JP2007175649A - Solid acid, its manufacturing method, and solid acid catalyst - Google Patents
Solid acid, its manufacturing method, and solid acid catalyst Download PDFInfo
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- JP2007175649A JP2007175649A JP2005378982A JP2005378982A JP2007175649A JP 2007175649 A JP2007175649 A JP 2007175649A JP 2005378982 A JP2005378982 A JP 2005378982A JP 2005378982 A JP2005378982 A JP 2005378982A JP 2007175649 A JP2007175649 A JP 2007175649A
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- 239000011973 solid acid Substances 0.000 title claims abstract description 72
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 38
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 18
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims abstract description 15
- -1 tungstic acid compound Chemical class 0.000 claims abstract description 14
- 238000001179 sorption measurement Methods 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010304 firing Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- BKUSIKGSPSFQAC-RRKCRQDMSA-N 2'-deoxyinosine-5'-diphosphate Chemical compound O1[C@H](CO[P@@](O)(=O)OP(O)(O)=O)[C@@H](O)C[C@@H]1N1C(NC=NC2=O)=C2N=C1 BKUSIKGSPSFQAC-RRKCRQDMSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、新規な固体酸及びその製造方法、並びに該固体酸からなる固体酸触媒に関し、特に材料としての安定性に優れ、かつ高い表面酸性度を有する新規固体酸に関するものである。 The present invention relates to a novel solid acid and a method for producing the same, and a solid acid catalyst comprising the solid acid, and particularly relates to a novel solid acid having excellent stability as a material and high surface acidity.
従来、アルミナ、シリカ−アルミナ、シリカ−マグネシア等の物質が、固体酸として機能することがよく知られている。これらの物質は、固体酸としての性質を利用して、各種反応の触媒や吸着剤などとして広く利用されている。 Conventionally, it is well known that substances such as alumina, silica-alumina, and silica-magnesia function as solid acids. These substances are widely used as catalysts and adsorbents for various reactions by utilizing the properties as solid acids.
ところで、上記固体酸からなる固体酸触媒は、固体であるため回収が容易で、また、反応装置を腐食することがなく、環境に優しい触媒であるため、いわゆるグリーンケミストリーの観点からも着目されている。 By the way, the solid acid catalyst composed of the above-mentioned solid acid is easy to recover because it is a solid, and does not corrode the reaction apparatus and is an environment-friendly catalyst. Therefore, it is also attracting attention from the viewpoint of so-called green chemistry. Yes.
上記固体酸は、通常５００〜６００℃前後の温度で原料を焼成することにより製造される。例えば、特開平７−１９４９７６号公報（特許文献１）には、アルミナ水和物の表面にシリカ水和物を沈着させた後、酸素の存在下、５５０〜６５０℃の温度で焼成することにより、シリカ−アルミナを製造できることが開示されている。 The solid acid is usually produced by firing the raw material at a temperature of about 500 to 600 ° C. For example, in JP-A-7-194976 (Patent Document 1), silica hydrate is deposited on the surface of alumina hydrate and then fired at a temperature of 550 to 650 ° C. in the presence of oxygen. It is disclosed that silica-alumina can be produced.
しかしながら、従来の固体酸は、より高温で焼成すると表面の酸性度が低下し、その結果、該固体酸を触媒として使用した場合に活性が低下してしまう問題があった。また、５００〜６００℃で焼成して得られる通常のアルミナは、γ−アルミナなどの中間的な結晶状態にあるため、使用中に高温に曝されたり、或いは熱履歴を受けることにより、結晶状態が変化してしまうという問題があった。更に、上記固体酸は、触媒として使用した場合に、反応系中の水分によって酸強度が低下してしまうという問題もあった。 However, when the conventional solid acid is baked at a higher temperature, the acidity of the surface is lowered. As a result, there is a problem that the activity is lowered when the solid acid is used as a catalyst. Moreover, since the normal alumina obtained by baking at 500-600 degreeC exists in intermediate | middle crystalline states, such as (gamma) -alumina, it is exposed to high temperature during use, or receives a thermal history, and a crystalline state There was a problem that changed. Furthermore, when the solid acid is used as a catalyst, there is also a problem that the acid strength is lowered by moisture in the reaction system.
