L is fired at 1200℃,
・Theta alumina bimulite is used, and the specific surface area is 20.
A catalyst carrier made of a heat-resistant inorganic porous composition having a weight of 7 g or more. 4) JB1, which is a fire insect.
Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel heat-resistant inorganic porous composition and a catalyst carrier comprising the same, which is suitable for use at high temperatures. [Prior art and its disadvantages] Catalysts used at high temperatures, such as gas turbines, kerosene and gas heaters, oil and gas refueling equipment, heavy oil combustion equipment,
Cordierite (2Mg0, 2Al
zOs・5SiO*) and mullite (3Al*0s-2
SiOs1 and the like are used, but since these are not porous, they are coated with a porous substance. Alumina is generally used as the porous material. A catalytically active metal is supported on this coating agent and used as a catalyst. However, alumina has a small surface area at high temperatures, and active metals become poorly dispersed during use and are quickly deactivated. In addition, lanthanum beta alumina (La*Os・11A1
．． o, l and barium alumina [BaO・6AliOs)
Although there are reports that these have high heat resistance, the specific surface area after high-temperature firing is not sufficiently large, and the cost is too high for commercial use. [Problems to be Solved by the Invention] An object of the present invention is to provide a heat-resistant porous composition that can maintain a large specific surface area even when kept at high temperatures for a long time. A further object of the present invention is to provide a catalyst carrier made of a heat-resistant porous composition that can maintain a large specific surface area even when kept at high temperatures for a long time. [Means for Solving the Problems] As a result of intensive research, the inventors of the present application have found that a silica-alumina composition obtained by adding a certain range of 5iOa to Al*Os is further fired at 1000°C to 1200°C. The present invention was completed based on the discovery that a composition having a specific crystal structure obtained by the method can maintain a high specific surface area when used under high temperature conditions. That is, this invention consists of SiOx and Al10m, the content of 5ins is 2% to 30% by weight, is obtained by firing in air at 1000°C to 1200°C, and substantially contains θ alumina and mullite. The present invention provides a heat-resistant inorganic porous composition having a specific surface area of 20 m"7 g or more. Furthermore, the present invention provides a catalyst carrier comprising the heat-resistant inorganic porous composition. [Effects of the Invention] ] According to this invention, a new heat-resistant porous composition with a large specific surface area at high temperatures is provided. When the porous composition of this invention is used as a catalyst carrier,
Because of its porosity, it can support the catalyst metal in a well-dispersed state, increasing its catalytic ability. moreover,
Since it maintains a large specific surface area even after long periods of use at high temperatures, it maintains good dispersibility of the catalyst and does not cause a decrease in catalytic performance. [Detailed Description of the Invention] As mentioned above, the first aspect of the heat-resistant porous composition of the present invention
is characterized by consisting of 5ins and Al2O3, with a proportion of SiO2 in the range of 2% to 30% by weight, preferably 2.5% to 25% by weight. The second feature of the heat-resistant inorganic porous composition of the present invention is 1.
It is obtained by high-temperature combustion at 000°C to 1200°C and is a specific composition containing substantially θ alumina and mullite. This can be understood by 11 diffraction analysis as shown in the example below. The heat-resistant inorganic porous composition of the present invention is characterized by a very large specific surface area at high temperatures. The specific surface area after firing at 1000° C. to 1200° C. is 20 m”/g or more, preferably 50 m”/g or more, and more preferably 70 m”/g or more.As will be clear from the examples below. , A1.O, 12 when alone
When fired at 00°C, All0I becomes α-Altos, whereas in the heat-resistant inorganic porous composition of this invention, when fired at the same temperature, it becomes mullite (3AIJs-2SiO
ml and θ-Al*Os exist, and SiO□ is A
It was found that the gelatinization of l*0* was suppressed and a high surface area was maintained. If the content of SiO in the heat-resistant inorganic porous composition of the present invention is outside the above range, that is, 2% by weight is ungrooved, A1
．． 0. Mullite, which can suppress the sintering of α-AIJs and the formation of α-AIJs, is not produced, and therefore, as will be seen in the examples below, use at high temperatures results in a drastic decrease in the specific surface area.On the other hand, when the Sing content is 30 If it exceeds % by weight,
Almost all of the AItos is converted to mullite, and the content of high specific surface θ-AIJs is reduced, reducing the specific surface area of the composition. Next, to explain the crystal structure of the heat-resistant inorganic porous composition of the present invention, the composition exhibits the X-ray diffraction patterns shown in FIGS. 7 to 10 of Examples, and in the X-ray diffraction pattern, Grid spacing 3.39 people. 2.21 people showed the presence of mullite (3AlIO, -23iO,), the lattice spacing was 2.84 A, and 2.73 people showed the presence of θ-
A1.0. It is a remarkable feature that the high-temperature calcined product of the composition of the present invention, which exhibits This is also clear from the fact that all peaks of -Alto do not appear. In addition, the reference peak of mullite (d -3,39 people, 2θ = 2
It has been confirmed that those having a height ratio of 0.1 to 5, particularly those having a height ratio of 4 or less, exhibit a remarkable effect in achieving the object of the present invention. The heat-resistant inorganic porous composition of the present invention can be produced by mixing aluminum hydrate and a silicate compound and drying the mixture. Aluminum hydrate can be produced, for example, by dissolving aluminum salt in water and adding aqueous ammonia to the solution. As the aluminum salt, aluminum sulfate, aluminum chloride, aluminum nitrate and aluminum acetate are preferred, and the concentration when dissolved in water is preferably 0.05 mol to 0.4 mol, particularly 0.13 mol to 0.15 mol, and , the concentration of ammonia water is not particularly important, but for example 0.05N to 2N.
