JP2010036140A - Catalyst and method for manufacturing the same - Google Patents
Catalyst and method for manufacturing the same Download PDFInfo
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- JP2010036140A JP2010036140A JP2008203850A JP2008203850A JP2010036140A JP 2010036140 A JP2010036140 A JP 2010036140A JP 2008203850 A JP2008203850 A JP 2008203850A JP 2008203850 A JP2008203850 A JP 2008203850A JP 2010036140 A JP2010036140 A JP 2010036140A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 123
- 238000000034 method Methods 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 143
- 239000002184 metal Substances 0.000 claims abstract description 142
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 131
- 239000010936 titanium Substances 0.000 claims abstract description 119
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 112
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000010419 fine particle Substances 0.000 claims abstract description 39
- 239000000725 suspension Substances 0.000 claims abstract description 10
- 230000001678 irradiating effect Effects 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 133
- 239000000377 silicon dioxide Substances 0.000 claims description 63
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 56
- 239000010931 gold Substances 0.000 claims description 37
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 29
- 229910052737 gold Inorganic materials 0.000 claims description 29
- 229910052697 platinum Inorganic materials 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 238000004438 BET method Methods 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 239000011859 microparticle Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 27
- 239000007788 liquid Substances 0.000 abstract 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 22
- 239000011148 porous material Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- -1 platinum group metals Chemical class 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 5
- 238000006664 bond formation reaction Methods 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000000833 X-ray absorption fine structure spectroscopy Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 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 1
- 238000001914 filtration Methods 0.000 description 1
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- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 125000005624 silicic acid group Chemical group 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
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- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Abstract
Description
本発明は、チタン含有ケイ酸塩多孔体を担体とする触媒の製造方法、並びにその方法によって得られた触媒に関する。 The present invention relates to a method for producing a catalyst using a titanium-containing porous silicate as a carrier, and a catalyst obtained by the method.
高活性触媒を調製するためには、触媒活性物質を微粒化し、単位質量当りの表面積を大きくすることが必要である。そこで、工業的には、比表面積の大きな担体に活性金属を担持する方法が多く用いられている。活性金属を担体に担持する方法としては、蒸発乾固法、平衡吸着法、ポアフィリング法といったいわゆる含浸法や、イオン交換法などが知られている。 In order to prepare a highly active catalyst, it is necessary to atomize the catalytically active substance and increase the surface area per unit mass. Therefore, industrially, many methods of supporting an active metal on a carrier having a large specific surface area are used. As a method for supporting an active metal on a carrier, a so-called impregnation method such as an evaporation to dryness method, an equilibrium adsorption method, and a pore filling method, an ion exchange method, and the like are known.
しかしながら、担体を金属含有溶液に浸漬した後に溶媒を蒸発させて活性金属を担体に担持せしめる蒸発乾固法は、活性金属の凝集が起こり易く、活性金属の分散性が比較的低くなり、触媒活性の向上に限界があった。また、金属含有溶液に担体を浸漬した後に過剰の溶液を濾過等により除去し、担体に吸着した活性金属のみを担持せしめる平衡吸着法は、蒸発乾固法と比較すると活性金属の分散度を高くすることが可能であるが、部分的に見ると活性金属が凝集した部分と比較的均一に分散した部分が存在してしまい、担体全体に亘って活性金属を均一に分散させることは困難であり、やはり触媒活性の向上に限界があった。さらに金属含有溶液を僅かずつ担体に加え、担体表面が均一に濡れ始めた状態で含浸を終了するポアフィリング法は、活性金属を比較的分散性よく担体上に担持させることができるが、活性金属の担持量が比較的低く、やはり触媒活性の向上に限界があった。また、担体に含まれる金属カチオンと担持しようとする金属カチオンとのイオン交換を利用して担体に活性金属を担持せしめるイオン交換法は、前記含浸法と比較して比較的高分散状態で活性金属を担体に担持せしめることができる傾向にあるが、イオン交換が平衡反応である場合に交換率を上げて活性金属の担持量を増やすためには、イオン交換操作を繰返し行う必要があり、前記含浸法に比べて触媒の調製が煩雑であるという問題があった。 However, the evaporation to dryness method in which the active metal is supported on the support by evaporating the solvent after immersing the support in the metal-containing solution is likely to cause aggregation of the active metal, resulting in relatively low dispersibility of the active metal, and catalytic activity. There was a limit to improvement. In addition, the equilibrium adsorption method, in which the excess solution is removed by filtration after immersing the carrier in a metal-containing solution and only the active metal adsorbed on the carrier is supported, has a higher degree of dispersion of the active metal than the evaporation to dryness method. However, it is difficult to disperse the active metal uniformly over the entire carrier because there are a part where the active metal is aggregated and a part where the active metal is relatively uniformly dispersed. After all, there was a limit in improving the catalytic activity. Further, the pore filling method in which the metal-containing solution is added to the carrier little by little and the impregnation is completed in a state where the surface of the carrier begins to be uniformly wet can support the active metal on the carrier with relatively high dispersibility. The amount of supported was relatively low, and there was a limit to the improvement in catalytic activity. Further, an ion exchange method in which an active metal is supported on a carrier by utilizing ion exchange between a metal cation contained in the carrier and a metal cation to be supported is an active metal in a relatively high dispersion state compared to the impregnation method. However, when the ion exchange is an equilibrium reaction, in order to increase the exchange rate and increase the amount of active metal supported, it is necessary to repeat the ion exchange operation. There was a problem that the preparation of the catalyst was complicated compared to the method.
また、従来から種々の触媒が開発されており、例えば、特開平１１−７６８２０号公報（特許文献１）には、チタン含有ケイ酸塩多孔体に金微粒子を固定化した炭化水素部分酸化用触媒が開示されている。また、特表２００７−５３０６７７号公報（特許文献２）には、担体となるチタノシリケートをマイクロ波加熱により製造し、これに金を担持した炭化水素ヒドロ酸化用触媒が開示されている。更には、特開２００７−３０７４３６号公報（特許文献３）にも、含浸法により担体に金属を担持させて触媒前駆体を形成した後、この触媒前駆体を空気中でマイクロ波により加熱し、更に還元して得られるフィッシャー・トロプシュ合成用触媒が開示されている。しかしながら、特許文献１〜３に記載の触媒は、いわゆる含浸法により製造されたものであり、やはり触媒活性の向上には限界があった。 Various catalysts have been developed in the past. For example, JP-A-11-76820 (Patent Document 1) discloses a hydrocarbon partial oxidation catalyst in which gold fine particles are immobilized on a titanium-containing silicate porous body. Is disclosed. JP-T-2007-530677 (Patent Document 2) discloses a hydrocarbon hydrooxidation catalyst in which titanosilicate serving as a carrier is produced by microwave heating and gold is supported thereon. Furthermore, Japanese Patent Application Laid-Open No. 2007-307436 (Patent Document 3) also discloses that a catalyst precursor is formed by supporting a metal on a support by an impregnation method, and then the catalyst precursor is heated by microwaves in air, Further, a Fischer-Tropsch synthesis catalyst obtained by reduction is disclosed. However, the catalysts described in Patent Documents 1 to 3 are produced by a so-called impregnation method, and there is a limit to improving the catalytic activity.
これに対して本発明者らは、国際公開第ＷＯ２００７／０３７０２６号パンフレット（特許文献４）において、活性金属を担持する方法として、金属塩を溶解した溶液中にチタン含有ケイ酸塩多孔体を懸濁させ、この懸濁液に２００ｎｍ〜４５０ｎｍの波長成分を含む紫外線を照射することにより、前記多孔体の表面上に金属微粒子を析出させる方法を提案した。この方法によれば、活性金属を平均直径１０ｎｍ以下の超微粒子として担体表面に高分散化させることができ、これを触媒として用いることにより、前記含浸法による触媒に比較して触媒活性を充分に向上させることが可能であることを見出した。しかしながら、前記方法では触媒調製に１０時間以上かかるという難点があった。 On the other hand, in the pamphlet of International Publication No. WO2007 / 037026 (Patent Document 4), the present inventors suspended a titanium-containing silicate porous body in a solution in which a metal salt is dissolved as a method for supporting an active metal. A method was proposed in which metal fine particles are deposited on the surface of the porous body by turbidity and irradiating the suspension with ultraviolet rays containing a wavelength component of 200 nm to 450 nm. According to this method, the active metal can be highly dispersed on the surface of the support as ultrafine particles having an average diameter of 10 nm or less. By using this as a catalyst, the catalytic activity is sufficiently higher than that of the catalyst by the impregnation method. It was found that it can be improved. However, the above method has a drawback that it takes 10 hours or more to prepare the catalyst.
