JPWO2008108398A1 - Method for producing oxygenated organic compound by oxidation of hydrocarbon and oxidation catalyst used therefor - Google Patents
Method for producing oxygenated organic compound by oxidation of hydrocarbon and oxidation catalyst used therefor Download PDFInfo
- Publication number
- JPWO2008108398A1 JPWO2008108398A1 JP2009502604A JP2009502604A JPWO2008108398A1 JP WO2008108398 A1 JPWO2008108398 A1 JP WO2008108398A1 JP 2009502604 A JP2009502604 A JP 2009502604A JP 2009502604 A JP2009502604 A JP 2009502604A JP WO2008108398 A1 JPWO2008108398 A1 JP WO2008108398A1
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- Prior art keywords
- oxygen
- organic compound
- producing
- containing organic
- hydrocarbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 48
- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 42
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 39
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- 239000004215 Carbon black (E152) Substances 0.000 title claims description 30
- 238000007254 oxidation reaction Methods 0.000 title claims description 20
- 230000003647 oxidation Effects 0.000 title claims description 17
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- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 12
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
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- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
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Abstract
高い触媒安定性に加えて、高い原料転化率を可能とした、含酸素有機化合物を製造する方法を提供する。酸素源と還元剤を含む反応流体により炭化水素を酸化して、含酸素有機化合物を製造する方法において、メソ細孔構造を有する壁材がミクロ細孔構造を有するチタノシリケートの種結晶を含有する担体、いわゆるミクロ−メソハイブリッド担体を用い、これに微細な金粒子を担持させたものを触媒とすることにより、原料転化率の向上と、触媒寿命の向上の両方を達成する。Provided is a method for producing an oxygen-containing organic compound that enables high raw material conversion in addition to high catalyst stability. In a method for producing an oxygen-containing organic compound by oxidizing hydrocarbons with a reaction fluid containing an oxygen source and a reducing agent, the wall material having a mesoporous structure contains a titanosilicate seed crystal having a microporous structure. By using a carrier to be supported, a so-called micro-meso hybrid carrier and carrying a fine gold particle on this catalyst as a catalyst, both improvement of the raw material conversion rate and improvement of the catalyst life are achieved.
Description
本発明は、酸素源と還元剤を含む反応流体により、炭化水素を酸化して含酸素有機化合物を製造する方法、及びそのための酸化用触媒に関し、特に、酸素−水素混合物を用いて、プロピレンなどのオレフィンから、プロピレンオキシドなどのオレフィン酸化物を製造する方法、及びそのための酸化用触媒に関する。 The present invention relates to a method for producing an oxygen-containing organic compound by oxidizing a hydrocarbon with a reaction fluid containing an oxygen source and a reducing agent, and an oxidation catalyst therefor, in particular, using an oxygen-hydrogen mixture, propylene, etc. The present invention relates to a process for producing an olefin oxide such as propylene oxide from the olefin, and an oxidation catalyst therefor.
プロピレンオキシド（PO）は重要な化学品であり、多くの用途がある。現在、プロピレンオキシドは、塩素と水を使用するクロロヒドリン法または有機ヒドロペルオキシドを使用するハルコン法の変法により製造されている。これらの方法は複雑な多段法であり、塩素化炭化水素などの副生成物を伴うか、処理またはリサイクルが必要であるｔ−ブチルアルコール、α−ヒドロキシエチルベンゼン、またはα−ヒドロキシクメンなどを同時に生産するという、欠点がある。したがって、ＰＯの一段製法がきわめて望ましく、このためにはプロピレンを水素と酸素との混合物と直接反応させる方法が、簡単で直接的である。 Propylene oxide (PO) is an important chemical and has many uses. Currently, propylene oxide is produced by a modification of the chlorohydrin method using chlorine and water or the Halcon method using organic hydroperoxide. These methods are complex multi-stage processes that simultaneously produce t-butyl alcohol, α-hydroxyethylbenzene, α-hydroxycumene, etc. that involve by-products such as chlorinated hydrocarbons or that require treatment or recycling. There is a drawback of doing. Therefore, a one-step process for the production of PO is highly desirable, for which the process of reacting propylene directly with a mixture of hydrogen and oxygen is simple and straightforward.
水素と酸素の混合物によるＰＯ製造の最初の報告は、チタニアに担持した金ナノ粒子を使用する方法であり（非特許文献１）、これに続いてＴｉ−ＭＣＭ−４１、Ｔｉ−ＭＣＭ−４８（非特許文献２）、Ｔｉ−ＴＵＤ（非特許文献３）及びメソ細孔Ｔｉ−Ｓｉ酸化物 （非特許文献４）などのメソ細孔材料のみならず、ＴＳ−１（非特許文献５）、ＴＳ−２、Ｔｉ−β（非特許文献６）などのミクロ細孔を有する材料を含む表面積の大きい支持体を使用する多くの研究がある。ミクロ細孔およびメソ細孔材料に関しては、レビューが報告されており（非特許文献７）、該文献に記載されたゼオライトは結晶性のミクロ細孔材料である。
国際純正応用化学連合（ＩＵＰＡＣ）は、ミクロ細孔材料を細孔直径が２．０ｎｍ未満の材料として、またメソ細孔材料を細孔が２．０〜５０ｎｍの材料として定義しているが、本発明においては、メソ細孔材料の定義を１００ｎｍまでと定義する。The first report of PO production using a mixture of hydrogen and oxygen is a method using gold nanoparticles supported on titania (Non-Patent Document 1), followed by Ti-MCM-41, Ti-MCM-48 ( Non-patent document 2), not only mesoporous materials such as Ti-TUD (non-patent document 3) and mesoporous Ti-Si oxide (non-patent document 4), but also TS-1 (non-patent document 5), There are many studies using a high surface area support including materials having micropores such as TS-2, Ti-β (Non-Patent Document 6). A review has been reported on micropore and mesoporous materials (Non-Patent Document 7), and the zeolite described in the literature is a crystalline microporous material.
The International Union of Applied Chemistry (IUPAC) defines microporous material as a material having a pore diameter of less than 2.0 nm, and mesoporous material as a material having a pore of 2.0 to 50 nm. In the present invention, the definition of the mesoporous material is defined as up to 100 nm.
こうした触媒担体については、すでに幾つかの特許も提案されており、例えば、特許文献１は、チタン含有酸化物及び金を含む溶液から析出沈殿により酸化物上に金を析出し、溶液と酸化物を遠心分離処理して得た、金を含む触媒について述べており、そのパラグラフ（００１９）には、酸化物は好ましくはケイ酸チタンを含むが、シリカ上の酸化チタンのモノレイヤーおよびサブモノレイヤーコーティングを含む他のチタン含有酸化物を含むことができると記載されている。それらの代表例として、ＭＦＩ−型のゼオライト触媒でミクロ細孔の細孔ネットワークを有する、チタンシリカライト、ＴＳ−１が上げられている。 Several patents have already been proposed for such a catalyst carrier. For example, Patent Document 1 discloses that gold is deposited on an oxide by precipitation from a solution containing a titanium-containing oxide and gold. The catalyst containing gold obtained by centrifuging is described in paragraph (0019), in which paragraph (0019) the oxide preferably comprises titanium silicate, but the titanium oxide monolayer and submonolayer on silica. It is described that other titanium-containing oxides including coatings can be included. A typical example of these is titanium silicalite, TS-1, which has an MFI-type zeolite catalyst and has a microporous network.
特許文献２は、酸化チタン担体に担持された半径が１０ｎｍ以下の超微細金粒子を含む触媒について述べており、１０から２００ｎｍの範囲の、好ましくはアナターゼ型の、ＴｉＯ２粒子からなるバルクの担体について論じているが、ミクロ細孔またはメソ細孔を有するものではない。Patent document 2 describes a catalyst comprising ultrafine gold particles having a radius of 10 nm or less supported on a titanium oxide support, and a bulk support made of TiO 2 particles, preferably in the range of 10 to 200 nm, of anatase type. However, it does not have micropores or mesopores.
特許文献３は、金、酸化チタン（チタニア）、及び比表面積が少なくとも５０ｍ２／ｇである担体を含有する、炭化水素の部分酸化用触媒について述べている。この酸化チタンは、無定形または好ましくはアナターゼ型であってもよいが、いずれにしろ触媒はミクロ細孔を有しない。酸化チタンは他の酸化物との複合物として存在してもよい。上記担体としては、ゼオライト性物質などの結晶性金属シリケートのみならず、酸化ケイ素、酸化アルミニウム、酸化ジルコニウム、およびこれらの複合材料などであることが挙げられ、前記酸化チタンは、該担体上に析出しているが、組成物は、ミクロ細孔及びメソ細孔のいずれも含有していない。Patent Document 3, gold, titanium oxide (titania), and a specific surface area comprises a carrier of at least 50 m 2 / g, describes a catalyst for partial oxidation of hydrocarbons. The titanium oxide may be amorphous or preferably anatase type, but in any case the catalyst does not have micropores. Titanium oxide may be present as a composite with other oxides. Examples of the support include not only crystalline metal silicates such as zeolitic substances, but also silicon oxide, aluminum oxide, zirconium oxide, and composite materials thereof. The titanium oxide is precipitated on the support. However, the composition contains neither micropores nor mesopores.