It is within the prescribed range. When aqueous ammonia is added to an aluminum salt solution, aluminum hydrate precipitates. Water glass is preferred as the silicic acid compound. Water glass is added dropwise to the aluminum hydrate. The amount of water glass added is selected so that the amount of 5LOW falls within the above range. After adding water glass, adjust the pH of the mixture to about 7 to 8 to form a silica-alumina precipitate.
Next, this precipitate is calcined at 1000°C to 1200°C to obtain the heat-resistant inorganic porous composition of the present invention. When the composition of the present invention is used as a catalyst carrier, the precipitate is collected by filtration and molded into an appropriate form. The porous composition of the present invention can be molded into any shape such as a honeycomb, a cylinder, a sphere, or any other shape in the same manner as conventional catalyst carriers. It can also be used as a catalyst carrier by coating the surface of a non-porous material such as cordierite or mullite. That is, according to a conventional method, for example, a precipitate collected by filtration is dried, and if necessary, pulverized, and water is added to the resulting powder and mixed to control the humidity. Alternatively, a precipitate may be mixed. This mixture may be extruded into a shape such as an extrusion molded body, a honeycomb, a granule, etc., and this can be fired in air. In addition, when wash-coating a support such as mullite, silica alumina, cordierite honeycomb, etc. according to a conventional method, for example, the above-mentioned Ato and an acid (acetic acid, nitric acid, hydrochloric acid, etc.) or a base (ammonium hydroxide, etc.) can be used. ) and/or to which a hydrogel is added. Excess deposits are purged with an inert gas (nitrogen gas, etc.), and then dried and fired. Since the catalyst carrier of the present invention has a large specific surface area at high temperatures, it is particularly suitable as a carrier for catalysts used at high temperatures. Examples of such catalysts include gas turbines, kerosene and gas heaters, oil and gas refueling equipment, heavy oil combustion equipment, high temperature combustion catalysts such as reformer combustion catalysts for fuel cells, steam reformer catalysts, and odor, Catalysts for waste gas purification and the like can be mentioned, and metal catalysts, particularly group II metals, are usually used as these catalysts. The coating of the metal catalyst on the catalyst carrier can be carried out in the same manner as conventional methods. [Examples and Comparative Examples] Next, Examples and Comparative Examples of the present invention will be shown to specifically demonstrate the effects of the present invention. Deionized water prepared by ion exchange method is heated to about 30°C, and 633g of aluminum sulfate is heated to 0.13 to 0.15%.
M was dissolved to a concentration of M, and 6000 ml of aqueous ammonia with a specified concentration of 1 was added thereto to precipitate aluminum hydrate. Next, drop water glass No. 3 so that the content of 510m becomes the value shown in Table 1, and adjust the pH to 7 to 8 with nitric acid as necessary.
The mixture was adjusted so that the precipitate was produced. The precipitate was filtered and washed, dried at 120°C, and heated at 1200°C.