一方、マイクロ波を利用して貴金属を担体に担持させた触媒として、Ｇｕｉｗａｎｇ Ｚｈａｏらは、メソポーラスカーボンやメソポーラスカーボンナノファイバー上に白金ナノ粒子を高分散させた触媒を提案している〔Ｇｕｉｗａｎｇ Ｚｈａｏら、Ｊ．Ｐｈｙｓ．Ｃｈｅｍ．Ｃ、２００８年、第１１２巻、１０２８〜１０３３頁（非特許文献１）〕。しかしながら、この触媒はエチレングリコール中でマイクロ波を照射して調製されており、水溶液中で調製した例は少なく、これまで、水溶液中でマイクロ波を照射してシングルサイト触媒に金属を担持させる方法についての報告例はなかった。 Meanwhile, as a catalyst in which a noble metal is supported on a carrier using microwaves, Guiwang Zhao et al. Have proposed a catalyst in which platinum nanoparticles are highly dispersed on mesoporous carbon or mesoporous carbon nanofiber [Guiwang Zhao et al. , J .; Phys. Chem. C, 2008, 112, 1028-1033 (Non-patent Document 1)]. However, this catalyst is prepared by irradiating microwaves in ethylene glycol, and there are few examples prepared in an aqueous solution. So far, a method of irradiating microwaves in an aqueous solution and supporting a metal on a single site catalyst. There was no report about.
本発明は、上記従来技術の有する課題に鑑みてなされたものであり、比較的簡易な操作で、紫外線を利用した方法よりも短時間且つ省エネルギーでチタン含有ケイ酸塩多孔体の表面上に高分散状態で金属微粒子を担持させることができ、触媒活性を充分に向上させることが可能な触媒の製造方法、並びにそれによって得られる触媒活性が充分に向上した触媒を提供することを目的とする。 The present invention has been made in view of the above-described problems of the prior art, and is relatively easy to operate on the surface of a titanium-containing porous silicate in a shorter time and with less energy than a method using ultraviolet rays. It is an object of the present invention to provide a method for producing a catalyst capable of supporting metal fine particles in a dispersed state and capable of sufficiently improving the catalyst activity, and a catalyst having a sufficiently improved catalyst activity.
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、チタン含有ケイ酸塩多孔体を金属含有溶液に懸濁させた状態で、紫外線よりも発生エネルギーの少ないマイクロ波を照射することによって短時間でチタン含有ケイ酸塩多孔体の表面上に高分散状態で金属微粒子を担持させることができ、触媒活性を充分に向上させることが可能であることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors irradiate microwaves with less generated energy than ultraviolet rays in a state where the porous titanium-containing silicate is suspended in a metal-containing solution. It is found that the metal fine particles can be supported in a highly dispersed state on the surface of the porous titanium-containing silicate in a short time, and the catalytic activity can be sufficiently improved, thereby completing the present invention. It came to.
すなわち、本発明の触媒の製造方法は、金属塩を溶解した溶液中にチタン含有ケイ酸塩多孔体を懸濁させ、該懸濁液にマイクロ波を照射することにより前記多孔体の表面上に金属微粒子を析出させることを特徴とする方法である。 That is, the catalyst production method of the present invention suspends a titanium-containing silicate porous body in a solution in which a metal salt is dissolved, and irradiates the suspension with microwaves on the surface of the porous body. It is a method characterized by precipitating metal fine particles.
このような製造方法においては、温度が２０〜１２０℃の前記懸濁液に、前記チタン含有ケイ酸塩多孔体１ｇ当たり１０〜１００００Ｗのマイクロ波を１分間〜３時間照射することが好ましい。 In such a production method, it is preferable to irradiate the suspension having a temperature of 20 to 120 ° C. with microwaves of 10 to 10,000 W per 1 g of the titanium-containing porous silicate for 1 minute to 3 hours.
また、本発明の触媒は、前記本発明の製造方法により得られたものであり、チタン含有ケイ酸塩多孔体と、前記多孔体の表面上に析出された金属微粒子とからなることを特徴とするものである。このような触媒のうち、ＣＯパルス吸着法により測定した金属分散度が２０％以上であるものが好ましい。 The catalyst of the present invention is obtained by the production method of the present invention, and is characterized by comprising a titanium-containing silicate porous body and metal fine particles deposited on the surface of the porous body. To do. Among such catalysts, those having a metal dispersion measured by CO pulse adsorption method of 20% or more are preferable.
本発明に用いられる金属としては、金、銀、白金族金属及び鉄族金属からなる群から選択される少なくとも１種の金属が好ましく、中でも白金及び／又は金がより好ましい。 The metal used in the present invention is preferably at least one metal selected from the group consisting of gold, silver, platinum group metals and iron group metals, and more preferably platinum and / or gold.
本発明に用いられるチタン含有ケイ酸塩多孔体としては、ケイ素原子の一部がチタン原子で置換されているシリカ骨格を有するものが好ましく、また、チタン含有メソポーラスシリカ又はチタン含有ゼオライトも好ましく、ＢＥＴ法により測定された比表面積が１００ｍ２／ｇ以上のチタン含有メソポーラスシリカがより好ましい。 As the titanium-containing silicate porous material used in the present invention, those having a silica skeleton in which a part of silicon atoms are substituted with titanium atoms are preferable, titanium-containing mesoporous silica or titanium-containing zeolite is also preferable, and BET Titanium-containing mesoporous silica having a specific surface area measured by the method of 100 m 2 / g or more is more preferable.
なお、上記本発明の方法によって、チタン含有ケイ酸塩多孔体の表面上に高分散状態で金属微粒子が担持され、得られる触媒の触媒活性が充分に向上するようになる理由は必ずしも定かでないが、本発明者らは以下のように推察する。すなわち、金属塩を溶解し溶液中にチタン含有ケイ酸塩多孔体を懸濁させ、この懸濁液にマイクロ波を照射すると、溶液中の金属カチオンが、マイクロ波照射により励起活性化された前記多孔体表面のチタン原子と反応してＴｉ−金属結合を形成するため、チタン含有ケイ酸塩多孔体の表面のチタン原子が存在する部分に金属が選択的に析出する。つまり、本発明の方法では、前記多孔体表面のチタンサイトのみに選択的に金属を結合させることができるため、チタン原子が表面上に均一に分散しているチタン含有ケイ酸塩多孔体を用いれば、触媒活性成分である金属を前記多孔体表面上に均一に分散させることが可能となる。 In addition, although the metal fine particles are supported in a highly dispersed state on the surface of the titanium-containing silicate porous body by the method of the present invention, the reason why the catalytic activity of the resulting catalyst is sufficiently improved is not necessarily clear. The present inventors infer as follows. That is, by dissolving the metal salt and suspending the titanium-containing silicate porous body in the solution and irradiating the suspension with microwaves, the metal cations in the solution are excited and activated by microwave irradiation. Since it reacts with the titanium atoms on the surface of the porous body to form Ti-metal bonds, the metal is selectively deposited on the surface of the titanium-containing silicate porous body where the titanium atoms are present. That is, in the method of the present invention, a metal can be selectively bonded only to the titanium sites on the surface of the porous body, and therefore a titanium-containing silicate porous body in which titanium atoms are uniformly dispersed on the surface is used. For example, the metal that is a catalytically active component can be uniformly dispersed on the surface of the porous body.
また、前記多孔体表面のチタン原子は、マイクロ波によって励起活性化されやすく、短時間でより多くの活性サイトが形成され、多くの金属カチオンがチタン原子と反応する。その結果、金属微粒子の担持量が増大し、触媒活性がより向上するものと推察される。 In addition, the titanium atoms on the surface of the porous body are easily excited and activated by microwaves, so that more active sites are formed in a short time, and many metal cations react with the titanium atoms. As a result, it is presumed that the amount of metal fine particles supported increases and the catalytic activity is further improved.
さらに、析出した金属はチタン原子をアンカーとして前記多孔体表面上に充分に固定化され、同時に金属−金属同士の結合形成が抑制されるため、凝集が防止された金属微粒子が高分散状態でチタン含有ケイ酸塩多孔体の表面上に担持された状態になる。そのため、本発明のマイクロ波照射により調製した触媒においては、従来の含浸法により調製した担持触媒より、金属原子当りの活性が高くなり、反応場が効率よく形成され、触媒活性の充分な向上が達成されるようになると本発明者らは推察する。 Further, the precipitated metal is sufficiently immobilized on the surface of the porous body using titanium atoms as anchors, and at the same time, the formation of metal-metal bonds is suppressed. It will be in the state carry | supported on the surface of the containing silicate porous body. Therefore, in the catalyst prepared by microwave irradiation of the present invention, the activity per metal atom is higher than the supported catalyst prepared by the conventional impregnation method, the reaction field is efficiently formed, and the catalytic activity is sufficiently improved. The inventors speculate that this will be achieved.