そこで、本発明の目的は、上記従来技術の問題を解決し、固体酸触媒として好適に使用するこができ、材料としての安定性に優れ、かつ高い表面酸性度を有する新規な固体酸を提供することにある。また、本発明の他の目的は、かかる固体酸の製造方法を提供することにある。 Accordingly, the object of the present invention is to provide a novel solid acid that solves the above-mentioned problems of the prior art, can be suitably used as a solid acid catalyst, has excellent stability as a material, and has high surface acidity. There is to do. Another object of the present invention is to provide a method for producing such a solid acid.
本発明者らは、上記目的を達成するために鋭意検討した結果、水酸化アルミニウムにタングステン酸化合物を含浸させて、１０００℃以上の高温で焼成することにより、アルミナがα−アルミナとして含有されるため材料として安定である一方、表面の酸性度が高い固体酸が得られることを見出し、本発明を完成させるに至った。 As a result of intensive studies to achieve the above object, the present inventors have impregnated aluminum hydroxide with a tungstic acid compound and calcined it at a high temperature of 1000 ° C. or higher, whereby alumina is contained as α-alumina. Therefore, it was found that a solid acid having a high surface acidity can be obtained while being stable as a material, and the present invention has been completed.
即ち、本発明は、
［１］α−アルミナ及びタングステン酸を含有し、比表面積が３〜５０ｍ2／ｇであり、かつアルゴン吸着熱が−１４.５ｋＪ／ｍｏｌ以下である固体酸、
［２］上記タングステン酸の含有量が、酸化物として０.１〜１０質量％である上記［１］の固体酸、
［３］上記［１］又は［２］の固体酸からなる固体酸触媒、
［４］水酸化アルミニウムにタングステン酸化合物を含浸させた後、１０００℃以上の焼成温度で焼成する上記［１］又は［２］の固体酸の製造方法、及び
［５］上記焼成温度が１０００〜１２００℃である上記［４］の固体酸の製造方法に関するものである。
That is, the present invention
[1] A solid acid containing α-alumina and tungstic acid, having a specific surface area of 3 to 50 m 2 / g and an argon adsorption heat of −14.5 kJ / mol or less,
[2] The solid acid according to the above [1], wherein the content of the tungstic acid is 0.1 to 10% by mass as an oxide,
[3] A solid acid catalyst comprising the solid acid of [1] or [2] above,
[4] A method for producing a solid acid according to [1] or [2] above, wherein aluminum hydroxide is impregnated with a tungstic acid compound and then calcined at a calcining temperature of 1000 ° C. or higher, and [5] the calcining temperature is 1000 to 1000. The present invention relates to the method for producing a solid acid according to the above [4], which is 1200 ° C.
本発明によれば、原料を高温で焼成して固体酸を調製するため、材料としての安定性、特に熱安定性が高く、加えて表面の酸性度が高い固体酸を提供することができる。また、本発明の固体酸は、表面の酸性度が高いので、異性化反応、クラッキング、不均化反応、エステル化反応、エステル交換反応などの反応の触媒として優れた触媒作用を発揮する。 According to the present invention, the solid acid is prepared by baking the raw material at a high temperature, so that it is possible to provide a solid acid having high stability as a material, in particular, high thermal stability and high surface acidity. Further, since the solid acid of the present invention has high surface acidity, it exhibits excellent catalytic action as a catalyst for reactions such as isomerization reaction, cracking, disproportionation reaction, esterification reaction and transesterification reaction.
