JP5645372B2 - Process for the preparation of heteropolyoxometalate compounds - Google Patents
Process for the preparation of heteropolyoxometalate compounds Download PDFInfo
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- JP5645372B2 JP5645372B2 JP2009141034A JP2009141034A JP5645372B2 JP 5645372 B2 JP5645372 B2 JP 5645372B2 JP 2009141034 A JP2009141034 A JP 2009141034A JP 2009141034 A JP2009141034 A JP 2009141034A JP 5645372 B2 JP5645372 B2 JP 5645372B2
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- 150000001875 compounds Chemical class 0.000 title description 61
- 238000002360 preparation method Methods 0.000 title description 7
- 238000000034 method Methods 0.000 title description 5
- 239000013078 crystal Substances 0.000 claims description 54
- -1 alkylammonium cations Chemical class 0.000 claims description 46
- 239000003054 catalyst Substances 0.000 claims description 35
- 150000001450 anions Chemical class 0.000 claims description 27
- 150000001768 cations Chemical class 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229910052792 caesium Inorganic materials 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 9
- 125000004429 atom Chemical group 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 238000006735 epoxidation reaction Methods 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 239000013460 polyoxometalate Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
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- 238000002441 X-ray diffraction Methods 0.000 description 10
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- 238000009826 distribution Methods 0.000 description 9
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- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 5
- 229940006165 cesium cation Drugs 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
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- 229910052783 alkali metal Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- NJWSNNWLBMSXQR-UHFFFAOYSA-N 2-hexyloxirane Chemical compound CCCCCCC1CO1 NJWSNNWLBMSXQR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
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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
Description
本発明は、ミクロ細孔構造を有する四価のα−ヘテロポリオキソメタレートアニオン及び少なくとも１個以上の一価のカチオンからなる新規な結晶体に関するものである。 The present invention relates to a novel crystal body comprising a tetravalent α-heteropolyoxometalate anion having a micropore structure and at least one monovalent cation.
ヘテロポリオキソメタレート化合物は、その特異な構造から酸性質及び／又は酸化性質等を発現し、各種触媒や担体等として用いることができる（特許文献１〜３、非特許文献１〜５参照）。 The heteropolyoxometalate compound expresses acid properties and / or oxidation properties and the like from its unique structure, and can be used as various catalysts, supports and the like (see Patent Documents 1 to 3 and Non-Patent Documents 1 to 5).
固体触媒や担体として用いる場合には、比表面積が大きい方が単位重量あたりの活性が高くなるので、より高比表面積であることが望まれているが、例えばゼオライトのように規則的なミクロ細孔構造を有する化合物は、その細孔構造による立体規制による反応基質選択性や生成物構造選択性による特異な触媒性能を発揮することが知られており、各種のミクロ細孔構造を有するゼオライトが開発されている。 When used as a solid catalyst or a support, the larger the specific surface area, the higher the activity per unit weight. Therefore, a higher specific surface area is desired. It is known that a compound having a pore structure exhibits a unique catalytic performance due to reaction substrate selectivity due to steric restriction by the pore structure and product structure selectivity. Has been developed.
本発明の課題は、ミクロ細孔構造を有する四価のα−ヘテロポリオキソメタレートアニオン及び少なくとも１個以上の一価のカチオンからなる新規な結晶体を提供することを目的としている。 An object of the present invention is to provide a novel crystal body comprising a tetravalent α-heteropolyoxometalate anion having a micropore structure and at least one monovalent cation.
本発明者は、α−ヘテロポリオキソメタレート化合物（以下、α−ＰＯＭと称することがある）の各種塩について鋭意検討した結果、四価のα−ヘテロポリオキソメタレートアニオンと一価のカチオンからなる特定のミクロ細孔構造を有する新規な結晶体を見出し、該結晶体を含む触媒が特異な性能を有することを見出し、本発明の完成に至った。 As a result of intensive studies on various salts of an α-heteropolyoxometalate compound (hereinafter sometimes referred to as α-POM), the present inventor has a tetravalent α-heteropolyoxometalate anion and a monovalent cation. The inventors have found a novel crystal having a specific micropore structure, and found that a catalyst containing the crystal has a unique performance, thereby completing the present invention.
すなわち、前記課題を解決する手段として、下記結晶体及び触媒とその製造方法を発明した。 That is, as means for solving the above-mentioned problems, the inventors have invented the following crystal and catalyst and a production method thereof.
（１）ミクロ細孔構造を有する結晶体であって、四価のα−ヘテロポリオキソメタレートアニオン及び少なくとも１個以上の一価のカチオンからなることを特徴とする結晶体。 (1) A crystal having a micropore structure, comprising a tetravalent α-heteropolyoxometalate anion and at least one monovalent cation.
（２）前記α−ヘテロポリオキソメタレートアニオンのヘテロ原子（Ａ）がケイ素、リン、ゲルマニウムから選ばれる原子であり、かつポリ原子（Ｂ）がタングステン及びモリブデンから選ばれる原子を９以上含むことを特徴とする（１）記載の結晶体。 (2) The heteroatom (A) of the α-heteropolyoxometalate anion is an atom selected from silicon, phosphorus and germanium, and the polyatom (B) contains 9 or more atoms selected from tungsten and molybdenum. The crystalline substance according to (1), which is characterized.
（３）前記一価のカチオンの少なくとも１個が、セシウムカチオン及び又は四級アルキルアンモニウムカチオンであることを特徴とする（１）又は（２）記載の結晶体。 (3) The crystal body according to (1) or (2), wherein at least one of the monovalent cations is a cesium cation and / or a quaternary alkyl ammonium cation.
（４）（１）〜（３）記載の結晶体を含む触媒。 (4) A catalyst containing the crystal according to (1) to (3).
（５）前記α−ヘテロポリオキソメタレートアニオンの酸又は水溶性塩と水溶性のセシウム化合物とを、アルコール化合物を含む媒体中で反応させることを特徴とする（１）〜（３）記載の結晶体の製造方法。 (5) The crystal according to (1) to (3), wherein the acid or water-soluble salt of the α-heteropolyoxometalate anion and a water-soluble cesium compound are reacted in a medium containing an alcohol compound. Body manufacturing method.
（６）前記α−ヘテロポリオキソメタレートアニオンの酸又は水溶性塩と水溶性のセシウム化合物とを、水媒体中でα−ヘテロポリオキソメタレートアニオンの酸又は水溶性塩の濃度を０．１Ｍ以下とし、かつ、室温で反応させることを特徴とする請求項１〜３記載の結晶体の製造方法
（７）前記α−ヘテロポリオキソメタレートアニオンの酸又は水溶性塩と四級アルキルアンモニウム化合物とを、ニトリル化合物を含む媒体中で反応させることを特徴とする（１）〜（３）記載の結晶体の製造方法。
(6) The acid or water-soluble salt of the α-heteropolyoxometalate anion and the water-soluble cesium compound, and the concentration of the acid or water-soluble salt of the α-heteropolyoxometalate anion in an aqueous medium is 0.1 M or less. And a reaction method at room temperature. (7) The acid or water-soluble salt of the α-heteropolyoxometalate anion and a quaternary alkylammonium compound. The method for producing a crystal as described in (1) to (3), wherein the reaction is carried out in a medium containing a nitrile compound.
（８）前記結晶体をエステル系化合物を含む媒体中に分散させる工程を含むことを特徴とする（４）記載の触媒の製造方法。 (8) The method for producing a catalyst according to (4), comprising a step of dispersing the crystal in a medium containing an ester compound.
本発明の四価のα−ヘテロポリオキソメタレートアニオンと少なくとも１個以上の一価のカチオンからなる新規な特定のミクロ細孔を有する結晶体は、高比表面積を有するため、触媒もしくはその担体として使用する場合、単位触媒重量あたりの触媒活性が高く、その特異な構造による特異な反応性が期待されると同時に、ミクロ孔の特性を生かした分離膜などの材料にも応用が期待される。 Since the crystal having a novel specific micropore composed of the tetravalent α-heteropolyoxometalate anion and at least one monovalent cation of the present invention has a high specific surface area, it can be used as a catalyst or its support. When used, it has a high catalytic activity per unit catalyst weight, and is expected to have a unique reactivity due to its unique structure. At the same time, it is expected to be applied to materials such as separation membranes that take advantage of the characteristics of micropores.