It was baked in air for 15 hours. On the other hand, for comparison, the above operation was performed without adding water glass. The specific surface area of the obtained fired product was measured by the BET method using N8 adsorption. The measurement was performed by vacuum drying the obtained baked product at 150° C. for 1 hour. The results are shown in Table 1. Table 1 Example 1 2.5 T. Example 2582 Example 3 10 87 Example 4
25 58 Comparative Example 1358 Comparative Example 2 0 5 In addition, from the results of the above BET method, the pore size distribution, pore volume, and average pore diameter of each fired product and the composition before firing of Examples 2 and 3 and Comparative Example 1 were determined. I asked for The results are shown in FIGS. 1 to 6. In addition, X-ray diffraction analysis was conducted on each of the above-mentioned fired products. The results are shown in FIGS. 7 to 12. The crystal structure determined from this X-ray diffraction analysis is summarized in Table 2. Table 2 Deception ■1 Example 1 3Al*Os'2510g, θ・AIJs
Example 2 3AlmOm・2siO*, θ・A1. O
. Example 3 3AlsOs・2SiO*, θ' Alt
on Example 4 3Al-Os・2SiO*, θ・A1
．． 0° Comparative Example 1 3AlsOs・2510m, θ・＾
1ids Comparative Example 2 α・AIJn 4, Brief Description of Drawings FIGS. 1, 3, and 5 show Example 2. FIG. 3 is a diagram showing the pore size distribution of the compositions of Example 3 and Comparative Example 1 before firing, respectively. 2, 4, and 6 are diagrams showing the pore size distributions of the compositions of Example 2, Example 3, and Comparative Example 1 after firing, respectively. 11 shows x11 diffractograms of the compositions of Example 4 and Comparative Examples 1 and 2, respectively.
Claims (6)
＿２の含量が２ないし３０重量％であり、空気中で１２
００℃で焼成した後の比表面積が２０ｍ＾２／ｇ以上で
ある耐熱性無機多孔組成物。(1) Consisting of SiO_2 and Al_2O_3, SiO
The content of _2 is 2 to 30% by weight, and 12% in air.
A heat-resistant inorganic porous composition having a specific surface area of 20 m^2/g or more after firing at 00°C.
る特許請求の範囲第１項記載の組成物。(2) The composition according to claim 1, wherein the content of SiO_2 is 2.5 to 25% by weight.
０ｍ＾２／ｇ以上である特許請求の範囲第１項又は第２
項記載の耐熱性無機多孔組成物。(3) Specific surface area after firing at 1200℃ in air is 5
Claim 1 or 2 which is 0m^2/g or more
The heat-resistant inorganic porous composition described in 1.
＿２の含量が２ないし３０重量％であり、空気中で１２
００℃で焼成した後の比表面積が２０ｍ＾２／ｇ以上で
ある耐熱性無機多孔組成物から成る触媒担体。(4) Consisting of SiO_2 and Al_2O_3, SiO
The content of _2 is 2 to 30% by weight, and 12% in air.
A catalyst carrier made of a heat-resistant inorganic porous composition having a specific surface area of 20 m^2/g or more after firing at 00°C.
る特許請求の範囲第４項記載の触媒担体。(5) The catalyst carrier according to claim 4, wherein the content of SiO_2 is 2.5 to 25% by weight.
０ｍ＾２／ｇ以上である特許請求の範囲第４項又は第５
項記載の触媒担体。(6) Specific surface area after firing at 1200℃ in air is 5
Claim 4 or 5 which is 0 m^2/g or more
Catalyst carrier as described in section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61310791A JPS63295484A (en) | 1986-12-29 | 1986-12-29 | Heat-resistant inorganic porous composition and carrier for catalyst consisting of it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61310791A JPS63295484A (en) | 1986-12-29 | 1986-12-29 | Heat-resistant inorganic porous composition and carrier for catalyst consisting of it |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63295484A true JPS63295484A (en) | 1988-12-01 |
| JPH0336789B2 JPH0336789B2 (en) | 1991-06-03 |
Family
ID=18009499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61310791A Granted JPS63295484A (en) | 1986-12-29 | 1986-12-29 | Heat-resistant inorganic porous composition and carrier for catalyst consisting of it |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63295484A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6011280A (en) * | 1983-06-20 | 1985-01-21 | エンゲルハ−ド・コ−ポレ−シヨン | Porous mullite |
-
1986
- 1986-12-29 JP JP61310791A patent/JPS63295484A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6011280A (en) * | 1983-06-20 | 1985-01-21 | エンゲルハ−ド・コ−ポレ−シヨン | Porous mullite |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0336789B2 (en) | 1991-06-03 |
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