＜固体酸＞
以下に、本発明の固体酸を詳細に説明する。本発明の固体酸は、α−アルミナ及びタングステン酸を含有し、比表面積が３〜５０ｍ2／ｇであり、かつアルゴン吸着熱が−１４.５ｋＪ／ｍｏｌ以下であることを特徴とする。ここで、本発明の固体酸においては、アルミナと酸化タングステンとの複合酸化物であるタングステン酸塩（又はタングステン酸化合物）が活性種として作用するものと考えられる。なお、固体酸中のアルミナがα−アルミナの形態で存在することは、ＸＲＤによって確認することができる。また、固体酸の比表面積は、Ｎ2吸着によるＢＥＴ法で測定することができる。更に、固体酸のアルゴン吸着熱は、J. Phys. Chem., B, vol.105, p9669 (2001) に記載の方法に従って測定することができる。
<Solid acid>
Below, the solid acid of this invention is demonstrated in detail. The solid acid of the present invention contains α-alumina and tungstic acid, has a specific surface area of 3 to 50 m 2 / g, and an argon adsorption heat of −14.5 kJ / mol or less. Here, in the solid acid of the present invention, it is considered that tungstate (or tungstic acid compound) which is a composite oxide of alumina and tungsten oxide acts as an active species. In addition, it can confirm by XRD that the alumina in a solid acid exists with the form of alpha alumina. The specific surface area of the solid acid can be measured by the BET method using N 2 adsorption. Furthermore, the heat of argon adsorption of the solid acid can be measured according to the method described in J. Phys. Chem., B, vol. 105, p9669 (2001).
本発明の固体酸は、アルミナとして熱的安定性の高いα−アルミナを含むため、材料としての安定性（特に熱的安定性）が非常に高い。なお、固体酸中のアルミナがγ−アルミナやδ−アルミナの形態で存在する場合、固体酸の表面の酸性度が不十分で、触媒としての活性が低くなる。また、本発明の固体酸は、アルゴン吸着熱が−１４.５ｋＪ／ｍｏｌ以下であるため、表面の酸性度が非常に高い。 Since the solid acid of the present invention contains α-alumina having high thermal stability as alumina, the material stability (particularly thermal stability) is very high. In addition, when the alumina in a solid acid exists with the form of (gamma) -alumina or (delta) -alumina, the acidity of the surface of a solid acid is inadequate, and the activity as a catalyst becomes low. Moreover, since the solid acid of the present invention has an argon adsorption heat of -14.5 kJ / mol or less, the acidity of the surface is very high.
上記固体酸の比表面積が３ｍ2／ｇ未満では、触媒として使用した場合の活性点が少ないため触媒活性が低くなり、一方、比表面積が５０ｍ2／ｇを超える固体酸を調製することは、高温で焼成するため、実際上困難である。また、アルゴン吸着熱が−１４.５ｋＪ／ｍｏｌより大きい固体酸は、表面の酸性度が低いため、各種酸触媒反応における触媒活性が低くなる。 If the specific surface area of the solid acid is less than 3 m 2 / g, the catalytic activity is low because there are few active sites when used as a catalyst, while preparing a solid acid with a specific surface area of more than 50 m 2 / g, Since it is fired at a high temperature, it is practically difficult. Moreover, since the acidity of the surface of the solid acid whose argon adsorption heat is larger than −14.5 kJ / mol is low, the catalytic activity in various acid catalytic reactions is low.
本発明の固体酸において、上記タングステン酸の含有量は、酸化物（ＷＯ3）として０.１〜１０質量％の範囲が好ましい。固体酸中のタングステン酸の含有量が酸化物として０.１質量％未満では、高温での焼成により３ｍ2／ｇ以上の比表面積を維持することが難しくなり、一方、１０質量％を超えると、十分な酸性度を得ることが難しくなる。これらの観点から、上記タングステン酸の含有量は、酸化物として１〜５質量％の範囲が更に好ましい。 In the solid acid of the present invention, the content of the tungstic acid is preferably in the range of 0.1 to 10% by mass as an oxide (WO 3 ). When the content of tungstic acid in the solid acid is less than 0.1% by mass as an oxide, it becomes difficult to maintain a specific surface area of 3 m 2 / g or more by firing at a high temperature, while when the content exceeds 10% by mass. It becomes difficult to obtain sufficient acidity. From these viewpoints, the content of the tungstic acid is more preferably in the range of 1 to 5% by mass as an oxide.