本発明に用いられる四価のα−ヘテロポリオキソメタレートアニオン（以下、α−ＰＯＭアニオンと称することがある）とは、式（１）［α−ＡＢ１２Ｏ４０］４−（式中、Ａはケイ素、リン、ゲルマニウムから選ばれるヘテロ原子をあらわし、Ｂはポリ原子をあらわし、Ｏは酸素をあらわす）であらわされる化合物である。該ポリ原子は、タングステン及びモリブデンから選ばれる原子を９以上含む。具体的には、［α−ＳｉＷ１２Ｏ４０］４−、［α−ＳｉＭｏ１２Ｏ４０］４−、［α−ＧｅＷ１２Ｏ４０］４−、［α−ＳｉＭｏ１２Ｏ４０］４−、［α−ＰＶＷ１１Ｏ４０］４−、［α−ＰＶＭｏ１１Ｏ４０］４−等が挙げられる。 The tetravalent α-heteropolyoxometalate anion (hereinafter sometimes referred to as α-POM anion) used in the present invention is a compound represented by the formula (1) [α-AB 12 O 40 ] 4− (wherein A Represents a heteroatom selected from silicon, phosphorus, and germanium, B represents a polyatom, and O represents oxygen. The poly atom contains 9 or more atoms selected from tungsten and molybdenum. Specifically, [α-SiW 12 O 40 ] 4− , [α-SiMo 12 O 40 ] 4− , [α-GeW 12 O 40 ] 4− , [α-SiMo 12 O 40 ] 4− , [ α-PVW 11 O 40 ] 4− , [α-PVMo 11 O 40 ] 4− and the like.
本発明に用いられる少なくとも１個以上の一価のカチオンは、カチオンであれば特に限定されないが、４個全てがプロトンではない。少なくとも１個以上の一価のカチオンは、プロトン、セシウムカチオン及び四級アルキルアンモニウムカチオンが挙げられ、セシウムカチオン又は四級アルキルアンモニウムカチオンから選ばれるいずれか一種を１個以上有することが好ましく、セシウムカチオン又は四級アルキルアンモニウムカチオンを２個以上有することがより好ましく、セシウムカチオン又は四級アルキルアンモニウムカチオンを３個以上有することが更に好ましい。また、一価のカチオンが四級アルキルアンモニウムカチオンである場合には、４個全てが該カチオンであることが最も好ましい。 The at least one monovalent cation used in the present invention is not particularly limited as long as it is a cation, but all four are not protons. The at least one monovalent cation includes a proton, a cesium cation, and a quaternary alkyl ammonium cation, and preferably has at least one selected from a cesium cation or a quaternary alkyl ammonium cation, Or it is more preferable to have two or more quaternary alkyl ammonium cations, and it is still more preferable to have three or more cesium cations or quaternary alkyl ammonium cations. When the monovalent cation is a quaternary alkylammonium cation, it is most preferable that all four are cations.
前記四級アルキルアンモニウムカチオンの４個のアルキル基は各々異なっても又は全て同じでも良く、全て同じアルキル基であることがより好ましい。前記アルキル基は、炭素数が４〜１２の直鎖及び／又は分岐を有するアルキル基が好ましく、炭素数が４〜１２の直鎖のアルキル基がより好ましく、炭素数が４〜８の直鎖のアルキル基が更に好ましく、炭素数が４のテトラ−ｎ−ブチルアンモニウムカチオンが最も好ましい。 The four alkyl groups of the quaternary alkylammonium cation may be different or all the same, and more preferably all are the same alkyl group. The alkyl group is preferably a straight chain and / or branched alkyl group having 4 to 12 carbon atoms, more preferably a straight chain alkyl group having 4 to 12 carbon atoms, and a straight chain having 4 to 8 carbon atoms. Are more preferable, and tetra-n-butylammonium cation having 4 carbon atoms is most preferable.
本発明に用いられるミクロ細孔構造を有するα−ＰＯＭアニオン及び少なくとも１個以上の一価のカチオンからなる結晶体を含む触媒とは、前記α−ＰＯＭアニオンと前記一価のカチオンを少なくとも１個以上含む結晶体のみからなる触媒若しくは、該結晶体とそれ以外の触媒成分が含まれている触媒をいう。前記結晶体とそれ以外の触媒成分が含まれている触媒とは、前記結晶体とそれ以外の触媒成分とが化学的にあるいは物理的に固定されている触媒だけでなく、前記結晶体とそれ以外に触媒成分とが固定されていない触媒、例えば、液相反応において固体成分である前記結晶体と溶解している触媒成分とに分離している形態をも含むものである。また、前記結晶体以外の触媒成分とは、触媒活性を有する成分だけでなく、助触媒成分、担体成分のいずれでも良く、複数の成分を含んでいてもよい。 The catalyst containing a crystal composed of an α-POM anion having a microporous structure and at least one monovalent cation used in the present invention is at least one of the α-POM anion and the monovalent cation. The catalyst which consists only of the crystal | crystallization which contains the above, or the catalyst containing this crystal | crystallization and other catalyst components is said. The catalyst containing the crystal and the other catalyst component is not only a catalyst in which the crystal and the other catalyst components are chemically or physically fixed, but also the crystal and the catalyst. In addition to the above, a catalyst in which the catalyst component is not fixed, for example, a form in which the crystal body which is a solid component and a dissolved catalyst component are separated in a liquid phase reaction is included. The catalyst component other than the crystal is not limited to a component having catalytic activity, and may be any of a promoter component and a carrier component, and may include a plurality of components.
本発明のミクロ細孔構造を有する結晶体の特性は、後に述べる調製方法により目的に応じて様々に変化させることができるが、そのＢＥＴ表面積は１〜２５０ｍ２／ｇであることが好ましい。より好ましくは、１．５〜２００ｍ２／ｇである。セシウムを一価のカチオンの一つとして使用した場合には、その結晶構造はｂｃｃ構造となり、Ｘ線回折（ＸＲＤ）等により確認することができる。 The characteristics of the crystal having a microporous structure of the present invention can be variously changed according to the purpose by a preparation method described later, but the BET surface area is preferably 1 to 250 m 2 / g. More preferably, it is 1.5-200 m < 2 > / g. When cesium is used as one of monovalent cations, the crystal structure becomes a bcc structure, which can be confirmed by X-ray diffraction (XRD) or the like.
前記α−ＰＯＭアニオンとセシウムカチオンとからなる結晶体は、α−ＰＯＭ化合物の酸又は水溶性塩と水溶性のセシウム化合物とを、アルコール化合物を含む媒体及び／又は水媒体中で反応させることにより得られる。前記α−ＰＯＭ化合物の水溶性塩として、α−ＰＯＭの部分酸塩やセシウム以外のアルカリ金属塩が例示され、該アルカリ金属としてはカリウム塩が例示される。水溶性のセシウム化合物としては、水酸化セシウム、硝酸セシウム、塩化セシウム、炭酸セシウム、炭酸水素セシウム、酢酸セシウム等が例示される。 The crystal comprising the α-POM anion and the cesium cation is obtained by reacting an acid or a water-soluble salt of an α-POM compound with a water-soluble cesium compound in a medium containing an alcohol compound and / or an aqueous medium. can get. Examples of the water-soluble salt of the α-POM compound include α-POM partial acid salts and alkali metal salts other than cesium, and examples of the alkali metal include potassium salts. Examples of the water-soluble cesium compound include cesium hydroxide, cesium nitrate, cesium chloride, cesium carbonate, cesium hydrogencarbonate, cesium acetate and the like.
アルコール化合物としては、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、ペンタノール、ヘキサノール、ヘプタノール、オクタノール、エチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、グリセリン等が例示され、特にメタノール、エタノール、イソプロパノール、エチレングリコールが好ましい。 Examples of the alcohol compound include methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, heptanol, octanol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, glycerin, and the like. Ethanol, isopropanol and ethylene glycol are preferred.