また、該特許文献３は、比表面積が５０ｍ２／ｇ以上の担体に担持した金および酸化チタンを含む炭化水素の部分酸化触媒の製造方法についても述べている。この方法は、（ａ）酸化チタンを担体に析出する工程、及び（ｂ）工程（ａ）の後、該担体を、金を含む水溶液に浸し、金を担体上に析出し、固定する工程を含んでいるが、用いられる担体は連結したメソ細孔およびミクロ細孔構造を有していない。Patent Document 3 also describes a method for producing a hydrocarbon partial oxidation catalyst containing gold and titanium oxide supported on a carrier having a specific surface area of 50 m 2 / g or more. This method includes the steps of (a) depositing titanium oxide on a support, and (b) after step (a), immersing the support in an aqueous solution containing gold to deposit and fix the gold on the support. Although included, the supports used do not have linked mesopore and micropore structures.
特許文献４には、金、チタン含有金属酸化物、ならびにアルカリ金属、アルカリ土類金属およびタリウムのグループから選択される少なくとも１種類の元素を含む炭化水素の部分酸化用触媒が記載されている。チタン含有金属酸化物は、酸化チタン、ＴｉＯ２として特定されるチタニア、および／またはチタン含有複合酸化物と称されるチタンを含む複合酸化物を含む、いかなる金属酸化物であってもよい。チタン含有複合酸化物は、チタニア−ジルコニア、ＦｅＴｉＯ３、ＣａＴｉＯ３、ＳｒＴｉＯ３などのチタンと他の金属との複合酸化物であってもよいが、これらはミクロ細孔を有しない化合物である。チタン含有複合酸化物は、チタノ−シリケートなどのようにチタンがゼオライト性化合物の内部で結合しているゼオライト性化合物であってもよいが、これらの化合物はメソ細孔を持たない。Patent Document 4 describes a catalyst for partial oxidation of hydrocarbons containing at least one element selected from the group consisting of gold, titanium-containing metal oxides, and alkali metals, alkaline earth metals, and thallium. The titanium-containing metal oxide may be any metal oxide including titanium oxide, titania specified as TiO 2 , and / or a composite oxide comprising titanium referred to as a titanium-containing composite oxide. The titanium-containing composite oxide may be a composite oxide of titanium and another metal such as titania-zirconia, FeTiO 3 , CaTiO 3 , SrTiO 3, etc., but these are compounds having no micropores. The titanium-containing composite oxide may be a zeolitic compound in which titanium is bound inside the zeolitic compound, such as titano-silicate, but these compounds do not have mesopores.
特許文献５は、一酸化炭素、アルコール、ギ酸、およびシクロヘキサジエンなどの還元剤の存在で酸素による炭化水素の酸化に使用される、チタン含有酸化物上に金の超微粒子を固定化した触媒について述べており、チタン含有酸化物は、酸化チタン、チタン含有複合酸化物、およびチタン含有シリケートのグループから選択される少なくとも１種類の酸化物からなる、としている。酸化チタンは、アナターゼまたはルチルなどの種々の形態のチタニアを意味し、チタン含有複合酸化物は、チタニア−シルカ、チタニア−アルミナ、チタニア−ジルコニア、およびこれらに類似の高い比表面積を持つ限定された固体からなる、とも記載されているが、固体中のチタンの状態または基質の細孔がよく制御されていない混合酸化物である。チタン含有複合酸化物は、ＦｅＴｉＯ３、ＣａＴｉＯ３、およびＳｒＴｉＯ３などの化合物を含むとも記載されているが、これらは化学量論的および結晶構造的によく定義された物質であり、細孔構造を有しない。また、この特許のチタン含有酸化物は、チタンをシリカネットワーク中に含む細孔材料と記述され、好ましくは、例えば、アルミニウムが部分的にチタンで置換された、Ｘ型、Ｙ型、ＺＳＭ―５、ＺＳＭ―４８などのゼオライト材料を含む、チタン含有シリケートを含んでいる。これらの物質は公知であり、ミクロ細孔の細孔ネットワークのみを有するものである。チタン含有シリケートは、シリカが部分的にチタン原子で置換された、MCM−４１、MCM−４８、MCM−５０などの大きなメソ細孔を有する、メソ細孔シリカを含むとも記載されている。またチタン含有シリケートは、いわゆるＴＳ−１、ＴＳ−２などのチタノシリケートを含むと言われている。これらはミクロ細孔のポアネットワークのみを有する結晶性のチタン含有石英質ゼオライトである。最後に、チタン含有シリケートは、少量の酸化チタンが高度に分散した化学種としてチタン含有シリケート上に担持された場合を含むと言われている。この特許における広い酸化チタン材料の記述から、表面積の小さいまたは大きい従来化合物のすべての形態、ミクロ細孔のポアネットワークのゼオライト材料、メソ細孔のポアネットワークのメソ細孔材料、およびこれらの組み合わせが含まれることは明らかであるが、メソ細孔およびミクロ細孔のポアネットワークの両方を内部で結合するものについては言及していない。Patent Document 5 describes a catalyst in which ultrafine gold particles are immobilized on a titanium-containing oxide, which is used for the oxidation of hydrocarbons by oxygen in the presence of a reducing agent such as carbon monoxide, alcohol, formic acid, and cyclohexadiene. It is stated that the titanium-containing oxide is composed of at least one oxide selected from the group consisting of titanium oxide, titanium-containing composite oxide, and titanium-containing silicate. Titanium oxide means various forms of titania, such as anatase or rutile, and titanium-containing composite oxides are limited in having high specific surface area similar to titania-silica, titania-alumina, titania-zirconia, and the like. Although described as consisting of a solid, it is a mixed oxide in which the state of titanium in the solid or the pores of the substrate are not well controlled. Although titanium-containing composite oxides are also described as including compounds such as FeTiO 3 , CaTiO 3 , and SrTiO 3 , these are well-defined substances in terms of stoichiometry and crystal structure, and have a pore structure. Does not have. The titanium-containing oxide of this patent is also described as a pore material containing titanium in a silica network, preferably, for example, X-type, Y-type, ZSM-5, in which aluminum is partially replaced by titanium. , Including titanium-containing silicates, including zeolite materials such as ZSM-48. These substances are known and have only a microporous pore network. Titanium-containing silicates are also described as including mesoporous silica with large mesopores such as MCM-41, MCM-48, MCM-50, where the silica is partially substituted with titanium atoms. Titanium-containing silicates are said to contain so-called TS-1, TS-2 and other titanosilicates. These are crystalline titanium-containing quartz zeolites that have only microporous pore networks. Finally, titanium-containing silicates are said to include cases where small amounts of titanium oxide are supported on titanium-containing silicates as highly dispersed chemical species. From the description of the broad titanium oxide material in this patent, all forms of conventional compounds with small or large surface area, microporous pore network zeolite materials, mesoporous pore network mesoporous materials, and combinations thereof are described. Obviously, it does not mention what internally binds both the mesopore and micropore pore networks.
特許文献６には、チタン含有支持体上の金酸化物を含む組成物についての記載があり、チタン含有支持体はチタノシリケートにグラフトしたチタンを含むと記載されている。チタン含有支持体の好ましい具体例は、チタノシリケート上にグラフトしたチタン、および支持体上に分散したチタンを含んでいる。チタノシリケートにグラフトしたチタンは、ミクロ細孔を有している。支持体としてはチタンが付着することのできるあらゆる材料が可能であり、無定形、もしくはシリカライトまたはＭＣＭ−４１などの結晶性シリカが含まれる。これらは、それぞれミクロ細孔およびメソ細孔のみである。また支持体としては、アルミナ；アルミノシリケートおよびチタノシリケートなどの金属シリケート；１族および２族シリケートなどの活性を増大させた金属シリケート；ランタニドおよびアクチニド元素；ならびに他の耐火酸化物および類似の支持体材料が、可能である。さらに他のチタン含有支持体としては、ＴＳ−１、ＴＳ−２、Ｔｉ−β、Ｔｉ−ＭＣＭ−４１、およびＴｉ−ＭＣＭ−４８などの従来技術の多孔性結晶性チタノシリケートがある。これらもまた、ミクロ細孔またはメソ細孔のみである。支持体は、結晶性または無定形の化学量論的および非化学量論的な、活性を増大させた金属チタネートでもよい。これらは、１族、２族、ランタニドおよびアクチニド金属のチタネートを含んでおり；好ましくは、マグネシウムチタネート、カルシウムチタネート、バリウムチタネート、ストロンチウムチタネート、ナトリウムチタネート、カリウムチタネート、ならびにエルビウム、ルテチウム、トリウム、およびウラニウムのチタネートなどの化合物である。代替化合物として、無定形ならびにアナターゼ、ルチル、およびブロッカイト型チタン型二酸化チタンを含む結晶性酸化チタンを、チタン含有支持体として使用することができる。これらは本来ミクロ細孔またはメソ細孔を持たない化合物である。チタン含有支持体は、結晶性、準結晶性、または無定形でもよく、連結していない、または内部で連結しているミクロ細孔および／またはメソ細孔の規則正しいまたは不規則な配置を含んでもよい。チタンはミクロ細孔中のみに存在する。
以上記載したとおり、従来の含酸素有機化合物の製造方法に用いる触媒の担体として、メソ細孔を有する担体或いはミクロ細孔を有する担体を用いることは、それぞれすでに知られている。しかしながら、従来のＡｕ／Ｔｉ−ＭＣＭ−４１などの、メソ細孔を有する担体を用いた触媒の場合には、初期活性は高いが、触媒寿命が短いという欠点がある。一方、従来のＡｕ／ＴＳ−１などの、ミクロ細孔を有する担体を用いた触媒の場合は、触媒安定性は高いが、原料転化率が低いという欠点があった。
本発明は、以上のような事情に鑑みてなされたものであって、高い触媒安定性に加えて、高い原料転化率を可能とした、含酸素有機化合物を製造する方法を提供することを目的とするものである。As described above, the use of a carrier having mesopores or a carrier having micropores is already known as a catalyst carrier used in a conventional method for producing an oxygen-containing organic compound. However, in the case of a catalyst using a support having mesopores such as conventional Au / Ti-MCM-41, the initial activity is high, but there is a drawback that the catalyst life is short. On the other hand, in the case of a catalyst using a carrier having micropores such as conventional Au / TS-1, the catalyst stability is high, but the raw material conversion rate is low.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing an oxygen-containing organic compound that enables high raw material conversion in addition to high catalyst stability. It is what.