本発明によれば、比較的簡易な操作で、紫外線を利用した方法よりも短時間且つ省エネルギーでチタン含有ケイ酸塩多孔体の表面上に高分散状態で金属微粒子を担持させることができ、触媒活性を充分に向上させることが可能な触媒を得ることが可能となる。 According to the present invention, the metal fine particles can be supported in a highly dispersed state on the surface of the porous titanium-containing silicate by a relatively simple operation and with a shorter time and energy saving than the method using ultraviolet rays. It becomes possible to obtain a catalyst capable of sufficiently improving the activity.
以下、本発明をその好適な実施形態に即して詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.
先ず、本発明の触媒製造方法について説明する。すなわち、本発明の触媒の製造方法は、金属塩を溶解した溶液中にチタン含有ケイ酸塩多孔体を懸濁させ、この懸濁液にマイクロ波を照射することにより前記多孔体の表面上に金属微粒子を析出させることを特徴とする方法である。 First, the method for producing a catalyst of the present invention will be described. That is, the catalyst production method of the present invention suspends a titanium-containing silicate porous body in a solution in which a metal salt is dissolved, and irradiates the suspension with microwaves on the surface of the porous body. It is a method characterized by precipitating metal fine particles.
本発明で用いるチタン含有ケイ酸塩多孔体の種類は、特に限定されるものではないが、ケイ素原子の一部がチタン原子で置換されているシリカ骨格を有する多孔体であることが好ましく、高い比表面積を有し、チタン原子が孤立してケイ酸骨格中に高分散しているものが特に好ましい。これにより、チタン含有ケイ酸塩多孔体の表面全体に亘って金属微粒子を高分散させることができ、触媒活性が充分に向上した触媒を得ることが可能となる。 The type of the titanium-containing silicate porous body used in the present invention is not particularly limited, but is preferably a porous body having a silica skeleton in which a part of silicon atoms are substituted with titanium atoms, and high Particularly preferred is one having a specific surface area and having titanium atoms isolated and highly dispersed in a silicate skeleton. Thereby, metal fine particles can be highly dispersed over the entire surface of the titanium-containing silicate porous body, and a catalyst with sufficiently improved catalytic activity can be obtained.
このようなチタン含有ケイ酸塩多孔体としては、例えば、ゼオライト（Ｘ、Ｙ型、ＺＳＭ−５、ＺＳＭ−４８など）系材料のアルミニウム原子及び／又はケイ素原子の一部がチタンで置き換わってチタンがゼオライト格子中に組み込まれたチタン含有ゼオライト、大きな細孔（メソポア）を有するメソポーラスシリカ（ＭＣＭ−４１、ＭＣＭ−４８、ＭＣＭ−５０など）の一部をチタン原子で置換したチタン含有メソポーラスシリカ、チタンとシリコンの複合酸化物であってミクロポーラスなチタノシリカライト（いわゆるＴＳ−１、ＴＳ−２）等が挙げられる。また、これらのチタン含有ケイ酸塩多孔体上に酸化チタンを微少量高分散担持させたものを用いることもできる。これらのうち、大きな比表面積を有し、チタン原子が孤立してケイ酸骨格中に高分散している、ケイ素原子の一部がチタン原子で置換されたメソポーラスシリカが好ましい。 As such a titanium-containing porous silicate, for example, a part of aluminum atoms and / or silicon atoms of a zeolite (X, Y type, ZSM-5, ZSM-48, etc.)-Based material is replaced with titanium. Titanium-containing zeolite in which is incorporated into the zeolite lattice, titanium-containing mesoporous silica in which a part of mesoporous silica (MCM-41, MCM-48, MCM-50, etc.) having large pores (mesopores) is substituted with titanium atoms, Examples thereof include titanium and silicon composite oxides and microporous titanosilicalite (so-called TS-1, TS-2). In addition, it is possible to use a titanium oxide silicate porous material in which a small amount of titanium oxide is supported in a highly dispersed manner. Of these, mesoporous silica having a large specific surface area, in which titanium atoms are isolated and highly dispersed in a silicic acid skeleton and in which some silicon atoms are substituted with titanium atoms is preferable.
本発明にかかるチタン含有ケイ酸塩多孔体におけるチタンの含有量は、ＴｉとＳｉの原子比率（Ｔｉ／Ｓｉと表わす）に換算して、Ｔｉ／Ｓｉ＝０．００１〜０．１の範囲内が好ましく、Ｔｉ／Ｓｉ＝０．００５〜０．０５の範囲内がより好ましい。チタンの含有量が前記下限よりも少ないと、単位表面積当たりのチタン原子が少なくなり、担持できる金属の量が減少して触媒活性が低下する傾向にある。一方、チタンの含有量が上記上限より多いと、全てのチタン原子がシリカ骨格に入らないため、多孔体の細孔内に酸化チタンの状態で存在するようになり、チタン原子の分散性が低下し、結果として金属微粒子の分散性が低下して触媒活性が低下する傾向になる。 The content of titanium in the porous titanium-containing silicate according to the present invention is within the range of Ti / Si = 0.001 to 0.1 in terms of the atomic ratio of Ti and Si (expressed as Ti / Si). Is preferable, and the range of Ti / Si = 0.005 to 0.05 is more preferable. When the content of titanium is less than the lower limit, the number of titanium atoms per unit surface area decreases, and the amount of metal that can be supported tends to decrease, leading to a decrease in catalytic activity. On the other hand, if the titanium content is higher than the above upper limit, all titanium atoms do not enter the silica skeleton, so that they are present in the state of titanium oxide in the pores of the porous body, and the dispersibility of the titanium atoms decreases. As a result, the dispersibility of the metal fine particles decreases, and the catalytic activity tends to decrease.
また、本発明にかかるチタン含有ケイ酸塩多孔体のうち、メソポーラスな材料については、ＢＥＴ法により測定された比表面積が１００ｍ２／ｇ以上のものがより好ましい。比表面積が前記下限未満では活性サイト数の減少を招く傾向にある。 Of the titanium-containing silicate porous bodies according to the present invention, the mesoporous material preferably has a specific surface area measured by the BET method of 100 m 2 / g or more. If the specific surface area is less than the lower limit, the number of active sites tends to decrease.
本発明にかかるチタン含有ケイ酸塩多孔体の形状は、特に限定されるものではなく、粉体状であっても、他の各種形状に成形したものであってもよい。また、本発明にかかるチタン含有ケイ酸塩多孔体は、予め形成された支持体に固定化した状態で用いることもできる。このような支持体としては、チタンを含まない金属酸化物や各種金属からなる材料を用いることができる。具体例としては、各種セラミックス（アルミナ、シリカ、マグネシア、コージエライト、酸化ジルコニウム等）、各種金属からなるハニカム状担体、ペレット状担体等が挙げられる。 The shape of the titanium-containing silicate porous body according to the present invention is not particularly limited, and may be a powder or may be formed into various other shapes. Moreover, the titanium containing silicate porous body concerning this invention can also be used in the state fixed to the support body formed previously. As such a support, a metal oxide not containing titanium or a material made of various metals can be used. Specific examples include various ceramics (alumina, silica, magnesia, cordierite, zirconium oxide, etc.), honeycomb-shaped carriers made of various metals, pellet-shaped carriers, and the like.
本発明で用いる金属塩としては、後述する溶媒に溶解し、優れた触媒作用を示す金属元素の塩であることが好ましい。このような触媒作用を示す金属元素のうち、環境浄化反応、エネルギー変換反応、選択的酸化反応等に高活性且つ高選択性を示す触媒材料として利用される機会が高いという観点から、金、銀、白金族金属（ルテニウム、ロジウム、パラジウム、白金、オスミウム及びイリジウム）及び鉄族金属（鉄、コバルト、ニッケル）からなる群から選択される１種又は２種以上の金属であることが好ましく、中でも白金及び／又は金が特に好ましい。従って、本発明においては、前記金属塩を１種単独で、又は２種類以上混合して用いることができる。 The metal salt used in the present invention is preferably a metal element salt which dissolves in a solvent described later and exhibits excellent catalytic action. Among the metal elements having such catalytic action, gold, silver are used from the viewpoint that they are highly utilized as catalyst materials having high activity and high selectivity in environmental purification reactions, energy conversion reactions, selective oxidation reactions, and the like. It is preferably one or more metals selected from the group consisting of platinum group metals (ruthenium, rhodium, palladium, platinum, osmium and iridium) and iron group metals (iron, cobalt, nickel). Platinum and / or gold are particularly preferred. Therefore, in this invention, the said metal salt can be used individually by 1 type or in mixture of 2 or more types.