前記アルコール化合物を含む媒体には、前記アルコール化合物以外に、水、エーテル化合物、有機酸化合物、ニトリル化合物、エステル化合物等が含まれていてもよい。 The medium containing the alcohol compound may contain water, an ether compound, an organic acid compound, a nitrile compound, an ester compound and the like in addition to the alcohol compound.
前記α−ＰＯＭアニオンとセシウムカチオンとからなる結晶体は、また、前記α−ＰＯＭ化合物の酸又は水溶性塩と前記水溶性のセシウム化合物とを、水媒体中でα−ヘテロポリオキソメタレートアニオンの酸又は水溶性塩の濃度を０．１Ｍ以下とし、かつ、室温で反応させることによっても得られる。α−ヘテロポリオキソメタレートアニオンの濃度は、生成物の粒子性状や平均粒子径に影響を与え、０．１Ｍ以下が好ましく、０．０５Ｍ以下がより好ましく、０．０３Ｍ以下が更に好ましい。 The crystal body composed of the α-POM anion and the cesium cation also contains an acid or a water-soluble salt of the α-POM compound and the water-soluble cesium compound in an aqueous medium with an α-heteropolyoxometalate anion. It can also be obtained by making the concentration of the acid or water-soluble salt 0.1M or less and reacting at room temperature. The concentration of the α-heteropolyoxometalate anion affects the particle properties and average particle size of the product, is preferably 0.1M or less, more preferably 0.05M or less, and even more preferably 0.03M or less.
該条件により、生成物の平均粒子径を２５０〜３０００ｎｍとすることができる。より好ましくは、４００〜２８００ｎｍであり、更に好ましくは、５００〜２５００ｎｍである。また、前記水溶性のセシウム化合物の加え方も生成物の粒子性状や平均粒子径に影響を与え、一般に前記水溶性のセシウム化合物を時間をかけて加えることにより、平均粒子径を小さく、また粒子径分布の標準偏差を小さくすることができる。 According to the conditions, the average particle size of the product can be 250 to 3000 nm. More preferably, it is 400-2800 nm, More preferably, it is 500-2500 nm. In addition, the method of adding the water-soluble cesium compound also affects the particle properties and average particle size of the product. Generally, by adding the water-soluble cesium compound over time, the average particle size is reduced, and the particles The standard deviation of the diameter distribution can be reduced.
前記α−ＰＯＭアニオンと四級アルキルアンモニウムカチオンとからなる結晶体は、α−ＰＯＭ化合物の酸又は水溶性塩と四級アルキルアンモニウム化合物とを、ニトリル化合物を含む媒体中で反応させることにより得られる。前記α−ＰＯＭ化合物の水溶性塩として、α−ＰＯＭの部分酸塩やセシウム以外のアルカリ金属塩が例示され、該アルカリ金属としてはカリウム塩が例示される。 The crystal comprising the α-POM anion and the quaternary alkyl ammonium cation can be obtained by reacting the acid or water-soluble salt of the α-POM compound with a quaternary alkyl ammonium compound in a medium containing a nitrile compound. . Examples of the water-soluble salt of the α-POM compound include α-POM partial acid salts and alkali metal salts other than cesium, and examples of the alkali metal include potassium salts.
前記四級アルキルアンモニウム化合物とは、前記四級アルキルアンモニウムカチオンを含む化合物であり、該カチオンの水酸化物やハロゲン塩であり、臭化テトラ−ｎ−ブチルアンモニウムが例示される。 The quaternary alkylammonium compound is a compound containing the quaternary alkylammonium cation, and is a hydroxide or a halogen salt of the cation, and examples thereof include tetra-n-butylammonium bromide.
前記ニトリル化合物としては、アセトニトリル、プロピオニトリル、アクリロニトリル、メタクリロニトリル、ベンゾニトリル等が例示され、特にアセトニトリルが好ましい。 Examples of the nitrile compound include acetonitrile, propionitrile, acrylonitrile, methacrylonitrile, benzonitrile and the like, and acetonitrile is particularly preferable.
前記結晶体調製時の反応温度は、前記媒体が凝固若しくは沸騰する温度でなければ特に制限は無いが、通常、０℃から１００℃が好ましく、１０℃から９０℃がより好ましく、１５℃から８０℃が更に好ましい。 The reaction temperature at the time of preparing the crystal body is not particularly limited as long as the medium is not solidified or boiled, but usually 0 ° C to 100 ° C is preferable, 10 ° C to 90 ° C is more preferable, and 15 ° C to 80 ° C. More preferred is ° C.
前記いずれかの方法で調製された結晶体は、エステル系化合物を含む媒体中に分散させることにより、エステル系溶媒が細孔内に入り込んで細孔径を広げるとともに表面積を大きくすることができる。 When the crystal prepared by any of the above methods is dispersed in a medium containing an ester compound, the ester solvent can enter the pores to widen the pore diameter and increase the surface area.
例えば触媒若しくは担体として使用する場合には、その性能が大幅に向上することができる。前記結晶体であればいずれも表面積を大きくすることができるが、中でも一価のカチオンが四級アルキルアンモニウムであるα−ＰＯＭ化合物の結晶体が好ましい。該エステル系化合物は、エステル基を有する化合物であればよく、蟻酸メチル、酢酸メチル、酢酸エチル、プロピオン酸メチル、プロピオン酸メチル、アクリル酸メチル、メタクリル酸メチル等が例示される。 For example, when used as a catalyst or a support, its performance can be greatly improved. Any of the above-mentioned crystals can increase the surface area, but among them, an α-POM compound crystal in which the monovalent cation is quaternary alkyl ammonium is preferable. The ester compound may be any compound having an ester group, and examples include methyl formate, methyl acetate, ethyl acetate, methyl propionate, methyl propionate, methyl acrylate, and methyl methacrylate.
本発明の結晶体を含む触媒を製造する方法に特に制限は無いが、前記結晶体をエステル系化合物を含む媒体中に分散させてから用いるのが好ましい。その後、必要に応じ乾燥させ、前記結晶体以外の触媒成分を分散させた溶媒に添加することで前記結晶体を含む触媒が得られる。 Although there is no restriction | limiting in particular in the method to manufacture the catalyst containing the crystal body of this invention, It is preferable to use, after disperse | distributing the said crystal body in the medium containing an ester type compound. Then, the catalyst containing the said crystal body is obtained by drying as needed and adding to the solvent in which catalyst components other than the said crystal body were disperse | distributed.
前記結晶体を含む触媒は、過酸化水素や酸素等を酸化剤とするオレフィン化合物のエポキシ化反応に好適に用いることができ、該オレフィン化合物は、炭素数２〜１０の直鎖及び／又は分岐鎖を有するオレフィン化合物が好ましく、炭素数２〜１０の直鎖のオレフィン化合物がより好ましい。 The catalyst containing the crystal can be suitably used for an epoxidation reaction of an olefin compound using hydrogen peroxide, oxygen, or the like as an oxidizing agent, and the olefin compound is a linear and / or branched chain having 2 to 10 carbon atoms. An olefin compound having a chain is preferable, and a linear olefin compound having 2 to 10 carbon atoms is more preferable.
前記エポキシ化反応においては、前記結晶体以外にリン、バナジウム、タングステンを必須成分とする触媒成分を用いるのが好ましく、式（２）Ｍｘ［γ−Ｈ２ＰＶ２Ｗ１０Ｏ４０］（式中、Ｍはカチオン成分を表し、ｘはｘ＝４÷Ｍの価数を満足する１〜４の数値をあらわし、Ｈは水素をあらわし、Ｐはリンをあらわし、Ｖはバナジウムをあらわし、Ｗはタングステンをあらわし、Ｏは酸素をあらわす）であらわされるγ−ヘテロポリオキソメタレート化合物が好ましく、Ｍが臭化テトラ−ｎ−ブチルアンモニウム（以下ＴＢＡと称することがある）がより好ましい。 In the epoxidation reaction, it is preferable to use a catalyst component containing phosphorus, vanadium, and tungsten as essential components in addition to the crystal, and the formula (2) Mx [γ-H 2 PV 2 W 10 O 40 ] (wherein , M represents a cation component, x represents a numerical value of 1 to 4 satisfying the valence of x = 4 ÷ M, H represents hydrogen, P represents phosphorus, V represents vanadium, and W represents tungsten. Γ-heteropolyoxometalate compound represented by the following formula: O represents oxygen), and M is more preferably tetra-n-butylammonium bromide (hereinafter sometimes referred to as TBA).