本発明者らは、上記課題を解決すべく鋭意検討したところ、メソ細孔を有する担体を用いた触媒であるＡｕ／Ｔｉ−ＭＣＭ−４１では、シリカのＳｉ骨格中のＴｉ原子の分散・固定のされ方が充分に制御されておらず、部分的にＴｉ−Ｏ−Ｔｉが形成され、その構造が、生成物の表面での重合反応を促進し、触媒活性の劣化をもたらす原因となるが、一方、ミクロ細孔を有する担体を用いた触媒であるＡｕ／ＴＳ−１では、シリカのＳｉ骨格中のＴｉ原子は、ゼオライト結晶構造中にしっかりと分散・固定されており、触媒活性の劣化をもたらす構造は形成されないが、孔径が小さく触媒反応に表面しか関与することができず、触媒活性（原料転化率）は充分ではないことが判明した。
そこで、本発明者らは、これらのそれぞれの長所を生かしつつ、欠点を克服する方法について研究を重ねたところ、ミクロ細孔を有する多孔体の微結晶を最初に生成し、それを種とした壁を形成するメソ細孔を有する多孔体の合成法を適用し、ミクロ−メソハイブリッド多孔体触媒を調製することにより、シリカのＳｉ骨格中のＴｉ原子は、ゼオライト結晶構造中にしっかりと分散・固定され、かつ、これらを壁材とするメソ構造体を形成することで、触媒活性部位を表面に多く露出させることができ、これにより上記の課題の解決が達成できることを見いだした。
更に、本発明者らは、メソ細孔を有する多孔体を合成するに際に用いるテンプレートが、アミン系界面活性剤である場合に、前述のハイブリッド効果が、顕著であることを見いだした。The inventors of the present invention have made extensive studies to solve the above-mentioned problems. As a result, Au / Ti-MCM-41, which is a catalyst using a support having mesopores, disperses and fixes Ti atoms in the Si skeleton of silica. However, Ti—O—Ti is partially formed, and the structure promotes the polymerization reaction on the surface of the product and causes deterioration of the catalytic activity. On the other hand, in Au / TS-1 which is a catalyst using a carrier having micropores, Ti atoms in the Si skeleton of silica are firmly dispersed and fixed in the zeolite crystal structure, and the catalytic activity is deteriorated. However, it was found that the pore size is small and only the surface can participate in the catalytic reaction, and the catalytic activity (raw material conversion) is not sufficient.
Therefore, the present inventors conducted research on a method for overcoming the drawbacks while taking advantage of each of these advantages, and firstly produced microcrystals of porous bodies having micropores, which were used as seeds. By applying a method for synthesizing a porous body having mesopores that form walls and preparing a micro-meso hybrid porous body catalyst, Ti atoms in the Si skeleton of silica are firmly dispersed in the zeolite crystal structure. It was found that by forming mesostructures that are fixed and using these as wall materials, a large number of catalytically active sites can be exposed on the surface, thereby achieving the solution to the above-mentioned problems.
Furthermore, the present inventors have found that the above-mentioned hybrid effect is remarkable when the template used for synthesizing a porous material having mesopores is an amine surfactant.
本発明は、かかる知見に基づいて、更に検討を重ねて完成されたものであって、以下の発明を提供するものである。
（１）メソ細孔構造を有する壁材がミクロ細孔構造を有するチタノシリケートの種結晶を含有する担体と、該担体上に分散担持された微細な金粒子とからなる触媒を用い、酸素源と還元剤を含む反応流体により炭化水素を酸化することを特徴とする含酸素有機化合物の製造方法。
（２）前記触媒が、さらに別の支持体上に保持されていることを特徴とする上記（１）の含酸素有機化合物の製造方法。
（３）前記金粒子の平均粒径が１０ｎｍ以下である上記（１）の含酸素有機化合物の製造方法。
（４）前記担体に、チタン原子が追加的にグラフトされていることを特徴とする上記（１１）の酸素有機化合物の製造方法。
（５）前記炭化水素が、飽和炭化水素である上記（１）の含酸素有機化合物の製造方法。
（６）前記炭化水素が、炭素数１〜４の飽和炭化水素である上記（１）の含酸素有機化合物の製造方法。
（７）前記炭化水素が、プロパンである上記（１）の含酸素有機化合物の製造方法。
（８）前記炭化水素が、不飽和炭化水素である上記（１）の含酸素有機化合物の製造方法。
（９）前記炭化水素が、炭素数２〜４の不飽和炭化水素である上記（１）の含酸素有機化合物の製造方法。
（１０）前記炭化水素が、プロピレンである上記（１）の含酸素有機化合物の製造方法。
（１１）前記酸素源が、酸素分子である上記（１）の含酸素有機化合物の製造方法。
（１２）前記酸素源が空気である上記（１）の含酸素有機化合物の製造方法。
（１３）前記酸素源が、オゾン及び亜酸化窒素を含む窒素酸化物である上記（１）の含酸素有機化合物の製造方法。
（１４）前記酸素源が、過酸化水素である上記（１）の含酸素有機化合物の製造方法。
（１５）前記還元剤が、水素である上記（１）の含酸素有機化合物の製造方法。
（１６）前記還元剤が、一酸化炭素、一酸化窒素、一酸化二窒素、アルコール、アルデヒド、フェノール、ギ酸、ギ酸エステル、シュウ酸、及びシクロヘキサジエンから選ばれるものである上記（１）の含酸素有機化合物の製造方法。
（１７）前記反応流体が、希釈剤を含む上記（１）の含酸素有機化合物の製造方法。
（１８）前記反応流体が、溶媒を含む上記（１）の含酸素有機化合物の製造方法。
（１９）前記担体が、アミン系界面活性剤を用いて合成したものであることを特徴とする上記（１）の含酸素有機化合物の製造方法。
（２０）酸素源と還元剤を含む反応流体により炭化水素を酸化して含酸素有機化合物を製造するのに用いられる触媒であって、メソ細孔構造を有する壁材がミクロ細孔構造を有するチタン含有シリケートの種結晶を含有する担体と、該担体上に分散担持された微細な金粒子とからなることを特徴とする炭化水素の酸化用触媒組成物。
（２１）前記触媒が、さらに別の支持体上に保持されていることを特徴とする上記（２０）の炭化水素の酸化用触媒組成物。
（２２）前記金粒子の平均粒子径が１０ｎｍ以下である上記（２０）の炭化水素の酸化用触媒組成物。
（２３）前記担体に、チタン原子が追加的にグラフトされていることを特徴とする上記（２０）の炭化水素の酸化用触媒組成物。
（２４）前記担体は、アミン系界面活性剤を用いて合成されたものであることを特徴とする上記（２０）の炭化水素の酸化用触媒組成物。The present invention has been completed through further studies based on such findings, and provides the following inventions.
(1) A wall material having a mesopore structure is composed of a support containing a titanosilicate seed crystal having a micropore structure and fine gold particles dispersed and supported on the support, and oxygen is used. A method for producing an oxygen-containing organic compound comprising oxidizing a hydrocarbon with a reaction fluid containing a source and a reducing agent.
(2) The method for producing an oxygen-containing organic compound according to (1), wherein the catalyst is held on another support.
(3) The method for producing an oxygen-containing organic compound according to (1), wherein the gold particles have an average particle size of 10 nm or less.
(4) The method for producing an oxygen organic compound according to (11) above, wherein titanium atoms are additionally grafted on the carrier.
(5) The method for producing an oxygen-containing organic compound according to (1), wherein the hydrocarbon is a saturated hydrocarbon.
(6) The method for producing an oxygen-containing organic compound according to (1), wherein the hydrocarbon is a saturated hydrocarbon having 1 to 4 carbon atoms.
(7) The method for producing an oxygen-containing organic compound according to (1), wherein the hydrocarbon is propane.
(8) The method for producing an oxygen-containing organic compound according to (1), wherein the hydrocarbon is an unsaturated hydrocarbon.
(9) The method for producing an oxygen-containing organic compound according to (1), wherein the hydrocarbon is an unsaturated hydrocarbon having 2 to 4 carbon atoms.
(10) The method for producing an oxygen-containing organic compound according to (1), wherein the hydrocarbon is propylene.
(11) The method for producing an oxygen-containing organic compound according to (1), wherein the oxygen source is an oxygen molecule.
(12) The method for producing an oxygen-containing organic compound according to (1), wherein the oxygen source is air.
(13) The method for producing an oxygen-containing organic compound according to (1), wherein the oxygen source is nitrogen oxide containing ozone and nitrous oxide.
(14) The method for producing an oxygen-containing organic compound according to (1), wherein the oxygen source is hydrogen peroxide.
(15) The method for producing an oxygen-containing organic compound according to (1), wherein the reducing agent is hydrogen.