また、本発明にかかる金属塩を構成する塩としては、硝酸塩等の鉱酸塩、酢酸塩等の有機酸塩、塩素化物等のハロゲン化物等を用いることができる。また、上記金属塩を溶解させる溶媒としては、水、水とアルコール（メタノール、エタノール等）との混合溶媒等が挙げられる。このように、本発明の触媒の製造方法においては、水または水を含む混合溶媒を用いることはできる。 Moreover, as a salt which comprises the metal salt concerning this invention, mineral acid salts, such as nitrate, organic acid salts, such as acetate, halides, such as chlorination, etc. can be used. Examples of the solvent for dissolving the metal salt include water, a mixed solvent of water and alcohol (methanol, ethanol, etc.), and the like. Thus, in the method for producing a catalyst of the present invention, water or a mixed solvent containing water can be used.
上記の金属塩を溶解した溶液の濃度は、特に制限されないが、０．００００１〜１ｍｏｌ／Ｌ程度であることが好ましく、０．０００１〜０．０２ｍｏｌ／Ｌ程度であることがより好ましい。また、前記溶液中に懸濁されるチタン含有ケイ酸塩多孔体の濃度も特に制限されないが、通常のマイクロ波発生装置を用いる場合、０．０１〜１００ｇ／Ｌ程度であることが好ましく、０．１〜５０ｇ／Ｌ程度であることがより好ましい。 Although the density | concentration of the solution which melt | dissolved said metal salt is not restrict | limited in particular, It is preferable that it is about 0.00001-1 mol / L, and it is more preferable that it is about 0.0001-0.02 mol / L. The concentration of the porous titanium-containing silicate suspended in the solution is not particularly limited, but is preferably about 0.01 to 100 g / L when an ordinary microwave generator is used. More preferably, it is about 1-50 g / L.
本発明においては、上記の金属塩を溶解した溶液中に上記のチタン含有ケイ酸塩多孔体を懸濁させ、この懸濁液にマイクロ波を照射することにより前記多孔体の表面上に金属微粒子を析出させることができる。マイクロ波は紫外線に比べて発生エネルギーが少ないため、本発明のようにマイクロ波を照射した場合には、紫外線を照射する場合に比べて省エネルギー化を図ることができる。また、マイクロ波照射の場合には、紫外線照射の場合に比べて短時間で金属微粒子を析出させることも可能となり、さらに、多く金属微粒子を担持することができ、触媒活性が充分に向上した触媒を得ることができる。 In the present invention, the titanium-containing silicate porous material is suspended in a solution in which the metal salt is dissolved, and the suspension is irradiated with microwaves to thereby form metal fine particles on the surface of the porous material. Can be deposited. Since microwaves generate less energy than ultraviolet rays, when microwaves are irradiated as in the present invention, energy saving can be achieved compared to irradiation with ultraviolet rays. In addition, in the case of microwave irradiation, it becomes possible to deposit metal fine particles in a shorter time than in the case of ultraviolet irradiation, and furthermore, a catalyst that can carry a large amount of metal fine particles and has sufficiently improved catalytic activity. Can be obtained.
本発明においては、特に制限されないが、触媒１ｇ当たり、１０〜１００００Ｗのマイクロ波を、照射することが好ましく、１００〜７０００Ｗのマイクロ波を照射することがより好ましい。マイクロ波の照射エネルギーが前記下限未満になると多孔体表面のチタン原子が充分に励起活性化されず、金属担持量が減少する傾向にある。他方、前記上限を超えてもＴｉ−金属結合形成速度の向上に対するマイクロ波照射エネルギーの効果は認められなくなる傾向にある。 Although it does not restrict | limit in this invention in particular, It is preferable to irradiate a 10-10000W microwave per 1g of catalyst, and it is more preferable to irradiate a 100-7000W microwave. When the microwave irradiation energy is less than the lower limit, titanium atoms on the surface of the porous body are not sufficiently excited and activated, and the metal loading tends to decrease. On the other hand, even if the upper limit is exceeded, the effect of microwave irradiation energy on the improvement of the Ti-metal bond formation rate tends not to be recognized.
また、マイクロ波の照射時間は、特に制限されないが、１分間〜３時間であることが好ましく、１〜３０分間であることがより好ましい。マイクロ波の照射時間が前記下限未満になると多孔体表面のチタン原子が充分に励起活性化されず、金属担持量が減少する傾向にある。他方、前記上限を超えてもＴｉ−金属結合形成速度の向上に対するマイクロ波照射時間の効果は認められなくなる傾向にある。 The microwave irradiation time is not particularly limited, but is preferably 1 minute to 3 hours, and more preferably 1 to 30 minutes. When the microwave irradiation time is less than the lower limit, titanium atoms on the surface of the porous body are not sufficiently excited and activated, and the amount of metal supported tends to decrease. On the other hand, even if the upper limit is exceeded, the effect of microwave irradiation time on the improvement of the Ti-metal bond formation rate tends not to be recognized.
また、マイクロ波を照射する際の溶液の温度としては、２０℃〜１２０℃の範囲が好ましく、２５〜１１０℃の範囲がより好ましい。かかる温度が上記下限温度より低い場合には、溶液中の金属イオンとチタン種との結合形成速度が遅くなり、触媒調製に要する時間が長くなる傾向にある。他方、溶液の温度を高くすることにより溶液中の金属イオンとチタン種との結合形成速度は速くなるが、上限温度を超える温度にしても結合形成速度向上に対する温度効果は認められなくなる傾向にある。 Moreover, as temperature of the solution at the time of irradiating a microwave, the range of 20 to 120 degreeC is preferable, and the range of 25 to 110 degreeC is more preferable. When such temperature is lower than the above lower limit temperature, the bond formation rate between the metal ion in the solution and the titanium species is slow, and the time required for catalyst preparation tends to be long. On the other hand, by increasing the temperature of the solution, the bond formation rate between the metal ions and the titanium species in the solution increases, but even if the temperature exceeds the upper limit temperature, the temperature effect on the bond formation rate tends not to be recognized. .
以上説明したマイクロ波照射析出法によりチタン含有ケイ酸塩多孔体の表面上に金属粒子を析出させた後、例えば、遠心分離により固形分を回収し、更に必要に応じて乾燥処理、焼成処理を施すことによって以下に説明する本発明の触媒が得られる。このような焼成処理は必ずしも必要でなく、その条件も特に限定されないが、空気雰囲気下１００℃〜８００℃で、０．５〜４８時間程度であることが好ましい。また、マイクロ波照射は、チタン含有ケイ酸塩多孔体の表面上に高分散して存在しているチタン種に作用し、金属前駆体（例えば、金属カチオン）との相互作用により金属粒子が還元され固定化されるため、水素還元処理は必ずしも必要ではなく、その条件も特に限定されないが、水素雰囲気下１００〜５００℃で、０．５〜２４時間程度であることが好ましい。 After the metal particles are deposited on the surface of the titanium-containing silicate porous body by the microwave irradiation precipitation method described above, for example, the solid content is recovered by centrifugation, and further, if necessary, a drying treatment and a firing treatment. By applying, the catalyst of the present invention described below is obtained. Such a baking treatment is not necessarily required, and the conditions are not particularly limited, but it is preferably 100 ° C. to 800 ° C. in an air atmosphere and about 0.5 to 48 hours. In addition, microwave irradiation acts on titanium species that are highly dispersed on the surface of the titanium-containing porous silicate, and metal particles are reduced by interaction with metal precursors (for example, metal cations). However, the hydrogen reduction treatment is not always necessary and the conditions are not particularly limited, but it is preferably 100 to 500 ° C. in a hydrogen atmosphere and about 0.5 to 24 hours.
上記本発明の方法により製造される本発明の触媒は、前記チタン含有ケイ酸塩多孔体と、前記多孔体の表面上に析出された金属微粒子とからなるものである。このような本発明の触媒は、金属微粒子が高分散状態でかつ多孔体表面上に担持されているため、従来の含浸法により調製した触媒より高い触媒活性を示すものである。また、本発明の触媒は、紫外線照射により調製したものより金属担持量が多い触媒であり、高い触媒活性を示すものである。 The catalyst of the present invention produced by the method of the present invention comprises the titanium-containing silicate porous body and metal fine particles deposited on the surface of the porous body. Such a catalyst of the present invention exhibits higher catalytic activity than a catalyst prepared by a conventional impregnation method because the metal fine particles are supported in a highly dispersed state on the surface of the porous body. Further, the catalyst of the present invention is a catalyst having a larger amount of metal supported than that prepared by ultraviolet irradiation, and exhibits high catalytic activity.
本発明の触媒における金属微粒子の担持量は、前記多孔体中に高分散状態で存在しているチタン種により制限されるが、０．００５〜５質量％程度であることが好ましく、０．０１〜３質量％程度であることがより好ましい。金属微粒子の担持量が前記下限未満になると触媒活性サイト数が少なくなり触媒活性が低下する傾向にあり、他方、前記上限を超えると金属種が凝集して粒子が大きくなりすぎ触媒活性が低下する傾向にある。なお、本発明において金属微粒子の担持量とは、触媒表面だけでなく、内部に担持されたものを含む値（トータル値）であり、ＩＣＰによる元素分析によって求めることができる。 The amount of the metal fine particles supported in the catalyst of the present invention is limited by the titanium species present in a highly dispersed state in the porous body, but is preferably about 0.005 to 5% by mass, More preferably, it is about ˜3 mass%. When the loading amount of the metal fine particles is less than the lower limit, the number of catalytically active sites tends to decrease and the catalytic activity tends to decrease. There is a tendency. In the present invention, the supported amount of the metal fine particles is a value (total value) including not only the catalyst surface but also the one supported inside, and can be determined by elemental analysis by ICP.