＜固体酸の製造方法＞
上述した本発明の固体酸は、水酸化アルミニウムにタングステン酸化合物を含浸させた後、１０００℃以上の焼成温度で焼成することにより製造することができる。例えば、水酸化アルミニウム粉末を１００℃で乾燥した後、メタタングステン酸アンモニウム水溶液を含浸させ、乾燥させた後、空気中、１０００℃以上で３時間焼成することにより、上記固体酸を製造することができる。なお、固体酸にタングステン酸を含有させることにより、理由は明らかではないが、α−アルミナ表面で強い酸性度を示すようになる。
<Method for producing solid acid>
The solid acid of the present invention described above can be produced by impregnating aluminum hydroxide with a tungstic acid compound and then firing at a firing temperature of 1000 ° C. or higher. For example, after the aluminum hydroxide powder is dried at 100 ° C., impregnated with an ammonium metatungstate aqueous solution and dried, the solid acid is produced by baking in air at 1000 ° C. or higher for 3 hours. it can. In addition, when tungstic acid is contained in the solid acid, the reason is not clear, but strong acidity is exhibited on the α-alumina surface.
上記固体酸の原料の水酸化アルミニウムとしては、特に限定されるものではないが、通常は、粉末を用いる。また、該水酸化アルミニウムの製造方法も、特に限定されるものではなく、一般的な方法で製造することができる。 Although it does not specifically limit as aluminum hydroxide of the said solid acid raw material, Usually, a powder is used. Moreover, the manufacturing method of this aluminum hydroxide is not specifically limited, either, It can manufacture by a general method.
上記固体酸の原料として使用するタングステン酸化合物は、焼成によりタングステン酸になり得る化合物であればよい。該タングステン酸化合物として、具体的には、三酸化タングステン（ＷＯ3）、タングステン酸アンモニウム［(ＮＨ4)ＷＯ4］、パラタングステン酸アンモニウム［５(ＮＨ4)2Ｏ・１２ＷＯ3・５Ｈ2Ｏ］、メタタングステン酸アンモニウム［(ＮＨ4)6(Ｈ2Ｗ12Ｏ40)・ｎＨ2Ｏ］などを使用することができ、これらの中でも、メタタングステン酸アンモニウムを使用することが好ましい。 The tungstic acid compound used as the raw material for the solid acid may be any compound that can be converted to tungstic acid by firing. Specific examples of the tungstic acid compound include tungsten trioxide (WO 3 ), ammonium tungstate [(NH 4 ) WO 4 ], and ammonium paratungstate [5 (NH 4 ) 2 O · 12WO 3 · 5H 2 O. ], Ammonium metatungstate [(NH 4 ) 6 (H 2 W 12 O 40 ) · nH 2 O], etc., among these, it is preferable to use ammonium metatungstate.
上記タングステン酸化合物は、最終的な固体酸においてタングステン酸含有量が酸化物として０.１〜１０質量％の範囲になるように、上記水酸化アルミニウムに含浸させることが好ましく、１〜５質量％の範囲になるように含浸させることが更に好ましい。また、水酸化アルミニウムへのタングステン酸化合物の担持方法は、特に限定されず、通常の担持方法で実施することができる。なお、通常は、タングステン酸化合物の水溶液を水酸化アルミニウムに含浸させて担持する。更に、水酸化アルミニウムへのタングステン酸化合物の含浸方法も、特に限定されず、通常の含浸方法で実施することができる。ここで、含浸方法としては、例えば、ポアフィリング法、加熱含浸法、真空含浸法、浸漬法、スプレー法等を挙げることができる。なお、通常は、水酸化アルミニウムにタングステン酸化合物を含む水溶液を含浸させた後、乾燥させる。 The tungstic acid compound is preferably impregnated in the aluminum hydroxide so that the tungstic acid content in the final solid acid is in the range of 0.1 to 10% by mass as an oxide, and is preferably 1 to 5% by mass. It is more preferable to impregnate so that it may become this range. Further, the method for supporting the tungstic acid compound on the aluminum hydroxide is not particularly limited, and can be carried out by a normal supporting method. Usually, an aqueous solution of a tungstic acid compound is impregnated with aluminum hydroxide and supported. Furthermore, the impregnation method of the tungstic acid compound into aluminum hydroxide is not particularly limited, and can be carried out by a normal impregnation method. Here, examples of the impregnation method include a pore filling method, a heating impregnation method, a vacuum impregnation method, an immersion method, and a spray method. Usually, aluminum hydroxide is impregnated with an aqueous solution containing a tungstic acid compound and then dried.