(16) The inclusion of (1) above, wherein the reducing agent is selected from carbon monoxide, nitric oxide, dinitrogen monoxide, alcohol, aldehyde, phenol, formic acid, formic acid ester, oxalic acid, and cyclohexadiene. A method for producing an oxygen organic compound.
(17) The method for producing an oxygen-containing organic compound according to (1), wherein the reaction fluid contains a diluent.
(18) The method for producing an oxygen-containing organic compound according to (1), wherein the reaction fluid contains a solvent.
(19) The method for producing an oxygen-containing organic compound according to (1), wherein the carrier is synthesized using an amine surfactant.
(20) A catalyst used for producing an oxygen-containing organic compound by oxidizing a hydrocarbon with a reaction fluid containing an oxygen source and a reducing agent, and a wall material having a mesoporous structure has a microporous structure A catalyst composition for oxidizing hydrocarbons, comprising: a support containing a seed crystal of titanium-containing silicate; and fine gold particles dispersed and supported on the support.
(21) The catalyst composition for oxidizing hydrocarbons according to (20) above, wherein the catalyst is held on another support.
(22) The catalyst composition for oxidizing hydrocarbon according to (20), wherein the gold particles have an average particle size of 10 nm or less.
(23) The catalyst composition for oxidizing hydrocarbon according to (20) above, wherein titanium atoms are additionally grafted on the carrier.
(24) The catalyst composition for oxidizing hydrocarbon according to the above (20), wherein the carrier is synthesized using an amine surfactant.
本発明の方法に用いる触媒は、担体として、ミクロ細孔構造を有するチタノシリケートの種結晶が、メソ細孔構造を有する壁材中に含有されている、いわゆるミクロ−メソハイブリッド基質を用い、これに微細な金粒子を分散担持させたものであるため、本発明の方法によれば、原料転化率の向上と、触媒寿命の向上の両方を達成することができる。 The catalyst used in the method of the present invention uses a so-called micro-meso hybrid substrate in which a seed crystal of titanosilicate having a microporous structure is contained in a wall material having a mesoporous structure as a support, Since fine gold particles are dispersed and supported thereon, according to the method of the present invention, it is possible to achieve both improvement of the raw material conversion rate and improvement of the catalyst life.
本発明で触媒担体として用いる基質は、壁材中にミクロ細孔構造を有するエレメントを組み込んだ、メソ細孔構造の酸化物からなる。すなわち、壁材がメソ細孔構造を有し、その壁材が、ミクロ細孔構造を有する物質を含有するものであって、従来の触媒担体にはみられない、「ミクロ細孔」と「メソ細孔」の両構造を有する、いわゆる、ミクロ−メソハイブリッド基質である。
本発明において、好ましいミクロ細孔構造を有する物質は、チタン原子が孤立しており四面体配置であるチタン含有シリケートであって、Ｔｉ／Ｓｉ原子比として計算されるシリケート中のチタンの割合は、好ましくは１／１０００〜２０／１００であり、さらに好ましくは１／４００〜１０／１００である。また、該ミクロ細孔構造を有する物質は、アルミノシリケート、ガリウムシリケート、ジルコニウムホスフェート、アルミニウムホスフェート、および種々の多元素組成物などの他の組成物を含んでもよい。The substrate used as a catalyst carrier in the present invention is made of an oxide having a mesoporous structure in which an element having a microporous structure is incorporated in a wall material. That is, the wall material has a mesopore structure, and the wall material contains a substance having a micropore structure, and is not found in conventional catalyst supports, “micropore” and “ It is a so-called micro-meso hybrid substrate having both “mesopore” structures.
In the present invention, the material having a preferred micropore structure is a titanium-containing silicate in which titanium atoms are isolated and tetrahedrally arranged, and the proportion of titanium in the silicate calculated as the Ti / Si atomic ratio is: Preferably it is 1 / 1000-20 / 100, More preferably, it is 1 / 400-10 / 100. The material having the micropore structure may also include other compositions such as aluminosilicate, gallium silicate, zirconium phosphate, aluminum phosphate, and various multi-element compositions.
前記メソ細孔構造を有する担体の骨格となる酸化物は、どのような組成および構造でもよく、結晶性でも、非結晶性でも、または半結晶性材料でもよい。メソ細孔酸化物の細孔構造は、ランダムでも秩序のあるものでもよい。秩序のある細孔構造は、２次元ネットワークを構成しても、３次元ネットワークを構成してもよく、シングルモーダル、バイモーダル、または多モーダルでもよい。
また、このメソ細孔構造を有する担体には、チタン原子を追加的にグラフトすることができる。チタン原子を追加的にグラフトすることにより、触媒活性点の数を増やすことができ、原料転化率を主とする触媒性能の向上を図ることができる。The oxide serving as the skeleton of the carrier having the mesopore structure may have any composition and structure, and may be crystalline, non-crystalline, or semi-crystalline. The pore structure of the mesoporous oxide may be random or ordered. The ordered pore structure may constitute a two-dimensional network or a three-dimensional network, and may be single modal, bimodal, or multimodal.
In addition, titanium atoms can be additionally grafted to the carrier having this mesoporous structure. By additionally grafting titanium atoms, the number of catalytically active sites can be increased, and the catalyst performance mainly including the raw material conversion rate can be improved.
本発明の触媒を、さらに別の支持体上に分散または析出させることにより保持させてもよい。支持体を用いる目的は、触媒へのまたは触媒からの物質および熱移動を向上させ、さらに基質の安定性を向上するためである。該支持体には活性があってもなくてもよい。該支持体は、金属酸化物、または炭化物および窒化物などの非酸化物、ならびに種々の金属から作られてもよく、またチタンを含んでいても含まなくてもよい。例えば、アルミナ、シリカ、マグネシア、コーディエライト、酸化ジルコニウム、窒化ホウ素、炭化ケイ素などの材料を支持体として使用してもよい。該支持体は、ゼオライトなどの結晶性金属シリケート、メソ細孔材料、種々の金属から作られる発泡材料、種々の金属から作られるハニカム担体、種々の金属から作られるペレットなどであってもよい。 You may hold | maintain the catalyst of this invention by disperse | distributing or depositing on another support body. The purpose of using the support is to improve the mass and heat transfer to and from the catalyst and to further improve the stability of the substrate. The support may or may not be active. The support may be made from metal oxides, or non-oxides such as carbides and nitrides, and various metals, and may or may not contain titanium. For example, materials such as alumina, silica, magnesia, cordierite, zirconium oxide, boron nitride, and silicon carbide may be used as the support. The support may be a crystalline metal silicate such as zeolite, a mesoporous material, a foam material made from various metals, a honeycomb carrier made from various metals, a pellet made from various metals, and the like.
上記のミクロ−メソハイブリッド基質は、後に記載する実施例１ないし４に詳しく述べるが、最初に、ミクロ細孔構造を有するチタノシリケートの微結晶を生成し、それを種として、壁にメソ細孔を有する多孔体を調製することにより得られる。この種結晶からメソ細孔構造を有する壁材を製造する際に用いる界面活性剤は、特に限定されないが、アミン系界面活性剤を用いた場合には、触媒活性が向上するという効果が得られるので、例えば、臭化セチルトリメチルアンモニウム、ドデシルアミンなどのアミン系界面活性剤が好ましく用いられる。 The above-mentioned micro-meso hybrid substrate is described in detail in Examples 1 to 4 described later. First, titanosilicate microcrystals having a microporous structure are formed and used as seeds to form meso-fine particles on the wall. It is obtained by preparing a porous body having pores. The surfactant used when producing the wall material having a mesopore structure from the seed crystal is not particularly limited, but when an amine-based surfactant is used, an effect of improving the catalytic activity is obtained. Therefore, for example, amine surfactants such as cetyltrimethylammonium bromide and dodecylamine are preferably used.
本発明の触媒は、こうして得られたハイブリッド基質を触媒担体とし、該担体上に、金微粒子を分散担持させたもの、或いはさらに別の支持体に保持させたものであるが、金微粒子を担持させる方法としては、金の担持に一般的に用いられるいかなる方法も使用することができる。例えば、これらの方法には、析出沈殿、インシピエント湿式含浸法、湿式含浸法、イオン交換法、および化学蒸着法が含まれるが、これらに限定されるものではない。本発明において、金微粒子の析出は、好ましくは、ハイブリッド基質の形成後に行われる。
担体に担持される金微粒子は、その平均粒径が１０ｎｍ以下の微細な粒子であることが好ましい。
触媒中の金の割合は、チタン含有シリケートに対する重量基準で、少なくとも０．００１％、より好ましくは０．００５〜５％、さらに好ましくは０．０１〜２％である。
金の析出に前駆体として使用される金化合物の例としては、塩化金酸（ＨＡｕＣｌ４）、塩化金酸ナトリウム（ＮａＡｕＣｌ４）、シアン化金（ＡｕＣＮ）、シアン化金カリウム（ＫＡｕ（ＣＮ）２）、トリクロロジエチルアミン金酸（（Ｃ２Ｈ５）２ＮＨＡｕＣｌ３）があるが、これらには限定されない。The catalyst of the present invention is obtained by using the hybrid substrate thus obtained as a catalyst carrier, on which the gold fine particles are dispersed and supported, or further supported on another support, but the gold fine particles are supported. As a method of making it, any method generally used for supporting gold can be used. For example, these methods include, but are not limited to, precipitation, incipient wet impregnation, wet impregnation, ion exchange, and chemical vapor deposition. In the present invention, the gold fine particles are preferably deposited after the formation of the hybrid substrate.