以下に実施例を挙げて、本発明をさらに詳細に説明するが、本発明はこれらにより何ら限定されるものではない。なお、「％」は「モル％」を意味し、「ＴＢＡ」は「テトラ−ｎ−ブチルアンモニウム」を意味するものとする。
Ｋ８［α−ＳｉＷ１２Ｏ４０］・１７Ｈ２Ｏ、Ｃｓ５［γ−ＰＶ２Ｗ１０Ｏ４０］６Ｈ２Ｏは、以下の文献を参考に調製した。
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. “%” Means “mol%” and “TBA” means “tetra-n-butylammonium”.
K 8 [α-SiW 12 O 40] · 17H 2 O, Cs 5 [γ-PV 2 W 10 O 40] 6H 2 O were prepared following literature references.
Ａ．Ｔｅｚｅ、Ｇ．Ｈｅｒｖｅ、「インオーガニック シンセシーズ（Ｉｎｏｒｇａｎｉｃ Ｓｙｎｔｈｅｓｅｓ）」（米国）、１９９０年、第２７０巻、ｐ．８５。 A. Tze, G.M. Herve, “Inorganic Syntheses” (USA), 1990, Vol. 270, p. 85.
（実施例１）（ＴＢＡ）４［α−ＳｉＷ１２Ｏ４０］・ａＨ２Ｏ（ａは０以上の正数）の合成方法
日本無機化学工業（株）より購入したＨ４［α−ＳｉＷ１２Ｏ４０］・２４Ｈ２Ｏ（１５ｇ）を水（１５０ｍＬ）に溶かし、不溶物を濾過して取り除いた。ここに臭化テトラ−ｎ−ブチルアンモニウム（１０ｇ）を加え、得られた白色沈殿を濾過により回収した。この沈殿をアセトニトリル（２５０ｍＬ）に溶かし、氷浴で冷却して再結晶した。結晶を濾過により回収し、風乾することにより、目的化合物である（ＴＢＡ）４［α−ＳｉＷ１２Ｏ４０］・ａＨ２Ｏ（１５ｇ）を得た。
(Example 1) Synthesis method of (TBA) 4 [α-SiW 12 O 40 ] .aH 2 O (a is a positive number of 0 or more) H 4 [α-SiW 12 purchased from Japan Inorganic Chemical Industry Co., Ltd. O 40 ] · 24H 2 O (15 g) was dissolved in water (150 mL), and the insoluble material was removed by filtration. To this was added tetra-n-butylammonium bromide (10 g), and the resulting white precipitate was collected by filtration. This precipitate was dissolved in acetonitrile (250 mL), recrystallized by cooling in an ice bath. The crystals were collected by filtration and air-dried to obtain the target compound (TBA) 4 [α-SiW 12 O 40 ] · aH 2 O (15 g).
（実施例２）（ＴＢＡ）４［α−ＳｉＷ１２Ｏ４０］・ａＨ２Ｏ（ａは０以上の正数）の合成方法
Ｋ８［α−ＳｉＷ１２Ｏ４０］・１７Ｈ２Ｏ（５ｇ）を１Ｍ ＣＨ３ＣＯＯＨ／ＣＨ３ＣＯＯＮａ溶液（１００ｍＬ）に溶解させ、ここに臭化テトラ−ｎ−ブチルアンモニウム（５ｇ）を加えた。得られた固体を濾過し、熱アセトニトリル（１００ｍＬ）に溶かして室温まで放冷した。この溶液を６℃で２４時間放置した後、得られた結晶を濾過により回収し、風乾することにより、目的化合物である（ＴＢＡ）４［α−ＳｉＷ１２Ｏ４０］・ａＨ２Ｏ（４ｇ）を得た。この化合物を３０℃で３時間真空排気した後、ＢＥＴ表面積を測定（ＳＨＩＭＡＤＺＵ社製 ｍｉｃｒｏｍｅｔｒｉｃｓ ＡＳＡＰ２０１０使用）した所、１．６ｍ２／ｇであった。また、この化合物についての吸着等温線を測定した結果を図１に示した。（ａ）は窒素、（ｂ）は水、（ｃ）は酢酸エチル、（ｄ）はアセトニトリルに対する吸着等温線である。
Example 2 Synthesis Method of (TBA) 4 [α-SiW 12 O 40 ] · aH 2 O (a is a Positive Number of 0 or More) K 8 [α-SiW 12 O 40 ] · 17H 2 O (5 g) was dissolved in 1M CH 3 COOH / CH 3 COONa solution (100 mL), was added here tetra -n- butylammonium the (5 g). The resulting solid was filtered, dissolved in hot acetonitrile (100 mL) and allowed to cool to room temperature. The solution was allowed to stand at 6 ° C. for 24 hours, and the obtained crystals were collected by filtration and air-dried to obtain the target compound (TBA) 4 [α-SiW 12 O 40 ] .aH 2 O (4 g). Got. This compound was evacuated at 30 ° C. for 3 hours, and then the BET surface area was measured (using micrometrics ASAP2010 manufactured by SHIMADZU), which was 1.6 m 2 / g. Moreover, the result of having measured the adsorption isotherm about this compound was shown in FIG. (A) is nitrogen, (b) is water, (c) is ethyl acetate, and (d) is an adsorption isotherm for acetonitrile.
（実施例３）ＣｓｂＨ４−ｂ［α−ＳｉＷ１２Ｏ４０］・ｃＨ２Ｏ（０＜ｂ＜４、ｃは０以上の正数）の合成方法
日本無機化学工業（株）より購入したＨ４［α−ＳｉＷ１２Ｏ４０］・２４Ｈ２Ｏ（０．３ｇ）を２００℃で真空排気処理した。この化合物をエチレングリコール／水＝１／１溶液（２ｍＬ）に溶解させ、ここに酢酸セシウム（０．１ｇ）を溶かしたエチレングリコール／水＝１／１溶液（４ｍＬ）を１滴ずつ５分間かけて攪拌しながら滴下した。得られた沈殿を濾過により回収し、風乾することにより、目的化合物であるＣｓｂＨ４−ｂ［α−ＳｉＷ１２Ｏ４０］・ｃＨ２Ｏを定量的に得た。この化合物を３０℃で３時間真空排気した後、ＢＥＴ表面積を測定（ＳＨＩＭＡＤＺＵ社製 ｍｉｃｒｏｍｅｔｒｉｃｓ ＡＳＡＰ２０１０使用）した所、１８４ｍ２／ｇであり、［α−ＳｉＷ１２Ｏ４０］をアニオン部位に持つヘテロポリオキソメタレート化合物としては最高表面積であることが明らかとなった。また、この化合物についての窒素吸着等温線を測定した結果を図２に示した。
(Example 3) Cs b H 4-b [α-SiW 12 O 40] · cH 2 O (0 <b <4, c is 0 or a positive number) purchased from Synthetic method Nippon Inorganic Color & Chemical Industry Co., The H 4 [α-SiW 12 O 40 ] .24H 2 O (0.3 g) was evacuated at 200 ° C. This compound was dissolved in an ethylene glycol / water = 1/1 solution (2 mL), and an ethylene glycol / water = 1/1 solution (4 mL) in which cesium acetate (0.1 g) was dissolved was dropped for 5 minutes. And added dropwise with stirring. The resulting precipitate was collected by filtration and air-dried to quantitatively obtain Cs b H 4-b [α -SiW 12 O 40] · cH 2 O target compound. After the compound was 3 hours evacuated at 30 ° C., the BET surface area measurement (SHIMADZU Corp. Micrometrics ASAP2010 used) was place a 184m 2 / g, heteropolyoxometallates with the anionic sites of the [α-SiW 12 O 40] It became clear that it was the highest surface area as a metalate compound. Moreover, the result of having measured the nitrogen adsorption isotherm about this compound was shown in FIG.