上記のようにして、水酸化アルミニウムにタングステン酸化合物を含む水溶液を含浸させた後、１０００℃以上で焼成することにより、固体酸中のアルミナが熱的安定性の高いα−アルミナとして存在するようになる。なお、焼成温度が１０００℃未満では、固体酸中のアルミナがγ−アルミナやδ−アルミナの形態で存在するようになるため、固体酸の酸性度が不十分となり、触媒としての活性が低くなる。ここで、上記焼成温度は、１０００〜１２５０℃の範囲が好ましく、１０００〜１２００℃の範囲が更に好ましい。焼成温度が１２００℃を超えると、比表面積の低下が観察され始め、また、１２５０℃を超えると、急激な比表面積の低下が起こることがある。なお、焼成時間は、１〜５時間の範囲が好ましく、２〜４時間の範囲が更に好ましい。 As described above, after impregnating aluminum hydroxide with an aqueous solution containing a tungstic acid compound and firing at 1000 ° C. or higher, alumina in the solid acid is present as α-alumina having high thermal stability. become. If the calcination temperature is less than 1000 ° C., alumina in the solid acid is present in the form of γ-alumina or δ-alumina, so that the acidity of the solid acid becomes insufficient and the activity as a catalyst is lowered. . Here, the firing temperature is preferably in the range of 1000 to 1250 ° C, and more preferably in the range of 1000 to 1200 ° C. When the firing temperature exceeds 1200 ° C., a decrease in specific surface area starts to be observed, and when it exceeds 1250 ° C., a rapid decrease in specific surface area may occur. The firing time is preferably in the range of 1 to 5 hours, and more preferably in the range of 2 to 4 hours.
＜固体酸触媒＞
上述した本発明の固体酸は、高い表面酸性度を有するため、異性化反応、クラッキング、不均化反応、エステル化反応、エステル交換反応などの種々の反応の触媒として好適に使用することができる。また、本発明の固体酸は、α−アルミナを含み、材料としての安定性に優れるため、触媒として安定に使用することができ、触媒寿命が長い。また、本発明の固体酸は、耐水性や耐熱性に優れているので、水性ガスシフト反応やジメチルエーテル水蒸気改質触媒をはじめ、触媒燃焼、水和反応、脱水反応などの触媒、あるいは担体として使用することができる。
<Solid acid catalyst>
Since the solid acid of the present invention described above has high surface acidity, it can be suitably used as a catalyst for various reactions such as isomerization reaction, cracking, disproportionation reaction, esterification reaction and transesterification reaction. . In addition, the solid acid of the present invention contains α-alumina, and is excellent in stability as a material. Therefore, it can be used stably as a catalyst and has a long catalyst life. In addition, since the solid acid of the present invention is excellent in water resistance and heat resistance, it is used as a catalyst or a carrier for catalytic combustion, hydration reaction, dehydration reaction, etc., including water gas shift reaction and dimethyl ether steam reforming catalyst. be able to.
以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。なお、調製した触媒の比表面積及びアルゴン吸着熱は下記の方法で測定した。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples. In addition, the specific surface area and argon adsorption heat of the prepared catalyst were measured by the following method.
［分析方法］
（１）比表面積
Ｎ2吸着によるＢＥＴ法で比表面積を測定した。
[Analysis method]
(1) Specific surface area The specific surface area was measured by the BET method using N 2 adsorption.
（２）アルゴン吸着熱
J. Phys. Chem., B vol.105, p9669 (2001) に記載の方法に従って、−３０〜−６０℃の温度範囲におけるＡｒの吸着量を測定し、吸着量の温度依存性から吸着熱を求めた。
(2) Heat of argon adsorption
According to the method described in J. Phys. Chem., B vol.105, p9669 (2001), the adsorption amount of Ar in the temperature range of −30 to −60 ° C. is measured, and the heat of adsorption is determined from the temperature dependence of the adsorption amount. Asked.