The gold fine particles supported on the carrier are preferably fine particles having an average particle size of 10 nm or less.
The proportion of gold in the catalyst is at least 0.001%, more preferably 0.005 to 5%, still more preferably 0.01 to 2%, based on the weight with respect to the titanium-containing silicate.
Examples of gold compounds used as precursors for gold precipitation include chloroauric acid (HAuCl 4 ), sodium chloroaurate (NaAuCl 4 ), gold cyanide (AuCN), potassium gold cyanide (KAu (CN) 2 ), trichlorodiethylamineauric acid ((C 2 H 5 ) 2 NHAuCl 3 ), but is not limited to these.
本発明の方法において、炭化水素の酸化は気相で行っても、液相で行ってもよい。酸化剤としては、酸素を使用することができ、オプションとして還元剤を併用してもよい。
好ましい還元剤は水素であるが、一酸化炭素、一酸化窒素、シュウ酸、亜酸化窒素、オゾンなどの他の分子種でもよい。酸化剤として水または他の溶媒中の過酸化水素、ならびに反応系で作られる過酸化水素を使用することもできる。In the method of the present invention, the hydrocarbon oxidation may be carried out in the gas phase or in the liquid phase. As the oxidizing agent, oxygen can be used, and a reducing agent may be used in combination as an option.
The preferred reducing agent is hydrogen, but other molecular species such as carbon monoxide, nitric oxide, oxalic acid, nitrous oxide, and ozone may be used. Hydrogen peroxide in water or other solvents as well as hydrogen peroxide produced in the reaction system can be used as the oxidizing agent.
通常酸化反応は、反応物が可燃性または爆発性となる濃度範囲を避けるため、希釈剤を加えて行われる。また希釈剤は、発熱酸化反応により生成する熱の除去にも役立つ。使用される希釈剤は反応プロセスにより異なる。気相反応の場合、適切な希釈剤にはヘリウム、窒素、アルゴン、メタン、一酸化炭素、水蒸気、およびこれらの混合物が含まれるが、これに限定されない。液相反応の場合、希釈剤としては酸化および温度に安定である液体が使用できる。適切な液体希釈剤の例には、液体ポリエーテル、エステル、およびポリアルコールのみならず、脂肪族アルコール、塩素化脂肪族アルコール、塩素化炭化水素、芳香族炭化水素が含まれるが、これらに限定されない。 Usually, the oxidation reaction is performed with the addition of a diluent to avoid a concentration range in which the reactants are flammable or explosive. Diluents also help remove heat generated by the exothermic oxidation reaction. The diluent used depends on the reaction process. For gas phase reactions, suitable diluents include but are not limited to helium, nitrogen, argon, methane, carbon monoxide, water vapor, and mixtures thereof. In the case of a liquid phase reaction, a liquid that is stable to oxidation and temperature can be used as a diluent. Examples of suitable liquid diluents include but are not limited to liquid polyethers, esters, and polyalcohols, as well as aliphatic alcohols, chlorinated aliphatic alcohols, chlorinated hydrocarbons, aromatic hydrocarbons. Not.
本発明の方法において、炭化水素の使用量は、炭化水素、酸化剤、オプションとして使用される還元剤および希釈剤の全モル数の１モルパーセントを超え、９９モルパーセント未満としてもよい。酸化剤の使用量は、同じ基準で０．１モルパーセントを超え、５０モルパーセント未満とすることができる。オプションの還元剤の使用量は、同じ基準で０〜５０モルパーセントの範囲とすることができる。オプションである希釈剤の使用量は０〜９０モルパーセントの範囲とすることができる。 In the process of the present invention, the amount of hydrocarbon used may be greater than 1 mole percent and less than 99 mole percent of the total moles of hydrocarbon, oxidant, optional reducing agent and diluent. The amount of oxidant used can be greater than 0.1 mole percent and less than 50 mole percent on the same basis. The amount of optional reducing agent used can range from 0 to 50 mole percent on the same basis. The amount of diluent used as an option can range from 0 to 90 mole percent.
炭化水素としては、どのようなパラフィンまたはオレフィン、もしくは芳香族成分または非芳香族成分折との組み合わせも可能である。炭素数は２またはそれ以上である。炭化水素は、環式であることも非環式であることも可能であり、また官能基が置換されていても可能である。置換基には、ハロゲン、エーテル、エステル、アルコール、および他の成分が含まれるが、これに限定されない。 The hydrocarbon can be any paraffin or olefin, or combination with aromatic or non-aromatic components. The number of carbons is 2 or more. Hydrocarbons can be cyclic or acyclic, and can be substituted with functional groups. Substituents include, but are not limited to, halogens, ethers, esters, alcohols, and other components.
以下、本発明を実施例によってさらに具体的に説明するが、本発明はこれら実施例により何ら限定されるものではない。
<実施例１〜４に用いるチタノシリケート（ＴＳ−１）シードを組み込んだハイブリッドメソ多孔体の調製>
ＴＳ−１ゼオライトシードを含む前駆体溶液の調製は、１００ｇの水酸化テトラプロピルアンモニウム(ＴＰＡＯＨ，２０〜２５％、ＴＣＩ製)及び４０ｇの水を、４．１ｇのオルトチタン酸テトラブチル(ＴＢＯＴ、ＴＣＩ製)及び８３．２ｇのオルトケイ酸テトラエチル(ＴＥＯＳ，和光製)の混合物に、０℃で強く攪拌しながら滴下して加えて行った。
この混合物のモル組成は、ＳｉＯ２：ＴｉＯ２：ＴＰＡＯＨ：Ｈ２Ｏ＝１：０．０３：０．２７：１７であった。室温で１〜２時間連続して撹拌後、この澄んだ溶液を静置し１００℃で３時間熟成した。最終製品もまた透明な溶液であった。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
<Preparation of hybrid mesoporous material incorporating titanosilicate (TS-1) seed used in Examples 1-4>
The preparation of the precursor solution containing TS-1 zeolite seeds consisted of 100 g tetrapropylammonium hydroxide (TPAOH, 20-25%, manufactured by TCI) and 40 g water, 4.1 g tetrabutyl orthotitanate (TBOT, TCI). And 83.2 g of tetraethyl orthosilicate (TEOS, manufactured by Wako) was added dropwise at 0 ° C. with vigorous stirring.
The molar composition of this mixture was SiO 2 : TiO 2 : TPAOH: H 2 O = 1: 0.03: 0.27: 17. After stirring continuously at room temperature for 1-2 hours, the clear solution was allowed to stand and aged at 100 ° C. for 3 hours. The final product was also a clear solution.
（実施例１）
前記ＴＳ−１ゼオライトシードを使用して、ＭＣＭ−４１ハイブリッド（以下、「Ti-MCM-41 (H)」と表記する。）を合成した。
界面活性剤溶液の調製は、１１ｇのアミン系界面活性剤である臭化セチルトリメチルアンモニウム(ＣＴＡＢｒ、Aldrich製)を２８０ｍｌの水と７０ｍｌのＮＨ３・Ｈ２Ｏ(２５％水溶液、和光製)に、室温でマグネチックスターラーで撹拌しながら溶解して行った。この澄んだ界面活性剤溶液に、前記ＴＳ−１シードを含む５６．８ｇの前駆体溶液を強く撹拌ながら、滴下して加えた。得られた白色の混合物を室温で２４時間撹拌し、テフロン（登録商標）で内張りしたオートクレーブに入れ、１００℃で３０時間熟成した。最終生成物をろ過し、水で洗浄し、室温で一晩乾燥し、ついで５４０℃で４時間焼成した。Example 1
Using the TS-1 zeolite seed, an MCM-41 hybrid (hereinafter referred to as “Ti-MCM-41 (H)”) was synthesized.
The surfactant solution was prepared by adding 11 g of amine surfactant cetyltrimethylammonium bromide (CTABr, manufactured by Aldrich) to 280 ml of water and 70 ml of NH 3 .H 2 O (25% aqueous solution, manufactured by Wako). The solution was dissolved while stirring with a magnetic stirrer at room temperature. To this clear surfactant solution, 56.8 g of the precursor solution containing the TS-1 seed was added dropwise with vigorous stirring. The resulting white mixture was stirred at room temperature for 24 hours, placed in an autoclave lined with Teflon (registered trademark), and aged at 100 ° C. for 30 hours. The final product was filtered, washed with water, dried at room temperature overnight and then calcined at 540 ° C. for 4 hours.
（実施例２）
前記ＴＳ−１ゼオライトシードを使用して、ＨＭＳハイブリッド（以下、「Ti-HMS (H)」と表記する。）を合成した。
界面活性剤溶液の調製は、５．７ｇのアミン系界面活性剤であるドデシルアミン(ＤＤＡ、和光製)を６５ｇの水と６５ｇのエタノール(ＥｔＯＨ、和光製)に、室温でマグネチックスターラーで撹拌しながら溶解して行った。この澄んだ溶液に、前記ＴＳ−１シードを含む５６．８ｇの前駆体溶液を強く撹拌しながら、滴下して加えた。ｐＨは、ＨＣｌ水溶液(１Ｍ)を用い、約７〜８に調節した。得られた白色の混合物は、室温で２４時間撹拌した。最終生成物をろ過し、水で十分に洗浄し、室温で一夜乾燥し、ついで５４０℃で４時間焼成した。(Example 2)
Using the TS-1 zeolite seed, an HMS hybrid (hereinafter referred to as “Ti-HMS (H)”) was synthesized.