（実施例４）（ＴＢＡ）３［γ−Ｈ２ＰＶ２Ｗ１０Ｏ４０］／（ＴＢＡ）４［α−ＳｉＷ１２Ｏ４０］の合成方法
実施例２で得られた（ＴＢＡ）４［α−ＳｉＷ１２Ｏ４０］・ａＨ２Ｏ（１．５ｇ）を酢酸エチル（３０ｍＬ）に加えて４時間攪拌し、デカンテーションで溶媒を除いた後に真空で乾燥した。この化合物についてＢＥＴ表面積を測定（ＳＨＩＭＡＤＺＵ社製 ｍｉｃｒｏｍｅｔｒｉｃｓ ＡＳＡＰ２０１０使用）した所、４．７ｍ２／ｇであった。
(Example 4) Synthesis method of (TBA) 3 [γ-H 2 PV 2 W 10 O 40 ] / (TBA) 4 [α-SiW 12 O 40 ] (TBA) 4 [α obtained in Example 2 -SiW 12 O 40 ] · aH 2 O (1.5 g) was added to ethyl acetate (30 mL), and the mixture was stirred for 4 hours. After removing the solvent by decantation, the mixture was dried in vacuum. It was 4.7 m < 2 > / g when the BET surface area was measured about this compound (micrometrics ASAP2010 made by SHIMADZU).
（実施例５）
（触媒調製）
０．０１Ｍ ＮａＶＯ３水溶液（１２０ｍＬ）に３Ｍ ＨＣｌ水溶液を加えてｐＨを２に調節し、続いてＣｓ５［γ−ＰＶ２Ｗ１０Ｏ４０］６Ｈ２Ｏ（４ｇ）を加えて溶解させた。濁りを濾過して取り除き、臭化テトラ−ｎ−ブチルアンモニウム（２ｇ）を加えたところ、黄色沈殿が生成した。この沈殿をガラスフィルター上に取り出し、水（４００ｍＬ）で洗浄し、真空下で１時間乾燥した。粗生成物収量は５ｇであった。この粗生成物（１５０ｍｇ）をアセトン（１５ｍＬ）に溶かし、メンブレンフィルターで濾過してスクリュー瓶に入れた後、ジエチルエーテル雰囲気下で３日間静置した。黄色柱状結晶が生成し、結晶を回収・風乾した。（ＴＢＡ）４［γ−ＨＰＶ２Ｗ１０Ｏ４０］・Ｈ２Ｏを８０ｍｇ得た（Ｃｓ塩からの収率６０％）。５１Ｖ−ＮＭＲ分析結果（アセトニトリル）： −５８１ｐｐｍ。次に、得られた（ＴＢＡ）４［γ−ＨＰＶ２Ｗ１０Ｏ４０］・Ｈ２Ｏ（１４ｍｇ）をアセトニトリル（２ｍＬ）に溶かした。７０％ＨＣｌＯ４をアセトニトリルで希釈して０．２Ｍにした溶液（２０μＬ）を加え、ジエチルエーテル（２０ｍＬ）を加えた。この操作により、Ｖ間を結合する酸素（μ−オキソ）がプロトン化され、（ＴＢＡ）３［γ−Ｈ２ＰＶ２Ｗ１０Ｏ４０］となる。遠心分離により懸濁した固体を沈降させ、デカンテーションにより無色透明の上澄み液を除いた。ジエチルエーテル（２０ｍＬ）で固体を洗浄し、ジクロロエタン（１ｍＬ）を加えて固体を溶解させた後、この溶液を実施例４の酢酸エチル処理して得た（ＴＢＡ）４［α−ＳｉＷ１２Ｏ４０］・ａＨ２Ｏ（１ｇ）に対し激しく攪拌しながら滴下し、真空乾燥することにより、目的化合物である（ＴＢＡ）３［γ−Ｈ２ＰＶ２Ｗ１０Ｏ４０］／（ＴＢＡ）４［α−ＳｉＷ１２Ｏ４０］を定量的に得た。
(Example 5)
(Catalyst preparation)
The pH was adjusted to 2 by adding 3 M HCl aqueous solution to 0.01 M NaVO 3 aqueous solution (120 mL), and then Cs 5 [γ-PV 2 W 10 O 40 ] 6H 2 O (4 g) was added and dissolved. Turbidity was removed by filtration and tetra-n-butylammonium bromide (2 g) was added, resulting in the formation of a yellow precipitate. The precipitate was taken out on a glass filter, washed with water (400 mL), and dried under vacuum for 1 hour. The crude product yield was 5 g. This crude product (150 mg) was dissolved in acetone (15 mL), filtered through a membrane filter, put into a screw bottle, and allowed to stand in a diethyl ether atmosphere for 3 days. Yellow columnar crystals were formed, and the crystals were collected and air-dried. 80 mg of (TBA) 4 [γ-HPV 2 W 10 O 40 ] · H 2 O was obtained (yield from Cs salt 60%). 51 V-NMR analysis result (acetonitrile): −581 ppm. Next, the obtained (TBA) 4 [γ-HPV 2 W 10 O 40 ] · H 2 O (14 mg) was dissolved in acetonitrile (2 mL). A solution (20 μL) of 70% HClO 4 diluted with acetonitrile to 0.2 M was added, followed by diethyl ether (20 mL). By this operation, oxygen (μ-oxo) bonding between V is protonated to become (TBA) 3 [γ-H 2 PV 2 W 10 O 40 ]. The suspended solid was settled by centrifugation, and the colorless and transparent supernatant was removed by decantation. The solid was washed with diethyl ether (20 mL), dichloroethane (1 mL) was added to dissolve the solid, and this solution was obtained by treating with ethyl acetate in Example 4 (TBA) 4 [α-SiW 12 O 40 ] · AH 2 O (1 g) was added dropwise with vigorous stirring and vacuum dried to obtain the target compound (TBA) 3 [γ-H 2 PV 2 W 10 O 40 ] / (TBA) 4 [α -SiW 12 O 40] was obtained quantitatively.
（触媒反応）
（ＴＢＡ）３［γ−Ｈ２ＰＶ２Ｗ１０Ｏ４０］／（ＴＢＡ）４［α−ＳｉＷ１２Ｏ４０］（（ＴＢＡ）３［γ−Ｈ２ＰＶ２Ｗ１０Ｏ４０］：４μｍｏｌ分を使用）を試験管に採り、ここに酢酸エチル（３ｍＬ）、５０％過酸化水素水溶液（０．５ｍｍｏｌ）、１−オクテン（０．５ｍｍｏｌ）を加えて、３２℃で２４時間攪拌した。分析はガスクロマトグラフィーにより行い、目的化合物である１−オクテンオキシドの収率は８７％（過酸化水素基準）であった。
(Catalytic reaction)
(TBA) 3 [γ-H 2 PV 2 W 10 O 40 ] / (TBA) 4 [α-SiW 12 O 40 ] ((TBA) 3 [γ-H 2 PV 2 W 10 O 40 ]: 4 μmol Used) was put in a test tube, and ethyl acetate (3 mL), 50% aqueous hydrogen peroxide solution (0.5 mmol) and 1-octene (0.5 mmol) were added thereto, and the mixture was stirred at 32 ° C. for 24 hours. The analysis was performed by gas chromatography, and the yield of the target compound, 1-octene oxide, was 87% (based on hydrogen peroxide).
（比較例１）
実施例５で合成した（ＴＢＡ）３［γ−Ｈ２ＰＶ２Ｗ１０Ｏ４０］・Ｈ２Ｏ（４μｍｏｌ）のみを触媒として使用した以外は、実施例５と同様に反応を行った。分析はガスクロマトグラフィーにより行い、目的化合物である１−オクテンオキシドの収率は３１％（過酸化水素基準）であった。
(Comparative Example 1)
The reaction was conducted in the same manner as in Example 5 except that only (TBA) 3 [γ-H 2 PV 2 W 10 O 40 ] · H 2 O (4 μmol) synthesized in Example 5 was used as a catalyst. The analysis was performed by gas chromatography, and the yield of the target compound, 1-octene oxide, was 31% (based on hydrogen peroxide).