また、本発明の触媒における金属分散度は２０％以上であることが好ましい。金属分散度が前記下限未満になると触媒表面の活性サイト数が少なくなり触媒活性が低下する傾向にある。なお、「金属分散度」とは、触媒に担持された全金属原子数に対する触媒表面に露出している金属原子数の割合（露出金属原子数／全金属原子数［％］）を意味する。この金属分散度は、触媒を酸素雰囲気中、４００℃で１５分間保持し、次いで水素雰囲気中、４００℃で１５分間保持し、さらにヘリウム雰囲気中で５０℃に冷却した後、全自動触媒ガス吸着量測定装置（ＢＥＬ ＪＡＰＡＮ，ＩＮＣ社製「ＢＥＬ−ＭＥＴＡＬ−１」）を用いてＣＯパルス吸着法に従って前記露出金属原子数を測定し、この露出金属原子数と前記金属微粒子の担持量から計算される全金属原子数とから求めることができる。 Moreover, it is preferable that the metal dispersion degree in the catalyst of this invention is 20% or more. When the metal dispersity is less than the lower limit, the number of active sites on the catalyst surface decreases and the catalyst activity tends to decrease. “Metal dispersity” means the ratio of the number of metal atoms exposed on the catalyst surface to the total number of metal atoms carried on the catalyst (number of exposed metal atoms / total number of metal atoms [%]). This metal dispersibility is determined by maintaining the catalyst in an oxygen atmosphere at 400 ° C. for 15 minutes, then holding in a hydrogen atmosphere at 400 ° C. for 15 minutes, and further cooling to 50 ° C. in a helium atmosphere, and then fully automatic catalyst gas adsorption. The number of exposed metal atoms is measured according to the CO pulse adsorption method using a quantity measuring device (“BEL-METAL-1” manufactured by BEL JAPAN, INC), and is calculated from the number of exposed metal atoms and the supported amount of the metal fine particles. It can be calculated from the total number of metal atoms.
また、本発明の触媒において前記チタン含有ケイ酸塩多孔体に担持される金属微粒子の粒径は特に制限されないが、平均粒子径が１〜１００ｎｍ程度であることが好ましく、１〜２０ｎｍ程度であることがより好ましい。平均粒子径が前記下限未満では前記多孔体に金属種が埋もれたりして触媒活性サイト数が少なくなり触媒活性が低下する傾向にあり、他方、前記上限を超えると金属種が凝集して粒子が大きくなりすぎ触媒活性が低下する傾向にある。 In the catalyst of the present invention, the particle size of the metal fine particles supported on the titanium-containing silicate porous body is not particularly limited, but the average particle size is preferably about 1 to 100 nm, and about 1 to 20 nm. It is more preferable. If the average particle size is less than the lower limit, metal species are buried in the porous body and the number of catalytic active sites tends to decrease, and the catalytic activity tends to decrease. The catalyst activity tends to be too low.
このような本発明の触媒は、目的とする反応に対応して適宜金属元素を選択することにより、公知のあらゆる反応に用いることができる。例えば、パラジウム、ニッケル又は白金を含有する本発明の触媒は水素化反応、脱水素反応、酸化反応等に対して高活性を示す。また、コバルト又はロジウムを含有する本発明の触媒はヒドロホルミル化反応、ヒドロエステル化反応等に対して高活性を示す。 Such a catalyst of the present invention can be used for any known reaction by appropriately selecting a metal element corresponding to the target reaction. For example, the catalyst of the present invention containing palladium, nickel or platinum exhibits high activity for hydrogenation reaction, dehydrogenation reaction, oxidation reaction and the like. The catalyst of the present invention containing cobalt or rhodium exhibits high activity for hydroformylation reaction, hydroesterification reaction and the like.
以下、実施例及び比各例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、実施例等において、平均細孔径、比表面積、金属担持量、金属微粒子の平均粒子径、金属分散度及び金属表面積は、以下の方法により測定した。また、触媒担体（多孔体）として以下のものを使用した。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and each comparative example, this invention is not limited to a following example. In Examples and the like, the average pore diameter, specific surface area, metal loading, average particle diameter of metal fine particles, metal dispersity, and metal surface area were measured by the following methods. Moreover, the following were used as a catalyst carrier (porous body).
＜平均細孔径及び比表面積＞
触媒担体または得られた金属担持触媒を２００℃で５時間真空引きして測定用試料を調製し、この測定用試料についてＢＥＴ法（装置：ＢＥＬ ＪＡＰＡＮ，ＩＮＣ社製「ＢＥＬＳＯＲＰ−ｍａｘ」により平均細孔径及び比表面積を測定した。
<Average pore diameter and specific surface area>
A sample for measurement was prepared by evacuating the catalyst support or the obtained metal-supported catalyst at 200 ° C. for 5 hours, and the sample for measurement was averaged by the BET method (apparatus: BELSORP-max manufactured by BEL JAPAN, INC). The pore diameter and specific surface area were measured.
＜金属担持量＞
得られた金属担持触媒を、フッ酸を用いて溶解した後、王水を加えて担持金属を溶解し、さらに硫酸を加えてフッ酸及び王水を除去して測定用試料を調製し、この測定用試料についてＩＣＰによる元素分析（装置：Ｐｅｒｋｉｎ Ｅｌｍｅｒ社製「ＯＰＴＩＭＡ ３０００ ＸＬ」）を行ない、金属担持量を算出した。
<Metal loading>
After the obtained metal-supported catalyst is dissolved using hydrofluoric acid, aqua regia is added to dissolve the supported metal, and sulfuric acid is further added to remove hydrofluoric acid and aqua regia to prepare a sample for measurement. The measurement sample was subjected to elemental analysis by ICP (apparatus: “OPTIMA 3000 XL” manufactured by Perkin Elmer), and the metal loading was calculated.
＜金属微粒子の平均粒子径、金属分散度及び金属表面積＞
得られた金属担持触媒を、酸素雰囲気中、４００℃で１５分間保持し、次いで水素雰囲気中、４００℃で１５分間保持し、さらにヘリウム雰囲気中で５０℃に冷却した後、全自動触媒ガス吸着量測定装置（ＢＥＬ ＪＡＰＡＮ，ＩＮＣ社製「ＢＥＬ−ＭＥＴＡＬ−１」）を用いてＣＯパルス吸着法に従って、担持された金属微粒子の平均粒子径、金属分散度及び金属表面積を測定した。
<Average particle diameter of metal fine particles, metal dispersion degree, and metal surface area>
The obtained metal-supported catalyst was held in an oxygen atmosphere at 400 ° C. for 15 minutes, then held in a hydrogen atmosphere at 400 ° C. for 15 minutes, further cooled to 50 ° C. in a helium atmosphere, and then fully automatic catalyst gas adsorption The average particle diameter, metal dispersity, and metal surface area of the supported metal fine particles were measured according to the CO pulse adsorption method using a quantity measuring device (“BEL-METAL-1” manufactured by BEL JAPAN, INC).
（触媒担体）
＜チタン含有メソポーラスシリカ＞
国際公開第ＷＯ２００７／０３７０２６号パンフレットの実施例に記載された方法と同様の方法によりチタン含有メソポーラスシリカを合成した。得られたチタン含有メソポーラスシリカは、ケイ素原子の一部がチタン原子で置換されているシリカ骨格を有するもので、チタン原子とケイ素原子との比率（原子比）が（Ｔｉ／Ｓｉ）＝０．０１であり、平均細孔径が３．７１ｎｍ、比表面積が１１８７ｍ２／ｇである規則配列メソ孔を有するヘキサゴナル構造のチタン含有メソポーラスシリカ（表及び図中においては「１％Ｔｉ−ＨＭＳ」と略す。以下同様。）であった。
(Catalyst carrier)
<Titanium-containing mesoporous silica>
Titanium-containing mesoporous silica was synthesized by a method similar to the method described in the examples of International Publication No. WO2007 / 037026. The obtained titanium-containing mesoporous silica has a silica skeleton in which a part of silicon atoms is substituted with titanium atoms, and the ratio (atomic ratio) of titanium atoms to silicon atoms is (Ti / Si) = 0. The titanium-containing mesoporous silica having a hexagonal structure having ordered mesopores having an average pore diameter of 3.71 nm and a specific surface area of 1187 m 2 / g (abbreviated as “1% Ti-HMS” in the tables and drawings) The same applies hereinafter.)