The surfactant solution was prepared by stirring 5.7 g of amine surfactant dodecylamine (DDA, manufactured by Wako) into 65 g of water and 65 g of ethanol (EtOH, manufactured by Wako) with a magnetic stirrer at room temperature. While dissolving. To this clear solution, 56.8 g of the precursor solution containing the TS-1 seed was added dropwise with vigorous stirring. The pH was adjusted to about 7-8 using aqueous HCl (1M). The resulting white mixture was stirred at room temperature for 24 hours. The final product was filtered, washed thoroughly with water, dried at room temperature overnight and then calcined at 540 ° C. for 4 hours.
（実施例３）
前記ＴＳ−１ゼオライトシードを使用して、ＳＢＡＳ−１５ハイブリッド（以下、「Ti-SBA-15 (H)」と表記する。)を合成した。
界面活性剤溶液の調製は、１０．０ｇのエチレンオキサイド系界面活性剤であるPluronic 123 (P123、BASF製)を水２６６ｍｌと５０ｍｌのＨＣｌ(３６％，和光製)に、４０℃でマグネチックスターラーで撹拌しながら溶解して行った。この澄んだ溶液に、前記ＴＳ−１シードを含む５６．８ｇの前駆体溶液を強く撹拌しながら、滴下して加えた。得られた白色の混合物を４０℃で２４時間撹拌し、テフロン（登録商標）で内張りしたオートクレーブに入れ、１００℃でさらに２４時間熟成した。最終生成物をろ過し、水で十分に洗浄し、室温で一晩乾燥し、ついで５４０℃で４時間焼成した。(Example 3)
SBAS-15 hybrid (hereinafter referred to as “Ti-SBA-15 (H)”) was synthesized using the TS-1 zeolite seed.
The surfactant solution was prepared by adding 10.0 g of ethylene oxide surfactant Pluronic 123 (P123, manufactured by BASF) to 266 ml of water and 50 ml of HCl (36%, manufactured by Wako) at 40 ° C. at a magnetic stirrer. And dissolved with stirring. To this clear solution, 56.8 g of the precursor solution containing the TS-1 seed was added dropwise with vigorous stirring. The resulting white mixture was stirred at 40 ° C. for 24 hours, placed in an autoclave lined with Teflon (registered trademark), and aged at 100 ° C. for another 24 hours. The final product was filtered, washed thoroughly with water, dried at room temperature overnight and then calcined at 540 ° C. for 4 hours.
（実施例４）
前記ＴＳ−１ゼオライトシードを使用し、ＭＳＵハイブリッド（以下、「Ti-MSU (H)」と表記する。）を合成した。
界面活性剤溶液の調製は、７．２ｇのエチレンオキサイド系界面活性剤であるTergitol 15-S-12 (T15-S-12, Aldrich製)を１００ｍｌの水に、室温でマグネチックスターラーで撹拌しながら溶解して行った。この澄んだ溶液に、ＴＳ−１シードを含む５６．８ｇの前駆体溶液を強く撹拌しながら、滴下して加えた。ｐＨは、ＨＣｌ水溶液(１Ｍ)を用い、約７〜８に調節した。得られた白色の混合物を室温で４８時間撹拌した。最終生成物をろ過し、水で十分に洗浄し、室温で一夜乾燥し、ついで５４０℃で４時間焼成した。Example 4
Using the TS-1 zeolite seed, an MSU hybrid (hereinafter referred to as “Ti-MSU (H)”) was synthesized.
The surfactant solution was prepared by stirring 7.2 g of ethylene oxide surfactant Tergitol 15-S-12 (T15-S-12, Aldrich) in 100 ml of water at room temperature with a magnetic stirrer. While dissolving. To this clear solution, 56.8 g of the precursor solution containing TS-1 seed was added dropwise with vigorous stirring. The pH was adjusted to about 7-8 using aqueous HCl (1M). The resulting white mixture was stirred at room temperature for 48 hours. The final product was filtered, washed thoroughly with water, dried at room temperature overnight and then calcined at 540 ° C. for 4 hours.
〈比較例１〜４に用いる従来型メソ多孔体の調製〉
実施例１〜４のミクロ細孔／メソ細孔ハイブリッドチタノシリケート基質との比較例を得るために、既存のＭＣＭ−４１、ＳＢＡ−１５、ＨＭＳ、及びＭＳＵ構造のメソ細孔チタノシリケートを、ＴＳ−１ゼオライトシードを含む前駆体溶液を使用する代わりに、オルトケイ酸テトラエチル（ＴＥＯＳ）とオルトチタン酸テトラブチル（ＴＢＯＴ）の混合物を使用して合成した。<Preparation of conventional mesoporous material used in Comparative Examples 1 to 4>
In order to obtain a comparative example with the micropore / mesopore hybrid titanosilicate substrate of Examples 1 to 4, the existing MCM-41, SBA-15, HMS, and MSU structure mesopore titanosilicates were used. Instead of using a precursor solution containing TS-1 zeolite seed, it was synthesized using a mixture of tetraethyl orthosilicate (TEOS) and tetrabutyl orthotitanate (TBOT).
（比較例１：既存のTi-MCM-41 (C)）
１１ｇのＣＴＡＢｒ（アミン系界面活性剤）を２８０ｍｌの水および７０ｍｌのＮＨ３・Ｈ２Ｏに室温で溶解して調製した。ついで、２０．８ｇのＴＥＯＳと１．０２ｇのＴＢＯＴを強く撹拌しながら、滴下して加えた。生成した混合物を室温で２４時間撹拌し、テフロン（登録商標）を内張りしたオートクレーブに入れ１００℃で、３６時間熟成した。最終生成物をろ過し、水で十分に洗浄し、室温で一夜乾燥し、さらに５４０℃で４時間焼成した(W. Zhang, M. Froba, J. Wang, P. T. Tanev, J.Wong, T. J. Pinnavaia, J. Am. Chem. Soc., 1996, 118, 9164; K. Lin, Z. Sun, S. Lin, D. Jiang, F. S. Xiao, Micropor. Mesopor. Mater., 2004, 193, 201)。(Comparative Example 1: Existing Ti-MCM-41 (C))
11 g of CTABr (amine surfactant) was prepared by dissolving in 280 ml of water and 70 ml of NH 3 .H 2 O at room temperature. Then 20.8 g TEOS and 1.02 g TBOT were added dropwise with vigorous stirring. The resulting mixture was stirred at room temperature for 24 hours, placed in an autoclave lined with Teflon (registered trademark), and aged at 100 ° C. for 36 hours. The final product was filtered, washed thoroughly with water, dried overnight at room temperature and calcined at 540 ° C. for 4 hours (W. Zhang, M. Froba, J. Wang, PT Tanev, J. Wong, TJ Pinnavaia J. Am. Chem. Soc., 1996, 118, 9164; K. Lin, Z. Sun, S. Lin, D. Jiang, FS Xiao, Micropor. Mesopor. Mater., 2004, 193, 201).
（比較例２：既存のTi-HMS (C)）
５．４ｇのＤＤＡ（アミン系界面活性剤）を２５ｍｌの水、３４．９ｇのＥｔＯＨ、および４０ｍｌのＨＣｌ（０．０５Ｍ）に撹拌しながら溶解し、調製した。ついで、２０．８ｇのＴＥＯＳと１．０２ｇのＴＢＯＴを強く撹拌しながら、滴下して加えた。得られた混合物を室温で４８時間撹拌した。最終生成物をろ過し、水で十分に洗浄し、室温で一夜乾燥し、ついで５４０℃で４時間焼成した( P. T. Tanev, M. Chibwe, T. J. Pinnavaia, Nature, 1994, 368, 321)。(Comparative Example 2: Existing Ti-HMS (C))
5.4 g DDA (amine surfactant) was prepared by dissolving in 25 ml water, 34.9 g EtOH, and 40 ml HCl (0.05 M) with stirring. Then 20.8 g TEOS and 1.02 g TBOT were added dropwise with vigorous stirring. The resulting mixture was stirred at room temperature for 48 hours. The final product was filtered, washed thoroughly with water, dried overnight at room temperature and then calcined at 540 ° C. for 4 hours (PT Tanev, M. Chibwe, TJ Pinnavaia, Nature, 1994, 368, 321).
（比較例３：既存の Ti-SBA-15 (C)）
１０．０ｇのＰ１２３（エチレンオキサイド系界面活性剤）を１００ｍｌの水に４０℃で溶解して調製した。他の溶液の調製は、１．０２ｇのＴＢＯＴを５０ｍｌのＨＣｌ（３６％）および２００ｍｌの水中で加水分解して行った。強く撹拌しながらＴＢＯＴ溶液をＰ１２３（エチレンオキサイド系界面活性剤）溶液に滴下して加え、不透明なむらのない溶液を得た。ついで、撹拌しながら２０．８ｇのＴＥＯＳを滴下して加えた。濁った溶液を４０℃で２４時間撹拌し、１００℃でさらに２４時間静置熟成した。最終生成物をろ過し、水で十分洗浄し、室温で一夜乾燥し、５４０℃で４時間焼成した(P. Yang, D. Zhao, D. I. Margolese, B. F. Chmelka, G. D. Stucky, Nature, 1998, 396, 152)。(Comparative Example 3: Existing Ti-SBA-15 (C))
10.0 g of P123 (ethylene oxide surfactant) was prepared by dissolving in 100 ml of water at 40 ° C. Another solution was prepared by hydrolyzing 1.02 g TBOT in 50 ml HCl (36%) and 200 ml water. The TBOT solution was added dropwise to the P123 (ethylene oxide surfactant) solution with vigorous stirring to obtain an opaque, non-uniform solution. Subsequently, 20.8 g of TEOS was added dropwise with stirring. The cloudy solution was stirred at 40 ° C. for 24 hours and aged by standing at 100 ° C. for another 24 hours. The final product was filtered, washed thoroughly with water, dried at room temperature overnight and calcined at 540 ° C. for 4 hours (P. Yang, D. Zhao, DI Margolese, BF Chmelka, GD Stucky, Nature, 1998, 396, 152).