（実施例１）
［１％−ＷＯ3／Ａｌ2Ｏ3（１２００℃）の製造（触媒１）］
水酸化アルミニウム（高純度化学製、１００メッシュ以下）を１００℃で乾燥させた後、固体酸中のタングステン酸含有量が酸化物として１質量％になるように、メタタングステン酸アンモニウム（日本無機化学工業製）の水溶液を含浸した。その後、水分を蒸発させた後、乾燥した。次いで、空気中、１２００℃で３時間焼成して触媒１を得た。得られた触媒１は、比表面積が７.７ｍ2／ｇであり、Ａｒ吸着熱が−１４.７ｋＪ／ｍｏｌであった。また、得られた触媒１をＸＲＤ分析したところ、アルミナがα−アルミナの形態で存在することが確認された。
Example 1
[Production of 1% -WO 3 / Al 2 O 3 (1200 ° C.) (Catalyst 1)]
After aluminum hydroxide (product of high purity chemical, 100 mesh or less) is dried at 100 ° C., ammonium metatungstate (Nippon Inorganic Chemistry) is used so that the content of tungstic acid in the solid acid is 1% by mass as an oxide. (Made by Kogyo) was impregnated. Thereafter, the water was evaporated and dried. Subsequently, the catalyst 1 was obtained by calcining in air at 1200 ° C. for 3 hours. The obtained catalyst 1 had a specific surface area of 7.7 m 2 / g and an Ar adsorption heat of −14.7 kJ / mol. Further, when the obtained catalyst 1 was subjected to XRD analysis, it was confirmed that alumina was present in the form of α-alumina.
（実施例２）
［３％−ＷＯ3／Ａｌ2Ｏ3（１１００℃）の製造（触媒２）］
水酸化アルミニウム（高純度化学製、１００メッシュ以下）を１００℃で乾燥させた後、固体酸中のタングステン酸含有量が酸化物として３質量％になるように、メタタングステン酸アンモニウム（日本無機化学工業製）の水溶液を含浸した。その後、水分を蒸発させた後、乾燥した。次いで、空気中、１１００℃で３時間焼成して触媒２を得た。得られた触媒２は、比表面積が１５.０ｍ2／ｇであり、Ａｒ吸着熱が−１５.５ｋＪ／ｍｏｌであった。また、得られた触媒２をＸＲＤ分析したところ、アルミナがα−アルミナの形態で存在することが確認された。
(Example 2)
[Production of 3% -WO 3 / Al 2 O 3 (1100 ° C.) (Catalyst 2)]
After aluminum hydroxide (product of high purity chemical, 100 mesh or less) is dried at 100 ° C., ammonium metatungstate (Nippon Inorganic Chemistry) is used so that the content of tungstic acid in the solid acid becomes 3% by mass as an oxide. (Made by Kogyo) was impregnated. Thereafter, the water was evaporated and dried. Subsequently, the catalyst 2 was obtained by calcining in air at 1100 ° C. for 3 hours. The obtained catalyst 2 had a specific surface area of 15.0 m 2 / g and an Ar adsorption heat of −15.5 kJ / mol. Further, when the obtained catalyst 2 was subjected to XRD analysis, it was confirmed that alumina was present in the form of α-alumina.
（実施例３）
［５％−ＷＯ3／Ａｌ2Ｏ3（１０００℃）の製造（触媒３）］
水酸化アルミニウム（高純度化学製、１００メッシュ以下）を１００℃で乾燥させた後、固体酸中のタングステン酸含有量が酸化物として５質量％になるように、メタタングステン酸アンモニウム（日本無機化学工業製）の水溶液を含浸した。その後、水分を蒸発させた後、乾燥した。次いで、空気中、１０００℃で３時間焼成して触媒３を得た。得られた触媒３は、比表面積が３０.２ｍ2／ｇであり、Ａｒ吸着熱が−１６.４ｋＪ／ｍｏｌであった。また、得られた触媒３をＸＲＤ分析したところ、アルミナがα−アルミナの形態で存在することが確認された。
(Example 3)
[Production of 5% -WO 3 / Al 2 O 3 (1000 ° C.) (Catalyst 3)]
After aluminum hydroxide (product of high purity chemical, 100 mesh or less) is dried at 100 ° C., ammonium metatungstate (Nippon Inorganic Chemistry) is used so that the content of tungstic acid in the solid acid is 5% by mass as an oxide. (Made by Kogyo) was impregnated. Thereafter, the water was evaporated and dried. Subsequently, the catalyst 3 was obtained by calcining in air at 1000 ° C. for 3 hours. The obtained catalyst 3 had a specific surface area of 30.2 m 2 / g and an Ar adsorption heat of −16.4 kJ / mol. Further, when the obtained catalyst 3 was subjected to XRD analysis, it was confirmed that alumina was present in the form of α-alumina.