＜チタンを含まないメソポーラスシリカ＞
チタン源としてのチタンテトライソプロポキシドを用いなかった以外は、国際公開第ＷＯ２００７／０３７０２６号パンフレットの実施例に記載された方法と同様の方法によりメソポーラスシリカを合成した。得られたメソポーラスシリカは、規則配列メソ孔を有するヘキサゴナル構造のメソポーラスシリカ（ＨＭＳ）であった。
<Mesoporous silica containing no titanium>
Mesoporous silica was synthesized by the same method as that described in Examples of International Publication No. WO2007 / 037026 except that titanium tetraisopropoxide as a titanium source was not used. The obtained mesoporous silica was hexagonal structure mesoporous silica (HMS) having ordered mesopores.
＜チタノシリカライト＞
チタンとシリコンの複合酸化物であってミクロポーラスなシリカ骨格を有するチタノシリカライト（ＴＳ−１）として、触媒学会の参照触媒ＡＲＣ−ＴＳ１ＣＬ（Ｓｉ／Ｔｉ＝３５）を使用した。このチタノシリカライトにおけるチタン原子とケイ素原子との比率（原子比）は（Ｔｉ／Ｓｉ）＝０．０２９であり、比表面積は３９０ｍ２／ｇであった。
<Titanosilica Light>
As titanosilicalite (TS-1), which is a composite oxide of titanium and silicon and has a microporous silica skeleton, a reference catalyst ARC-TS1CL (Si / Ti = 35) of the Catalytic Society was used. In this titanosilicalite, the ratio (atomic ratio) between titanium atoms and silicon atoms was (Ti / Si) = 0.029, and the specific surface area was 390 m 2 / g.
（実施例１）
本発明のマイクロ波照射析出法により、以下のようにして、白金担持チタン含有メソポーラスシリカ触媒を得た。すなわち、０．５２ｍＭの塩化白金酸水溶液１６０ｍＬ（白金換算で０．１０１ｇ）に０．５ｇの前記チタン含有メソポーラスシリカを懸濁させ、この懸濁液を１０５℃に保持しながら、マイクロ波反応装置（ＥＹＥＬＡ社製「ＭＷＯ−１００００Ｓ型」）を用いて出力４００Ｗ、周波数２．４５ＧＨｚのマイクロ波を１５分間照射した。その後、遠心分離により固形分を回収し、１１０℃で一晩乾燥した後、４５０℃で５時間焼成して白金担持チタン含有メソポーラスシリカ触媒（Ｍｗ−Ｐｔ／１％Ｔｉ−ＨＭＳ）を得た。
Example 1
By the microwave irradiation precipitation method of the present invention, a platinum-supported titanium-containing mesoporous silica catalyst was obtained as follows. That is, a microwave reactor was prepared by suspending 0.5 g of the titanium-containing mesoporous silica in 160 mL of 0.52 mM chloroplatinic acid aqueous solution (0.101 g in terms of platinum) and maintaining the suspension at 105 ° C. (EMWELA “MWO-10000S type”) was used to irradiate microwaves with an output of 400 W and a frequency of 2.45 GHz for 15 minutes. Then, solid content was collect | recovered by centrifugation, and after drying at 110 degreeC overnight, it baked at 450 degreeC for 5 hours, and obtained platinum carrying | support titanium containing mesoporous silica catalyst (Mw-Pt / 1% Ti-HMS).
得られた白金担持チタン含有メソポーラスシリカ触媒の平均細孔径、比表面積、白金担持量、金属微粒子の平均粒子径、金属分散度及び金属表面積を前記方法により測定した。その結果を表１に示す。なお、表１には、触媒担体として用いたチタン含有メソポーラスシリカ触媒の平均細孔径及び比表面積も示した。 The obtained platinum-supported titanium-containing mesoporous silica catalyst was measured for the average pore diameter, specific surface area, platinum-supported amount, average particle diameter of metal fine particles, metal dispersion, and metal surface area by the above methods. The results are shown in Table 1. Table 1 also shows the average pore diameter and specific surface area of the titanium-containing mesoporous silica catalyst used as the catalyst carrier.
また、得られた白金担持チタン含有メソポーラスシリカ触媒を透過型顕微鏡により観察した結果を図１に示し、Ｐｔ ＬＩＩＩ−ｅｄｇｅ ＦＴ−ＥＸＡＦＳ分析した結果を図２に示す。 Moreover, the results of the platinum-supported titanium-containing mesoporous silica catalysts obtained was observed by a transmission electron microscope shown in FIG. 1, showing the Pt L III -edge FT-EXAFS analysis result in FIG.
さらに、得られた白金担持チタン含有メソポーラスシリカ触媒のＸ線回折測定を行なった結果、チタン含有メソポーラスシリカに特有なピークのみが認められた。このこと、及び、表１に示すように、白金担持チタン含有メソポーラスシリカ触媒の平均細孔径が３．７１ｎｍ、比表面積が９２６ｍ２／ｇであり、白金担持前のチタン含有メソポーラスシリカの測定値とほとんど変わらなかったことから、白金担持後もチタン含有メソポーラスシリカ自体のメソポーラス構造が保持されていることが確認された。 Furthermore, as a result of X-ray diffraction measurement of the resulting platinum-supported titanium-containing mesoporous silica catalyst, only a peak peculiar to titanium-containing mesoporous silica was recognized. As shown in Table 1, the platinum-supported titanium-containing mesoporous silica catalyst has an average pore diameter of 3.71 nm and a specific surface area of 926 m 2 / g. Since there was almost no change, it was confirmed that the mesoporous structure of the titanium-containing mesoporous silica itself was retained even after platinum was supported.
＜ニトロベンゼンの水素化還元反応＞
得られた白金担持チタン含有メソポーラスシリカ触媒の触媒活性を評価するために、以下のようにしてニトロベンゼンの水素化反応を実施した。すなわち、得られた白金担持チタン含有メソポーラスシリカ触媒を２００℃で、１２０分間水素還元処理した後、この触媒０．０１５４ｇとニトロベンゼン２ｍＭ（０．２４６ｇ）とを５０ｍｌのガラス製反応器に入れ、これに溶媒としてエタノールを１０ｍｌ加えて、水素圧１ａｔｍ、温度５０℃の条件で攪拌した。この間、一定時間毎にニトロベンゼンの消費量及びアニリンの生成量をガスクロマトグラフィー（（株）島津製作所製「ＧＣ−１４Ｂ」、ＦＩＤ検出、ＴＣ−１カラムを使用）で分析した。その結果を図３に示す。この結果から算出したニトロベンゼンの消費速度を表１に示す。
<Hydrogen reduction of nitrobenzene>
In order to evaluate the catalytic activity of the obtained platinum-supported titanium-containing mesoporous silica catalyst, a hydrogenation reaction of nitrobenzene was carried out as follows. That is, the obtained platinum-supported titanium-containing mesoporous silica catalyst was subjected to hydrogen reduction treatment at 200 ° C. for 120 minutes, and then 0.0154 g of this catalyst and 2 mM (0.246 g) of nitrobenzene were placed in a 50 ml glass reactor. 10 ml of ethanol was added as a solvent, and the mixture was stirred under conditions of a hydrogen pressure of 1 atm and a temperature of 50 ° C. During this time, the consumption amount of nitrobenzene and the production amount of aniline were analyzed by gas chromatography (“GC-14B” manufactured by Shimadzu Corporation, using FID detection, TC-1 column) at regular intervals. The result is shown in FIG. The consumption rate of nitrobenzene calculated from this result is shown in Table 1.
（比較例１）
いわゆる含浸法により、以下のようにして、比較のための白金担持チタン含有メソポーラスシリカを得た。すなわち、０．５２ｍＭの塩化白金酸水溶液１６０ｍＬ（白金換算で０．１０１ｇ）に０．５ｇの前記チタン含有メソポーラスシリカを懸濁させた後、水浴を８０℃に保持しながらエバポレーターで溶媒を蒸発させ、乾固させた。その後、１１０℃で一晩乾燥した後、４５０℃で５時間焼成して白金担持チタン含有メソポーラスシリカ触媒（ｉｍｐ−Ｐｔ／１％Ｔｉ−ＨＭＳ）を得た。
(Comparative Example 1)
A platinum-supported titanium-containing mesoporous silica for comparison was obtained by a so-called impregnation method as follows. That is, after suspending 0.5 g of the titanium-containing mesoporous silica in 160 mL of 0.52 mM chloroplatinic acid aqueous solution (0.101 g in terms of platinum), the solvent was evaporated by an evaporator while maintaining a water bath at 80 ° C. And dried. Then, after drying at 110 degreeC overnight, it baked at 450 degreeC for 5 hours, and obtained platinum carrying | support titanium containing mesoporous silica catalyst (imp-Pt / 1% Ti-HMS).