（比較例４：既存のTi-MSU (C)）
７．２ｇのＴ１５−Ｓ−１２（エチレンオキサイド系界面活性剤）を１００ｇの水に溶解して、調製した。ついで、２０．８ｇのＴＥＯＳと１．０２ｇのＴＢＯＴを強く撹拌しながら、滴下して加えた。得られた混合物を、室温で２４時間撹拌した。最終生成物をろ過し、水で十分に洗浄し、室温で一夜乾燥し、ついで５４０℃で４時間焼成した(S. A. Bagshaw, E. Prouzet, T. J. Pinnavaia, Science, 1995, 269, 1242)。(Comparative Example 4: Existing Ti-MSU (C))
It was prepared by dissolving 7.2 g of T15-S-12 (ethylene oxide surfactant) in 100 g of water. Then 20.8 g TEOS and 1.02 g TBOT were added dropwise with vigorous stirring. The resulting mixture was stirred at room temperature for 24 hours. The final product was filtered, washed thoroughly with water, dried overnight at room temperature and then calcined at 540 ° C. for 4 hours (SA Bagshaw, E. Prouzet, TJ Pinnavaia, Science, 1995, 269, 1242).
（比較例５：従来型ミクロ多孔体（ゼオライト）の調製）
本比較例では、ミクロ細孔ＴＳ−１ゼオライトも比較のために調製した。代表的な調製方法では、２．０ｇのTween 20（Polyoxyethylene（20）Sorbitan Monolaurate、Aldrich製)を２４ｇの蒸留水と２７．３ｇの水酸化テトラプロピルアンモニウム(ＴＰＡＯＨ, ２０〜２５ｗｔ％水溶液、TCI製)との溶液に溶解した。ついで、強く撹拌しながら、３６ｇのＴＥＯＳを滴下して加えた。連続して１時間撹拌後、澄んだ溶液が得られた。約１．０２ｇのＴＢＯＴ(１８ｇの２−プロパノールに溶解)を強く撹拌しながら滴下して加えた。この混合物のモル組成はＳｉＯ２：ＴｉＯ２：ＴＰＡＨ：Tween 20：Ｈ２Ｏ＝１：０．０３：０．２７：０．００９：１４．５であった。撹拌を１時間継続した後、混合物をテフロン（登録商標）を内張りしたオートクレーブに移し、加熱炉に入れた。水熱反応による結晶化を１６０℃で１８時間行った。最終生成物を遠心分離により回収し、蒸留水で十分洗浄し、室温で一夜減圧乾燥し、ついで５４０℃で４時間焼成した(R. B. Khomane, B. D. Kulkarni, A. Paraskar, S. R. Sainkar, Mater. Chem. Phys., 2002, 76, 99)。(Comparative Example 5: Preparation of conventional microporous material (zeolite))
In this comparative example, microporous TS-1 zeolite was also prepared for comparison. In a typical preparation method, 2.0 g of Tween 20 (Polyoxyethylene (20) Sorbitan Monolaurate, manufactured by Aldrich) is mixed with 24 g of distilled water and 27.3 g of tetrapropylammonium hydroxide (TPAOH, 20-25 wt% aqueous solution, manufactured by TCI). ). Next, 36 g of TEOS was added dropwise with vigorous stirring. After stirring for 1 hour continuously, a clear solution was obtained. About 1.02 g TBOT (dissolved in 18 g 2-propanol) was added dropwise with vigorous stirring. The molar composition of this mixture was SiO 2 : TiO 2 : TPAH: Tween 20: H 2 O = 1: 0.03: 0.27: 0.009: 14.5. Stirring was continued for 1 hour, and then the mixture was transferred to an autoclave lined with Teflon (registered trademark) and placed in a heating furnace. Crystallization by hydrothermal reaction was performed at 160 ° C. for 18 hours. The final product was collected by centrifugation, washed thoroughly with distilled water, dried in vacuo at room temperature overnight, and then calcined at 540 ° C. for 4 hours (RB Khomane, BD Kulkarni, A. Paraskar, SR Sainkar, Mater. Chem. Phys., 2002, 76, 99).
ＵＶ−可視分光分析法による実施例１〜４及び比較例１〜４のキャラクタリゼーション結果を、それぞれ図1〜図４に示す。
図において、直線は、実施例のハイブリッド材料（Ｈ）と比較例の従来法によるもの（Ｃ）を示している。
２２０ｎｍ近傍のピークは、四面体構造のＴｉユニットの存在を示している。従来法によるもの（Ｃ）ではピークは長波長側へ広がっており、四面体ユニットは歪んでいることを示している。両方の材料で、３００ｎｍを超えるピークが存在しないことは、バルクのＴｉＯ２にあるようなＴｉ−Ｏ−Ｔｉ結合は存在しないことを示している。結論として、従来法によるもの（Ｃ）およびハイブリッド材料（Ｈ）ともに、四面体配置のＴｉを有するが、ハイブリッド材料（Ｈ）はより均一であり、Ｔｉが規則的なミクロ細孔としての存在することを示している。The characterization results of Examples 1 to 4 and Comparative Examples 1 to 4 by UV-visible spectroscopy are shown in FIGS.
In the figure, the straight line shows the hybrid material (H) of the example and the conventional method (C) of the comparative example.
The peak near 220 nm indicates the presence of a tetrahedral Ti unit. According to the conventional method (C), the peak spreads to the long wavelength side, indicating that the tetrahedral unit is distorted. In both materials, the absence of peaks above 300 nm indicates that there are no Ti—O—Ti bonds as in bulk TiO 2 . In conclusion, both the conventional method (C) and the hybrid material (H) have tetrahedrally arranged Ti, but the hybrid material (H) is more uniform and Ti exists as regular micropores. It is shown that.
異なるメソ細孔チタノシリケート基質の構造の、ＢＥＴ窒素吸着法によるキャラクタリゼーション結果を表１に示す。
平均細孔直径から（Ｄｐ＝４Ｖｐ／ＳＢＥＴ）の値からわかるように、材料の主な細孔はメソ細孔である。一方、実施例１〜４のハイブリッド材料（Ｈ）のミクロ細孔の割合は、Scatchard の方法 (P.J. Pomonis, D.E. Petrakis, A.K. Ladavos, K.M. Kolonia, G.S. Armatas, S.D. Sklari, P.C. Dragani, A. Zarlaha, V.N. Stathopoulus, A.T. Sdoukos, Micropor. Mesopor. Mater., 2004, 69, 97; J. Knowles, G. Armatas, M. Hudson, P. Pomonis, Langmuir, 2006, 22, 410) による計算から、比較例１〜４の従来法（Ｃ）の値より大きくなっており、このことから、ハイブリット材料（Ｈ）の壁にミクロ細孔を有するＴＳ−１構造を導入できていることが分かる。Table 1 shows the results of characterization of different mesoporous titanosilicate substrate structures by the BET nitrogen adsorption method.
As can be seen from the average pore diameter, the value of (D p = 4V p / S BET ), the main pores of the material are mesopores. On the other hand, the proportion of micropores in the hybrid materials (H) of Examples 1 to 4 was determined by the method of Scatchard (PJ Pomonis, DE Petrakis, AK Ladavos, KM Kolonia, GS Armatas, SD Sklari, PC Dragani, A. Zarlaha, VN Stathopoulus, AT Sdoukos, Micropor. Mesopor. Mater., 2004, 69, 97; J. Knowles, G. Armatas, M. Hudson, P. Pomonis, Langmuir, 2006, 22, 410), Comparative Example 1 It is larger than the value of the conventional method (C) of -4, and this shows that the TS-1 structure having micropores on the wall of the hybrid material (H) can be introduced.
（実施例５：Ａｕ担持法：ＤＰ法）
本実施例は、前記実施例及び比較例で調製した種々のチタノシリケート支持体上の、析出沈殿法（ＤＰ法）による金ナノ粒子触媒の調製方法の一般的な手法を示す。
代表的な調製方法においては、１００ｍｌの０．２４ｍＭ ＨＡｕＣｌ４・Ｈ２Ｏ(９９．０％、和光製)水溶液を強く撹拌しながら、７０℃に加熱した。溶液のｐＨは、１Ｍ Ｎａ２ＣＯ３溶液により８．７に調節した。ついで、１ｇの支持体を加え、懸濁液を１５分間撹拌した。５ｍｌの水に溶解した０．１９ｍｍｏｌのＢａ（ＮＯ３）２(Chamelon Reagent, 99.0%)を加え、ついで混合物をさらに４５分間、同じ温度およびｐＨで撹拌した。固体をろ過し、５０ｍｌの水で洗浄し、１２時間減圧乾燥し、ついで空気中で３００℃で４時間焼成した。(Example 5: Au support method: DP method)
This example shows a general method for preparing a gold nanoparticle catalyst by the precipitation method (DP method) on the various titanosilicate supports prepared in the above examples and comparative examples.