（実施例６）Ｃｓ３．３６Ｈ０．６４［α−ＳｉＷ１２Ｏ４０］・１１．５Ｈ２Ｏの合成方法
日本無機化学工業（株）より購入したＨ４［α−ＳｉＷ１２Ｏ４０］・２４Ｈ２Ｏ（０．３ｇ）を２００℃で真空排気処理した。この化合物をエタノール／水＝１／１溶液（４ｍＬ）に溶解させ、ここに酢酸セシウム（０．１ｇ）を溶かしたエタノール／水＝１／１溶液（４ｍＬ）を１滴ずつ５分間かけて攪拌しながら滴下した。１時間後、得られた沈殿を濾過により回収し、風乾することにより、目的化合物であるＣｓ３．３６Ｈ０．６４［α−ＳｉＷ１２Ｏ４０］・１１．５Ｈ２Ｏを９４％の収率で得た（Ｌｏｔ１２４）。この化合物を３０℃で３時間真空排気した後、ＢＥＴ表面積を測定（ＳＨＩＭＡＤＺＵ社製 ｍｉｃｒｏｍｅｔｒｉｃｓ ＡＳＡＰ２０１０使用）した所、１４８ｍ２／ｇであった。また、この化合物についての窒素吸着等温線を測定した結果を図３、ＸＲＤを測定（理学電機社製 Ｍｕｌｔｉｆｌｅｘ使用）した結果を図４、ＳＥＭを測定（日立製作所社製 Ｓ−４７００使用 ２００００倍）した結果を図５に示した。
(Example 6) Cs 3.36 H 0.64 [α-SiW 12 O 40 ] · 11.5 H 2 O Synthesis Method H 4 [α-SiW 12 O 40 ] purchased from Nippon Inorganic Chemical Industry Co., Ltd. · 24H evacuated treated with 2 O a (0.3g) 200 ℃. This compound was dissolved in an ethanol / water = 1/1 solution (4 mL), and an ethanol / water = 1/1 solution (4 mL) in which cesium acetate (0.1 g) was dissolved was stirred dropwise over 5 minutes. While dripping. After 1 hour, the obtained precipitate was collected by filtration and air-dried, whereby 94% yield of Cs 3.36 H 0.64 [α-SiW 12 O 40 ] · 11.5H 2 O as the target compound was obtained. (Lot124). This compound was evacuated at 30 ° C. for 3 hours, and then the BET surface area was measured (using micrometrics ASAP2010 manufactured by SHIMADZU). As a result, it was 148 m 2 / g. Moreover, the result of measuring the nitrogen adsorption isotherm for this compound is shown in FIG. 3, the result of measuring XRD (using Multiflex manufactured by Rigaku Corporation) is shown in FIG. The results are shown in FIG.
（実施例７）Ｃｓ３．４１Ｈ０．５９［α−ＳｉＷ１２Ｏ４０］・３．３ＥｔＯＨの合成方法
日本無機化学工業（株）より購入したＨ４［α−ＳｉＷ１２Ｏ４０］・２４Ｈ２Ｏ（０．３ｇ）を２００℃で真空排気処理した。この化合物をエタノール（４ｍＬ）に溶解させ、ここに酢酸セシウム（０．１ｇ）を溶かしたエタノール（４ｍＬ）を１滴ずつ５分間かけて攪拌しながら滴下した。１時間後、得られた沈殿を濾過により回収し、風乾することにより、目的化合物であるＣｓ３．４１Ｈ０．５９［α−ＳｉＷ１２Ｏ４０］・３．３ＥｔＯＨを８５％の収率で得た。この化合物を３０℃で３時間真空排気した後、ＢＥＴ表面積を測定（ＳＨＩＭＡＤＺＵ社製 ｍｉｃｒｏｍｅｔｒｉｃｓ ＡＳＡＰ２０１０使用）した所、１５４ｍ２／ｇであった。
(Example 7) Cs 3.41 H 0.59 [α-SiW 12 O 40 ] · 3.3 EtOH Synthesis Method H 4 [α-SiW 12 O 40 ] · 24 H purchased from Nippon Inorganic Chemical Industry Co., Ltd. 2 O (0.3 g) was evacuated at 200 ° C. This compound was dissolved in ethanol (4 mL), and ethanol (4 mL) in which cesium acetate (0.1 g) was dissolved was added dropwise with stirring over 5 minutes. After 1 hour, the obtained precipitate was collected by filtration and air-dried to obtain the target compound Cs 3.41 H 0.59 [α-SiW 12 O 40 ] · 3.3 EtOH in a yield of 85%. Obtained. The compound was evacuated at 30 ° C. for 3 hours, and then the BET surface area was measured (using micrometrics ASAP2010 manufactured by SHIMADZU). As a result, it was 154 m 2 / g.
（実施例８）Ｃｓ３．３６Ｈ０．６４［α−ＳｉＷ１２Ｏ４０］・９．３Ｈ２Ｏの合成方法
日本無機化学工業（株）より購入したＨ４［α−ＳｉＷ１２Ｏ４０］・２４Ｈ２Ｏ（０．３ｇ）を２００℃で真空排気処理した。この化合物を水（４ｍＬ）に溶解させ、ここに酢酸セシウム（０．１ｇ）を溶かした水（４ｍＬ）を１滴ずつ５分間かけて攪拌しながら滴下した。室温で１時間攪拌後、得られた沈殿を濾過により回収し、風乾することにより、目的化合物であるＣｓ３．３６Ｈ０．６４［α−ＳｉＷ１２Ｏ４０］・９．３Ｈ２Ｏを定量的に得た（Ｌｏｔ１２１）。この化合物を３０℃で３時間真空排気した後、ＢＥＴ表面積を測定した所、１４９ｍ２／ｇであった。この化合物についての窒素吸着等温線を測定した結果を図６、ＸＲＤを測定（理学電機社製 Ｍｕｌｔｉｆｌｅｘ使用）した結果を図７、ＳＥＭを測定（日立製作所社製 Ｓ−４７００使用 ２００００倍）した結果を図８−（ａ）、粒径分布を図９−（ａ）に示した。
(Example 8) Cs 3.36 H 0.64 [α-SiW 12 O 40 ] · 9.3 H 2 O Synthesis Method H 4 [α-SiW 12 O 40 ] purchased from Japan Inorganic Chemical Industry Co., Ltd. · 24H evacuated treated with 2 O a (0.3g) 200 ℃. This compound was dissolved in water (4 mL), and water (4 mL) in which cesium acetate (0.1 g) was dissolved was added dropwise with stirring over 5 minutes. After stirring at room temperature for 1 hour, the resulting precipitate was collected by filtration and air-dried to quantitatively determine the target compound, Cs 3.36 H 0.64 [α-SiW 12 O 40 ] · 9.3H 2 O. (Lot 121). The compound was evacuated at 30 ° C. for 3 hours, and the BET surface area was measured to find 149 m 2 / g. FIG. 6 shows the result of measuring the nitrogen adsorption isotherm for this compound, FIG. 7 shows the result of measuring XRD (using Multiflex manufactured by Rigaku Corporation), and the result of measuring SEM (using S-4700 manufactured by Hitachi, Ltd. 20000 times). 8- (a) and the particle size distribution are shown in FIG. 9- (a).