得られた白金担持チタン含有メソポーラスシリカ触媒の平均細孔径、比表面積、白金担持量、金属微粒子の平均粒子径、金属分散度及び金属表面積を前記方法により測定した。その結果を表１に示す。また、得られた白金担持チタン含有メソポーラスシリカ触媒についてＰｔ ＬＩＩＩ−ｅｄｇｅ ＦＴ−ＥＸＡＦＳ分析した結果を図２に示す。 The obtained platinum-supported titanium-containing mesoporous silica catalyst was measured for the average pore diameter, specific surface area, platinum-supported amount, average particle diameter of metal fine particles, metal dispersion, and metal surface area by the above methods. The results are shown in Table 1. Also, Figure 2 shows the Pt L III -edge FT-EXAFS analysis result of the obtained platinum-supported titanium-containing mesoporous silica catalyst.
また、得られた白金担持チタン含有メソポーラスシリカ触媒の触媒活性を、実施例１と同様にしてニトロベンゼンの水素化還元反応により評価した。ニトロベンゼンの消費量及びアニリンの生成量を図３に示し、この結果から算出したニトロベンゼンの消費速度を表１に示す。 Further, the catalytic activity of the obtained platinum-supported titanium-containing mesoporous silica catalyst was evaluated by a hydrogenation reduction reaction of nitrobenzene in the same manner as in Example 1. The consumption amount of nitrobenzene and the production amount of aniline are shown in FIG. 3, and the consumption rate of nitrobenzene calculated from this result is shown in Table 1.
（比較例２）
前記チタン含有メソポーラスシリカの代わりに前記チタンを含まないメソポーラスシリカ０．５ｇを用いた以外は実施例１と同様にして白金処理したチタン不含有メソポーラスシリカ（Ｍｗ−Ｐｔ／ＨＭＳ）を得た。
(Comparative Example 2)
Platinum-treated titanium-free mesoporous silica (Mw-Pt / HMS) was obtained in the same manner as in Example 1 except that 0.5 g of mesoporous silica not containing titanium was used instead of the titanium-containing mesoporous silica.
得られた白金処理したチタン不含有メソポーラスシリカの白金担持量を前記方法により測定したところ、白金は担持されていないことが確認された。 When the platinum carrying amount of the obtained platinum-treated titanium-free mesoporous silica was measured by the above method, it was confirmed that platinum was not carried.
表１に示した結果から明らかなように、触媒担体としてチタンを含有するメソポーラスシリカを用いた場合（実施例１）には白金が担持されているのに対して、チタンを含有しないメソポーラスシリカを用いた場合（比較例２）には白金が担持されておらず、本発明の製造方法のようにマイクロ波を照射して担体に白金を担持する場合にはチタン種が必須成分であることが示唆された。 As is apparent from the results shown in Table 1, when mesoporous silica containing titanium is used as the catalyst carrier (Example 1), platinum is supported, whereas mesoporous silica not containing titanium is used. When used (Comparative Example 2), platinum is not supported. When the platinum is supported on the carrier by irradiation with microwaves as in the production method of the present invention, the titanium species may be an essential component. It was suggested.
また、図１に示した結果から明らかなように、本発明の製造方法により得られた白金担持チタン含有メソポーラスシリカ触媒（実施例１）においては、白金が微粒子としてチタン含有メソポーラスシリカ表面上に高分散した状態で存在していることが確認された。 Further, as is clear from the results shown in FIG. 1, in the platinum-supported titanium-containing mesoporous silica catalyst (Example 1) obtained by the production method of the present invention, platinum is finely formed on the surface of the titanium-containing mesoporous silica as fine particles. It was confirmed to exist in a dispersed state.
さらに、表１に示した結果から明らかなように、本発明の製造方法のようにマイクロ波を照射して白金を担持した場合（実施例１）には、含浸法により担持した場合（比較例１）に比べて白金担持量が若干多いにも係わらず、金属分散度が高く、金属微粒子の平均粒子径が小さくなり、また、図２に示したように、Ｐｔ−Ｐｔ結合に起因するピーク強度が小さくなった。これらのことから、本発明の製造方法により得られた白金担持触媒は、白金微粒子同士で凝集することなく、高分散状態で存在していることが示唆された。 Further, as is clear from the results shown in Table 1, when platinum was supported by irradiation with microwaves as in the production method of the present invention (Example 1), when it was supported by the impregnation method (Comparative Example) Although the amount of platinum supported is slightly larger than that in 1), the metal dispersion degree is high, the average particle diameter of the metal fine particles is small, and, as shown in FIG. 2, the peak caused by the Pt-Pt bond Strength decreased. From these facts, it was suggested that the platinum-supported catalyst obtained by the production method of the present invention exists in a highly dispersed state without agglomerating between platinum fine particles.
表１に示した結果から明らかなように、本発明のマイクロ波を利用した製造方法により得られた触媒（実施例１）においては、含浸法により得られた触媒（比較例１）に比べて、ニトロベンゼンの消費速度が速く、触媒活性が向上していることが確認された。 As is apparent from the results shown in Table 1, the catalyst (Example 1) obtained by the production method using the microwave of the present invention was compared with the catalyst obtained by the impregnation method (Comparative Example 1). It was confirmed that the consumption rate of nitrobenzene was high and the catalytic activity was improved.
（実施例２）
本発明のマイクロ波照射析出法により、以下のようにして、金担持チタン含有メソポーラスシリカ触媒を得た。すなわち、０．５２ｍＭの塩化白金酸水溶液の代わりに０．５２ｍＭの塩化金酸水溶液１６０ｍＬ（金換算で０．１０２ｇ）を用いた以外は実施例１と同様にして金担持チタン含有メソポーラスシリカ触媒（Ｍｗ−Ａｕ／１％Ｔｉ−ＨＭＳ）を得た。
(Example 2)
By the microwave irradiation deposition method of the present invention, a gold-supported titanium-containing mesoporous silica catalyst was obtained as follows. That is, a gold-supported titanium-containing mesoporous silica catalyst (in the same manner as in Example 1 except that 160 mL of 0.52 mM chloroauric acid aqueous solution (0.102 g in terms of gold) was used instead of the 0.52 mM chloroplatinic acid aqueous solution ( Mw-Au / 1% Ti-HMS) was obtained.
得られた金担持チタン含有メソポーラスシリカ触媒の金担持量、金属微粒子の平均粒子径、金属分散度及び金属表面積を前記方法により測定した。その結果を表２に示す。また、得られた金担持チタン含有メソポーラスシリカ触媒の紫外可視吸収スペクトルを図４に示す。 The gold carrying amount of the obtained gold-supporting titanium-containing mesoporous silica catalyst, the average particle diameter of the metal fine particles, the metal dispersion degree, and the metal surface area were measured by the above methods. The results are shown in Table 2. Moreover, the ultraviolet visible absorption spectrum of the obtained gold | metal | money carrying | support titanium containing mesoporous silica catalyst is shown in FIG.
（比較例３）
比較例１と同様にして、いわゆる含浸法により、比較のための金担持チタン含有メソポーラスシリカを得た。すなわち、０．５２ｍＭの塩化白金酸水溶液の代わりに０．５２ｍＭの塩化金酸水溶液１６０ｍＬ（金換算で０．１０２ｇ）を用いた以外は比較例１と同様にして金担持チタン含有メソポーラスシリカ触媒（ｉｍｐ−Ａｕ／１％Ｔｉ−ＨＭＳ）を得た。
(Comparative Example 3)
Similar to Comparative Example 1, a gold-supported titanium-containing mesoporous silica for comparison was obtained by a so-called impregnation method. That is, a gold-supported titanium-containing mesoporous silica catalyst (similar to Comparative Example 1 except that 160 mL of 0.52 mM chloroauric acid aqueous solution (0.102 g in terms of gold) was used instead of 0.52 mM chloroplatinic acid aqueous solution ( imp-Au / 1% Ti-HMS).
得られた金担持チタン含有メソポーラスシリカ触媒の金属微粒子の平均粒子径、金属分散度及び金属表面積を前記方法により測定した。その結果を表２に示す。 The average particle diameter, metal dispersity, and metal surface area of the metal fine particles of the obtained gold-supported titanium-containing mesoporous silica catalyst were measured by the above methods. The results are shown in Table 2.