（比較触媒１）
５００℃で焼成された日本触媒学会の標準触媒［ＪＲＣ−ＳＡＬ−２、シリカ−アルミナ（ＳｉＯ2−Ａｌ2Ｏ3）］を比較触媒１とした。該比較触媒１は、比表面積が５６０ｍ2／ｇであり、Ａｒ吸着熱が−１４.４ｋＪ／ｍｏｌであった。
(Comparative catalyst 1)
A standard catalyst [JRC-SAL-2, silica-alumina (SiO 2 -Al 2 O 3 )] of the Japan Society for Catalysis was calcined at 500 ° C. was used as Comparative Catalyst 1. The comparative catalyst 1 had a specific surface area of 560 m 2 / g and an Ar adsorption heat of −14.4 kJ / mol.
（比較触媒２）
水酸化アルミニウムを、空気中、１２００℃で３時間焼成して、アルミナ（Ａｌ2Ｏ3）を調製し、比較触媒２とした。該比較触媒２は、比表面積が４.８ｍ2／ｇであり、Ａｒ吸着熱が−１２.５ｋＪ／ｍｏｌであった。
(Comparative catalyst 2)
Aluminum hydroxide was calcined in air at 1200 ° C. for 3 hours to prepare alumina (Al 2 O 3 ), which was used as Comparative Catalyst 2. The comparative catalyst 2 had a specific surface area of 4.8 m 2 / g and an Ar adsorption heat of −12.5 kJ / mol.
（実施例４〜１０及び比較例１〜４）
Chem. Commun., (1995), p789に開示の方法に従って、マイクロ触媒パルス反応器（キャリアガス：Ｈｅ、Ｈｅ流量：３０ｍｌ／ｍｉｎ、パルスサイズ：１μｌ）を用いてアルキルベンゼンの反応（トルエンの不均化反応、エチルベンゼン及びクメンの分解反応）を行った。なお、使用した各触媒は、反応前にＨｅ気流中で、３００℃で１時間加熱した。また、反応後、反応器から流出した生成物を直接ガスクロマトグラフのカラム（ＧＬサイエンス製；Ｂｅｎｔｏｎｅ ３４ ＋ ＤＩＤＰ（５＋５）％／Ｕｎｉｐｏｒｔ Ｂ ８０−１００、ステンレスカラム：２ｍ×３ｍｍＩＤ、カラム温度：８０〜１００℃）へ導入して、分析を行った。反応器に充填した触媒量、反応温度及び転化率を表１に示す。
(Examples 4 to 10 and Comparative Examples 1 to 4)
According to the method disclosed in Chem. Commun., (1995), p789, reaction of alkylbenzene (toluene disproportionate) using a microcatalyst pulse reactor (carrier gas: He, He flow rate: 30 ml / min, pulse size: 1 μl). Reaction, decomposition reaction of ethylbenzene and cumene). Each catalyst used was heated at 300 ° C. for 1 hour in a He stream before the reaction. In addition, after the reaction, the product flowing out from the reactor was directly converted into a gas chromatograph column (manufactured by GL Sciences; Bentone 34 + DIDP (5 + 5)% / Uniport B 80-100, stainless steel column: 2 m × 3 mm ID, column temperature: 80 to 100 ° C.) for analysis. Table 1 shows the amount of catalyst charged in the reactor, the reaction temperature, and the conversion rate.
表１の結果から、本発明に従う固体酸を種々の触媒反応の触媒として使用することで、一般的な固体酸であるシリカ−アルミナ（比較触媒１）を触媒として使用した場合に比べて、転化率が大幅に向上することが分る。また、比較例４の結果から、１２００℃で焼成して得たアルミナ（α−アルミナ）は、触媒作用がないことが分る。 From the results of Table 1, the use of the solid acid according to the present invention as a catalyst for various catalytic reactions results in conversion as compared with the case where silica-alumina (comparative catalyst 1), which is a general solid acid, is used as a catalyst. It can be seen that the rate is significantly improved. Moreover, it turns out that the alumina ((alpha) -alumina) obtained by baking at 1200 degreeC does not have a catalytic action from the result of the comparative example 4.
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