（実施例９）Ｃｓ３．３８Ｈ０．６２［α−ＳｉＷ１２Ｏ４０］・８．０Ｈ２Ｏの合成方法
日本無機化学工業（株）より購入したＨ４［α−ＳｉＷ１２Ｏ４０］・２４Ｈ２Ｏ（０．３ｇ）を２００℃で真空排気処理した。この化合物を水（４０ｍＬ）に溶解させ、ここに酢酸セシウム（０．１ｇ）を溶かした水（４０ｍＬ）を一気に加えた。室温で１時間攪拌後、得られた沈殿を濾過により回収し、風乾することにより、目的化合物であるＣｓ３．３８Ｈ０．６２［α−ＳｉＷ１２Ｏ４０］・８．０Ｈ２Ｏを定量的に得た（Ｌｏｔ１２９）。この化合物を３０℃で３時間真空排気した後、ＢＥＴ表面積を測定した所、８０．６ｍ２／ｇであった。この化合物についての窒素吸着等温線を測定した結果を図６、ＸＲＤを測定した結果を図７、ＳＥＭを測定した結果を図８−（ｂ）、粒径分布を図９−（ｂ）に示した。
(Example 9) Cs 3.38 H 0.62 [α-SiW 12 O 40 ] · 8.0 H 2 O Synthesis Method H 4 [α-SiW 12 O 40 ] purchased from Nippon Inorganic Chemical Industry Co., Ltd. · 24H evacuated treated with 2 O a (0.3g) 200 ℃. This compound was dissolved in water (40 mL), and water (40 mL) in which cesium acetate (0.1 g) was dissolved was added all at once. After stirring at room temperature for 1 hour, the resulting precipitate was collected by filtration and air-dried to quantitatively determine the target compound, Cs 3.38 H 0.62 [α-SiW 12 O 40 ] · 8.0H 2 O. (Lot129). This compound was evacuated at 30 ° C. for 3 hours, and then the BET surface area was measured. As a result, it was 80.6 m 2 / g. The result of measuring the nitrogen adsorption isotherm for this compound is shown in FIG. 6, the result of measuring XRD is shown in FIG. 7, the result of measuring SEM is shown in FIG. 8- (b), and the particle size distribution is shown in FIG. 9- (b). It was.
（実施例１０）Ｃｓ３．３４Ｈ０．６６［α−ＳｉＷ１２Ｏ４０］・１０．３Ｈ２Ｏの合成方法
日本無機化学工業（株）より購入したＨ４［α−ＳｉＷ１２Ｏ４０］・２４Ｈ２Ｏ（０．３ｇ）を２００℃で真空排気処理した。この化合物を水（１ｍＬ）に溶解させ、ここに酢酸セシウム（０．１ｇ）を溶かした水（１ｍＬ）を一気に加えた。室温で１時間攪拌後、得られた沈殿を濾過により回収し、風乾することにより、目的化合物であるＣｓ３．３４Ｈ０．６６［α−ＳｉＷ１２Ｏ４０］・１０．３Ｈ２Ｏを定量的に得た（Ｌｏｔ１３０）。この化合物を３０℃で３時間真空排気した後、ＢＥＴ表面積を測定した所、１７８．８ｍ２／ｇであった。この化合物についての窒素吸着等温線を測定した結果を図６、ＸＲＤを測定した結果を図７、ＳＥＭを測定した結果を図８−（ｃ）、粒径分布を図９−（ｃ）に示した。
(Example 10) Cs 3.34 H 0.66 [α-SiW 12 O 40 ] · 10.3 H 2 O synthesis method H 4 [α-SiW 12 O 40 ] purchased from Nippon Inorganic Chemical Industry Co., Ltd. · 24H evacuated treated with 2 O a (0.3g) 200 ℃. This compound was dissolved in water (1 mL), and water (1 mL) in which cesium acetate (0.1 g) was dissolved was added all at once. After stirring at room temperature for 1 hour, the resulting precipitate was collected by filtration and air-dried to quantitatively determine the target compound, Cs 3.34 H 0.66 [α-SiW 12 O 40 ] · 10.3H 2 O. (Lot130). This compound was evacuated at 30 ° C. for 3 hours, and the BET surface area was measured. As a result, it was 178.8 m 2 / g. The result of measuring the nitrogen adsorption isotherm for this compound is shown in FIG. 6, the result of measuring XRD is shown in FIG. 7, the result of measuring SEM is shown in FIG. 8- (c), and the particle size distribution is shown in FIG. 9- (c). It was.
（実施例１１）Ｃｓ３．４Ｈ０．６［α−ＳｉＷ１２Ｏ４０］・７．１Ｈ２Ｏの合成方法
日本無機化学工業（株）より購入したＨ４［α−ＳｉＷ１２Ｏ４０］・２４Ｈ２Ｏ（０．３ｇ）を２００℃で真空排気処理した。この化合物を水（１００ｍＬ）に溶解させ、ここに酢酸セシウム（０．１ｇ）を溶かした水（１００ｍＬ）を一気に加えた。室温で２４時間攪拌後、得られた沈殿を濾過により回収し、風乾することにより、目的化合物であるＣｓ３．４Ｈ０．６［α−ＳｉＷ１２Ｏ４０］・７．１Ｈ２Ｏを定量的に得た（Ｌｏｔ１３２）。この化合物を３０℃で３時間真空排気した後、ＢＥＴ表面積を測定した所、１６．８ｍ２／ｇであった。この化合物についての窒素吸着等温線を測定した結果を図６、ＸＲＤを測定した結果を図７、ＳＥＭを測定した結果を図８−（ｄ）、粒径分布を図９−（ｄ）に示した。
(Example 11) Cs 3.4 H 0.6 [α-SiW 12 O 40 ] · 7.1 H 2 O synthesis method H 4 [α-SiW 12 O 40 ] purchased from Nippon Inorganic Chemical Industry Co., Ltd. · 24H evacuated treated with 2 O a (0.3g) 200 ℃. This compound was dissolved in water (100 mL), and water (100 mL) in which cesium acetate (0.1 g) was dissolved was added all at once. After stirring at room temperature for 24 hours, the resulting precipitate was collected by filtration and air-dried to quantitatively determine the target compound, Cs 3.4 H 0.6 [α-SiW 12 O 40 ] · 7.1H 2 O. (Lot132). This compound was evacuated at 30 ° C. for 3 hours, and the BET surface area was measured. As a result, it was 16.8 m 2 / g. The result of measuring the nitrogen adsorption isotherm for this compound is shown in FIG. 6, the result of measuring XRD is shown in FIG. 7, the result of measuring SEM is shown in FIG. 8- (d), and the particle size distribution is shown in FIG. 9- (d). It was.
（実施例１２）Ｃｓ３．４Ｈ０．６［α−ＳｉＷ１２Ｏ４０］・７．７Ｈ２Ｏの合成方法
日本無機化学工業（株）より購入したＨ４［α−ＳｉＷ１２Ｏ４０］・２４Ｈ２Ｏ（０．３ｇ）を２００℃で真空排気処理した。この化合物を水（４０ｍＬ）に溶解させ、ここに酢酸セシウム（０．１ｇ）を溶かした水（４０ｍＬ）を７時間かけて攪拌しながら滴下した。室温で１時間攪拌後、得られた沈殿を濾過により回収し、風乾することにより、目的化合物であるＣｓ３．４Ｈ０．６［α−ＳｉＷ１２Ｏ４０］・７．７Ｈ２Ｏを定量的に得た（Ｌｏｔ１３５）。この化合物についての窒素吸着等温線を測定した結果を図１０、ＸＲＤを測定した結果を図１１、ＳＥＭを測定した結果と粒径分布を図１２に示した。
(Example 12) Cs 3.4 H 0.6 [α-SiW 12 O 40 ] · 7.7 H 2 O synthesis method H 4 [α-SiW 12 O 40 ] purchased from Nippon Inorganic Chemical Industry Co., Ltd. · 24H evacuated treated with 2 O a (0.3g) 200 ℃. This compound was dissolved in water (40 mL), and water (40 mL) in which cesium acetate (0.1 g) was dissolved was added dropwise over 7 hours with stirring. After stirring for 1 hour at room temperature, the resulting precipitate was collected by filtration and air-dried to quantitatively determine the target compound, Cs 3.4 H 0.6 [α-SiW 12 O 40 ] · 7.7H 2 O. Obtained (Lot135). The result of measuring the nitrogen adsorption isotherm for this compound is shown in FIG. 10, the result of measuring XRD is shown in FIG. 11, the result of measuring SEM and the particle size distribution are shown in FIG.
上述の実施例及び比較例から、次のように言えることが分かった。 From the above-mentioned Examples and Comparative Examples, it was found that the following can be said.