（実施例３）
本発明のマイクロ波照射析出法により、以下のようにして、金担持チタノシリカライト触媒を得た。すなわち、前記チタン含有メソポーラスシリカの代わりに前記チタノシリカライト（ＴＳ−１）０．５ｇを用いた以外は実施例１と同様にして金担持チタノシリカライト触媒（Ｍｗ−Ａｕ／ＴＳ−１）を得た。
(Example 3)
By the microwave irradiation precipitation method of the present invention, a gold-supported titanosilicalite catalyst was obtained as follows. That is, a gold-supported titanosilicalite catalyst (Mw-Au / TS-1) was used in the same manner as in Example 1 except that 0.5 g of the titanosilicalite (TS-1) was used instead of the titanium-containing mesoporous silica. )
得られた金担持チタノシリカライト触媒の金担持量を前記方法により測定した。その結果を表２に示す。また、得られた金担持チタノシリカライト触媒の紫外可視吸収スペクトルを図４に示し、Ｔｉ−ｅｄｇｅ ＸＡＦＳ分析した結果を図５に示す。なお、図５にはチタノシリカライト（ＴＳ−１）のみについてＴｉ−ｅｄｇｅ ＸＡＦＳ分析した結果も示した。さらに、図６には、得られた金担持チタノシリカライト触媒をＦＴ−ＥＸＡＦＳ分析した結果を示す。なお、図６には、チタニアのみ、チタノシリカライト（ＴＳ−１）のみについてＦＴ−ＥＸＡＦＳ分析した結果も示した。 The gold carrying amount of the obtained gold carrying titanosilicalite catalyst was measured by the above method. The results are shown in Table 2. Moreover, the ultraviolet visible absorption spectrum of the obtained gold | metal | money carrying | support titanosilicalite catalyst is shown in FIG. 4, and the result of having performed Ti-edge XAFS analysis is shown in FIG. FIG. 5 also shows the results of Ti-edge XAFS analysis of only titanosilicalite (TS-1). Further, FIG. 6 shows the result of FT-EXAFS analysis of the obtained gold-supported titanosilicalite catalyst. FIG. 6 also shows the results of FT-EXAFS analysis for only titania and only titanosilicalite (TS-1).
（比較例４）
前記チタン含有メソポーラスシリカの代わりに前記チタンを含まないメソポーラスシリカ０．５ｇを用いた以外は実施例２と同様にして金処理したチタン不含有メソポーラスシリカ（Ｍｗ−Ａｕ／ＨＭＳ）を得た。
(Comparative Example 4)
A titanium-free mesoporous silica (Mw-Au / HMS) treated with gold was obtained in the same manner as in Example 2 except that 0.5 g of mesoporous silica containing no titanium was used instead of the titanium-containing mesoporous silica.
得られた金処理したチタン不含有メソポーラスシリカの金担持量を前記方法により測定したところ、金は担持されていないことが確認された。また、得られた金処理したチタン不含有メソポーラスシリカの紫外可視吸収スペクトルを図４に示す。 When the gold carrying amount of the obtained gold-treated titanium-free mesoporous silica was measured by the above method, it was confirmed that no gold was carried. Further, FIG. 4 shows an ultraviolet-visible absorption spectrum of the obtained gold-treated titanium-free mesoporous silica.
表２に示した結果から明らかなように、触媒担体としてチタンを含有するメソポーラスシリカを用いた場合（実施例２）やチタノシリカライトを用いた場合（実施例３）には金が担持されているのに対して、チタンを含有しないメソポーラスシリカを用いた場合（比較例４）には金は担持されていないことが確認された。 As is apparent from the results shown in Table 2, gold is supported when mesoporous silica containing titanium is used as a catalyst carrier (Example 2) or when titanosilicalite is used (Example 3). On the other hand, when mesoporous silica containing no titanium was used (Comparative Example 4), it was confirmed that no gold was supported.
また、図４に示した結果から明らかなように、触媒担体としてチタン含有メソポーラスシリカやチタノシリカライトを用いた場合（実施例２〜３）には、得られた触媒の紫外可視吸収スペクトルにおいてプラズモンピークが５２０ｎｍ付近に観察されたことから、金が担持されていることが確認された。一方、チタンを含有していないメソポーラスシリカを用いた場合（比較例４）にはプラズモンピークが観察されず、金は担持されていないことが確認された。 Further, as is clear from the results shown in FIG. 4, when titanium-containing mesoporous silica or titanosilicalite was used as the catalyst carrier (Examples 2 to 3), in the ultraviolet-visible absorption spectrum of the obtained catalyst. Since the plasmon peak was observed around 520 nm, it was confirmed that gold was supported. On the other hand, when mesoporous silica not containing titanium was used (Comparative Example 4), no plasmon peak was observed, confirming that no gold was supported.
従って、本発明の製造方法のようにマイクロ波を照射して担体に金を担持する場合にはチタン種が必須成分であることが示唆された。また、このことから、本発明のマイクロ波照射を利用した触媒の製造方法においては、チタン種が必須成分であることが更に強く示唆された。 Therefore, it was suggested that the titanium species is an essential component when gold is supported on the carrier by irradiation with microwaves as in the production method of the present invention. This also strongly suggests that the titanium species is an essential component in the catalyst production method using microwave irradiation of the present invention.
また、表２に示した結果から明らかなように、本発明の製造方法のようにマイクロ波を照射して金を担持した場合（実施例２）、含浸法により担持した場合（比較例３）に比べて平均粒子径が非常に小さい金属微粒子が高分散状態で担持されていることが確認された。 Further, as is apparent from the results shown in Table 2, when gold was carried by irradiation with microwaves as in the production method of the present invention (Example 2), when carried by an impregnation method (Comparative Example 3) It was confirmed that metal fine particles having an extremely small average particle diameter were supported in a highly dispersed state.
また、図５に示した結果から明らかなように、プラズモンピークがより小さい金担持チタノシリカライト（Ｍｗ−Ａｕ／ＴＳ−１）においても、チタノシリカライト（ＴＳ−１）のみの場合に比べてＴｉ−ｅｄｇｅ ＸＡＦＳスペクトルのｐｒｅｅｄｇｅピーク強度が減少していることから、チタノシリカライト中の孤立Ｔｉ種とＡｕの相互作用が示唆された。さらに、図６に示した結果から明らかなように、金担持チタノシリカライト（Ｍｗ−Ａｕ／ＴＳ−１）のＦＴ‐ＥＸＡＦＳスペクトルの３Å付近にピークが観察され、上記と同様にチタノシリカライト中の孤立Ｔｉ種とＡｕの相互作用が示唆され、チタノシリカライトに金が担持されていることが確認された。 Further, as apparent from the results shown in FIG. 5, even in the case of gold-supported titanosilicalite (Mw-Au / TS-1) having a smaller plasmon peak, in the case of only titanosilicalite (TS-1). In comparison, the preedge peak intensity of the Ti-edge XAFS spectrum decreased, suggesting the interaction between the isolated Ti species in the titanosilicalite and Au. Further, as is apparent from the results shown in FIG. 6, a peak was observed in the vicinity of 3% of the FT-EXAFS spectrum of the gold-supported titanosilicalite (Mw-Au / TS-1). The interaction between the isolated Ti species in the light and Au was suggested, and it was confirmed that gold was supported on the titanosilicalite.
以上説明したように、本発明によれば、紫外線を利用した方法よりも短時間且つ省エネルギーでチタン含有ケイ酸塩多孔体の表面上に高分散状態で金属微粒子を担持させることができ、触媒活性を充分に向上させることが可能な触媒の製造方法を提供することが可能となる。従って、本発明の製造方法によって得られる触媒においては、チタン含有ケイ酸塩多孔体の表面上に高分散状態で金属微粒子を担持されており、触媒活性を充分に向上させることが可能となる。 As described above, according to the present invention, metal fine particles can be supported in a highly dispersed state on the surface of the titanium-containing silicate porous material in a shorter time and with less energy than the method using ultraviolet rays, and the catalytic activity It is possible to provide a method for producing a catalyst capable of sufficiently improving the above. Therefore, in the catalyst obtained by the production method of the present invention, metal fine particles are supported in a highly dispersed state on the surface of the titanium-containing silicate porous body, and the catalytic activity can be sufficiently improved.
従って、本発明は各種化成品を合成するための水素化触媒、あるいは酸化触媒、環境浄化触媒等を得るための技術として非常に有用である。 Therefore, the present invention is very useful as a technique for obtaining a hydrogenation catalyst, an oxidation catalyst, an environmental purification catalyst, or the like for synthesizing various chemical products.
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| JP2016507356A (en) * | 2012-12-27 | 2016-03-10 | エルジー・ケム・リミテッド | Catalyst comprising hollow metal nanoparticles supported on a support |
| JP2018187578A (en) * | 2017-05-09 | 2018-11-29 | トヨタ自動車株式会社 | Cluster carrying catalyst and manufacturing method therefor |
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|---|---|---|---|---|
| JP2016507356A (en) * | 2012-12-27 | 2016-03-10 | エルジー・ケム・リミテッド | Catalyst comprising hollow metal nanoparticles supported on a support |
| JP2018187578A (en) * | 2017-05-09 | 2018-11-29 | トヨタ自動車株式会社 | Cluster carrying catalyst and manufacturing method therefor |
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