実施例１及び実施例２に示すように、ヘテロ原子（Ａ）としてケイ素、ポリ原子（Ｂ）として１２個のタングステン、一価のカチオンとしてテトラ−ｎ−ブチルアンモニウムを用いたヘテロポリオキソメタレート化合物は、窒素もしくは水よりも、酢酸エチルやアセトニトリルのような極性有機化合物を吸着することが分かった（図１）。これは、該へテロポリオキソメタレート化合物がチャネル構造を有するホストとして働き、その細孔内に極性有機化合物（ゲスト）を選択的に取り込むことができることに起因するものと考えられる。 As shown in Example 1 and Example 2, a heteropolyoxometalate compound using silicon as a heteroatom (A), 12 tungstens as a polyatom (B), and tetra-n-butylammonium as a monovalent cation Was found to adsorb polar organic compounds such as ethyl acetate and acetonitrile rather than nitrogen or water (FIG. 1). This is considered to be due to the fact that the heteropolyoxometalate compound acts as a host having a channel structure, and a polar organic compound (guest) can be selectively taken into the pores.
実施例３において、ヘテロ原子（Ａ）としてケイ素、ポリ原子（Ｂ）として１２個のタングステン、一価のカチオンとしてセシウムを用いたα−ＰＯＭ化合物は、アルコール化合物（エチレングリコール）を含む媒体中で調製することにより、その表面積が著しく増大することが示されており、該セシウム塩の窒素吸着等温線（図２）の低圧側の立ち上がりが大きいことからミクロ孔を有することが判明し、このミクロ孔が表面積の増大に寄与していると推測される。 In Example 3, an α-POM compound using silicon as a heteroatom (A), 12 tungstens as a polyatom (B), and cesium as a monovalent cation is obtained in a medium containing an alcohol compound (ethylene glycol). It has been shown that the surface area of the cesium salt increases remarkably when it is prepared, and the rise of the nitrogen adsorption isotherm of the cesium salt (FIG. 2) is large, so that it has micropores. It is presumed that the pores contribute to the increase in surface area.
実施例２と実施例４を比較すると、（ＴＢＡ）４［α−ＳｉＷ１２Ｏ４０］・ａＨ２Ｏを酢酸エチルで処理することにより、ＢＥＴ表面積が１．６ｍ２／ｇから４．７ｍ２／ｇへ増加しており、一価のカチオンが四級アルキルアンモニウムであるα−ＰＯＭ化合物は、該処理によりＢＥＴ表面積が増加することが分かる。 When Example 2 and Example 4 are compared, by treating (TBA) 4 [α-SiW 12 O 40 ] · aH 2 O with ethyl acetate, the BET surface area is 1.6 m 2 / g to 4.7 m 2. The α-POM compound in which the monovalent cation is a quaternary alkyl ammonium is found to increase the BET surface area by the treatment.
実施例５と比較例１と比較すると、１−オクテンの過酸化水素によるエポキシ化反応を、本発明の結晶体を担体に用いた触媒を用いるとことにより触媒性能が飛躍的に向上することが示されている。 Compared with Example 5 and Comparative Example 1, the epoxidation reaction of 1-octene with hydrogen peroxide can dramatically improve the catalyst performance by using a catalyst using the crystal of the present invention as a support. It is shown.
実施例６〜７では、アルコール化合物としてエタノールも溶媒としてα−ＰＯＭ化合物の調製に使用できることが明らかとなり、特に５０％エタノール水溶液を使用した場合には、窒素吸着等温線は完全なＩ型となることが分かった。 In Examples 6 to 7, it is clear that ethanol as an alcohol compound can also be used as a solvent for the preparation of an α-POM compound, and particularly when a 50% ethanol aqueous solution is used, the nitrogen adsorption isotherm becomes a complete I type. I understood that.
実施例８〜１１では、調製時のα−ＰＯＭ化合物の濃度が低い（低濃度調製）ほど生成する結晶体のＢＥＴ表面積は小さくなり、調製した結晶体はミクロ細孔のみを有している。イオン濃度を低くしたり、溶媒粘度を高くして凝集速度を遅らせると、結晶子が配向しながら凝集し、結晶子間にミクロ細孔が選択的に形成されるものと推測される。結晶体ＣｓｂＨ４−ｂ［α−ＳｉＷ１２Ｏ４０］・ｃＨ２Ｏはｂｃｃ構造を有する結晶子からなり、結晶子が凝集した際の結晶子間に細孔が形成されるものと考えられる。一方、高濃度調製の場合には、結晶体のＢＥＴ表面積が大きく、ミクロ細孔だけでなくメソ細孔も有しており、また粒子径も小さく、その分布も狭いことが分かった。 In Examples 8 to 11, the lower the concentration of the α-POM compound at the time of preparation (lower concentration preparation), the smaller the BET surface area of the produced crystal, and the prepared crystal has only micropores. If the ion concentration is lowered or the solvent viscosity is increased to slow the aggregation rate, it is presumed that the crystallites aggregate while being oriented, and micropores are selectively formed between the crystallites. The crystal Cs b H 4-b [α-SiW 12 O 40 ] · cH 2 O is composed of crystallites having a bcc structure, and it is considered that pores are formed between the crystallites when the crystallites aggregate. It is done. On the other hand, in the case of high concentration preparation, it was found that the BET surface area of the crystal was large, it had not only micropores but also mesopores, the particle size was small, and the distribution was narrow.
実施例１２では、セシウム溶液を７時間かけてゆっくり滴下することにより、セシウム溶液を短時間で加えた場合よりも表面積及び平均粒子径が小さくなることが分かった。溶液中の結晶子濃度を低く保ち、凝集体の核生成よりも凝集体の結晶成長が優先して起こるためと考えられる。 In Example 12, it was found that by slowly dropping the cesium solution over 7 hours, the surface area and average particle size were smaller than when the cesium solution was added in a short time. This is probably because the crystallite concentration in the solution is kept low, and the crystal growth of the aggregate takes precedence over the nucleation of the aggregate.
本発明のヘテロポリオキソメタレート化合物は、特定のミクロ細孔構造を有する四価のα−ヘテロポリオキソメタレートアニオン及び少なくとも１個以上の一価のカチオンからなる結晶体であり、従来よりも大きな表面積を有し、触媒もしくはその担体として使用する場合、単位触媒重量あたりの触媒活性が高く、その特異な構造による特異な反応性が期待されると同時に、ミクロ細孔内に取り込む化合物を選択することが可能で、その特性を生かした分離膜などの材料にも応用することが期待できる。 The heteropolyoxometalate compound of the present invention is a crystal body composed of a tetravalent α-heteropolyoxometalate anion having a specific micropore structure and at least one monovalent cation, and has a larger surface area than the conventional surface area. When a catalyst or its support is used, the catalyst activity per unit catalyst weight is high, and a specific reactivity due to its unique structure is expected. It can be applied to materials such as separation membranes that take advantage of these properties.
Claims (7)
前記α−ヘテロポリオキソメタレートアニオンの酸又は水溶性塩と水溶性のセシウム化合物とを、アルコール化合物を含む媒体中で反応させることを特徴とする結晶体の製造方法。 A crystal having a microporous structure, comprising a tetravalent α-heteropolyoxometalate anion and at least one monovalent cation and having a BET surface area of 1.5 to 200 m 2 / g Is a manufacturing method of
The α- and heteropolyoxometalate anion of the acid or water soluble salt and a water-soluble cesium compound, method for producing a sintered Akirakarada you comprises reacting in a medium comprising an alcohol compound.
前記α−ヘテロポリオキソメタレートアニオンの酸又は水溶性塩と四級アルキルアンモニウム化合物とを、ニトリル化合物を含む媒体中で反応させることを特徴とする結晶体の製造方法。 A crystal having a microporous structure, comprising a tetravalent α-heteropolyoxometalate anion and at least one monovalent cation and having a BET surface area of 1.5 to 200 m 2 / g Is a manufacturing method of
The α- hetero polyoxometalate the anion of the acid or water soluble salt and quaternary alkyl ammonium compounds, method for producing a sintered Akirakarada you comprises reacting in a medium containing a nitrile compound.
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