In a typical preparation method, 100 ml of 0.24 mM HAuCl 4 .H 2 O (99.0%, manufactured by Wako) aqueous solution was heated to 70 ° C. with vigorous stirring. The pH of the solution was adjusted to 8.7 with 1M Na 2 CO 3 solution. Then 1 g of support was added and the suspension was stirred for 15 minutes. 0.19 mmol of Ba (NO 3 ) 2 (Chamelon Reagent, 99.0%) dissolved in 5 ml of water was added and the mixture was then stirred for an additional 45 minutes at the same temperature and pH. The solid was filtered, washed with 50 ml of water, dried under reduced pressure for 12 hours and then calcined at 300 ° C. for 4 hours in air.
（実施例６：触媒活性評価法）
直径６ｍｍ長さ１８０ｍｍの石英製の管状マイクロリアクターを使用して、実施例５で調製した触媒０．３ｇを使用して、プロピレンのエポキシ化を行った。Ａｒ(９９．９％)、Ｏ２(９９．５％)、Ｈ２(９９．５％)、およびＣ３Ｈ６(９９．８％)の流速は、それぞれ２４．５ｃｍ３／ｍｉｎ、３．５ｃｍ３／ｍｉｎ、３．５ｃｍ３／ｍｉｎ、及び３．５ｃｍ３／ｍｉｎであり、マスフローメータにより制御した。反応圧力は０．１ＭＰａに設定した。反応開始前に、触媒をＡｒ(２７ｃｍ３／ｍｉｎ)で１０容量％に希釈したＨ２、およびＡｒ(２７ｃｍ３／ｍｉｎ)で１０容量％に希釈したＯ２によりそれぞれ、２５０℃で０．５時間前処理した。温度を１５０℃に設定し、反応物を供給した。反応生成物は、２台のガスクロマトグラフ(Shimazu GC-14)を使用し、オンラインで分析した。それぞれのガスクロマトグラフには、水素炎イオン検出器(FID)および熱伝導度検出器(TCD)が装備されていた。一方の装置にはFFAPキャピラリーカラム(０．３２ｍｍ×６０ｍ)および Porapak Q コンパクトカラム(３ｍｍ×２ｍ)が取り付けられていた。他方の装置には、MS-5A 60/80 コンパクトカラム(３ｍｍ×２ｍ)および Gaskuropak 54 84/100 コンパクトカラム（３ｍｍ×２ｍ)が取り付けられていた。FFAPキャピラリーカラムおよび Porapak Q は、酸素付加化合物 (アセトアルデヒド、PO、アセトン、プロピオンアルデヒド、アクロレイン、酢酸、およびイソプロパノール) およびＣＯ２の検出に、一方 MS-5A および Gaskuropak カラムは、ＣＯおよび炭化水素 (プロパン、プロピレン、エチレン、およびエタン) の検出にそれぞれ使用した。カーボンバランスはほぼ１００±３％であった。(Example 6: Evaluation method of catalyst activity)
Propylene epoxidation was performed using 0.3 g of the catalyst prepared in Example 5 using a quartz tubular microreactor 6 mm in diameter and 180 mm in length. The flow rates of Ar (99.9%), O 2 (99.5%), H 2 (99.5%), and C 3 H 6 (99.8%) were 24.5 cm 3 / min, 3 .5cm a 3 /min,3.5cm 3 / min, and 3.5 cm 3 / min, was controlled by a mass flow meter. The reaction pressure was set to 0.1 MPa. Before the start of the reaction, the catalyst Ar (27cm 3 / min) with H 2 was diluted to 10 volume%, and Ar (27cm 3 / min), respectively by O 2 diluted to 10 volume%, 0.5 at 250 ° C. Time pretreated. The temperature was set at 150 ° C. and the reaction was fed. The reaction products were analyzed online using two gas chromatographs (Shimazu GC-14). Each gas chromatograph was equipped with a flame ion detector (FID) and a thermal conductivity detector (TCD). One apparatus was fitted with an FFAP capillary column (0.32 mm × 60 m) and a Porapak Q compact column (3 mm × 2 m). The other device was fitted with an MS-5A 60/80 compact column (3 mm × 2 m) and a Gaskuropak 54 84/100 compact column (3 mm × 2 m). FFAP capillary columns and Porapak Q are for the detection of oxygenated compounds (acetaldehyde, PO, acetone, propionaldehyde, acrolein, acetic acid, and isopropanol) and CO 2 , while MS-5A and Gaskuropak columns are for CO and hydrocarbons (propane, Propylene, ethylene, and ethane) were used respectively. The carbon balance was approximately 100 ± 3%.
実施例１〜４、及び比較例１〜５のチタノシリケート基質上にＤＰ法（実施例５）により調製した金ナノ粒子触媒の反応性の結果を表２に示す。ハイブリッド材料の性能は、チタニアで置換された単純な固体に比べて、概して改良されている。特に、アミン系界面活性剤を用いた場合（実施例１、２）に、顕著な活性向上が確認された。 The reactivity results of the gold nanoparticle catalysts prepared by the DP method (Example 5) on the titanosilicate substrates of Examples 1 to 4 and Comparative Examples 1 to 5 are shown in Table 2. The performance of hybrid materials is generally improved over simple solids substituted with titania. In particular, when an amine surfactant was used (Examples 1 and 2), a significant improvement in activity was confirmed.
（実施例７：プロパン酸化活性：飽和炭化水素）
本実施例では、実施例６で説明した方法で調製した金を担持したチタノシリケートハイブリッド材料を使用する飽和炭化水素、すなわちプロパンの酸化方法について述べる。
実施例６に記載と類似の、リアクターおよび生成物のオンラインのキャラクタリゼーションを使用した。
代表的な反応では、金を担持したTi-HMS (H) の０．５５ｇを石英製の管状マイクロ リアクターに充填した。反応の前に、触媒はＡｒ(99.9 %)気流中で (２１ｃｍ３／ｍｉｎ、室温)、１７０℃、０．１ＭＰａの条件で、０．５時間、前処理を行った。ついで、Ｏ２(99.5 %)、Ｈ２(99.5 %)、およびＣ３Ｈ６(99.5 %) を導入し、反応圧力を０．３ＭＰａに調節した。反応ガス、Ａｒ、Ｏ２、Ｈ２、およびＣ３Ｈ６の流量は、それぞれ２１．０ｃｍ３／ｍｉｎ、３．０ｃｍ３／ｍｉｎ、３．０ｃｍ３／ｍｉｎ、および３．０ｃｍ３／ｍｉｎであった。反応の３０分後に、ガスクロマトグラフによるサンプリングを行った。プロパンの転化率は０．４５％で、主な反応生成物はアセトンで、その選択率は５７．５％であり、アセトンの生成速度は２．９ｇ／ｈ・Kgcatであった。
このことより、本触媒は、飽和炭化水素の酸化反応に対しても部分活性を有することが明らかとなった。(Example 7: Propane oxidation activity: saturated hydrocarbon)
In this example, a saturated hydrocarbon, that is, propane oxidation method using the titanosilicate hybrid material carrying gold prepared by the method described in Example 6 will be described.
Reactor and product online characterization similar to that described in Example 6 was used.
In a typical reaction, 0.55 g of Ti-HMS (H) carrying gold was loaded into a quartz tubular microreactor. Prior to the reaction, the catalyst was pretreated in an Ar (99.9%) stream (21 cm 3 / min, room temperature) at 170 ° C. and 0.1 MPa for 0.5 hour. Subsequently, O 2 (99.5%), H 2 (99.5%), and C 3 H 6 (99.5%) were introduced, and the reaction pressure was adjusted to 0.3 MPa. In the reaction gas, Ar, O 2, H 2, and C 3 flow rate of H 6 are each 21.0cm 3 /min,3.0cm 3 /min,3.0cm 3 / min , and 3.0 cm 3 / min there were. Sampling by gas chromatography was performed 30 minutes after the reaction. The conversion rate of propane was 0.45%, the main reaction product was acetone, its selectivity was 57.5%, and the production rate of acetone was 2.9 g / h · Kgcat.
From this, it became clear that this catalyst has partial activity also for the oxidation reaction of saturated hydrocarbons.
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| JP2007054711 | 2007-03-05 | ||
| JP2009502604A JP5017619B2 (en) | 2007-03-05 | 2008-03-05 | Method for producing oxygenated organic compound by oxidation of hydrocarbon and oxidation catalyst used therefor |
| PCT/JP2008/053934 WO2008108398A1 (en) | 2007-03-05 | 2008-03-05 | Process for producing oxygenic organic compound by oxidation of hydrocarbon and oxidation catalyst for use therein |
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| JPWO2008108398A1 true JPWO2008108398A1 (en) | 2010-06-17 |
| JP5017619B2 JP5017619B2 (en) | 2012-09-05 |
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| JP5093647B2 (en) * | 2007-03-19 | 2012-12-12 | 株式会社豊田中央研究所 | Method for producing metal oxide porous body having mesopores and micropores, metal oxide porous body having mesopores and micropores, and gas purification material using the same |
| DE102007039874B9 (en) * | 2007-08-20 | 2010-12-09 | Zylum Beteiligungsgesellschaft Mbh & Co. Patente Ii Kg | Process for the preparation of epoxides by oxidation of olefins in the homogeneous gas phase |
| WO2011051643A1 (en) * | 2009-10-29 | 2011-05-05 | Dow Global Technologies Inc. | Selective catalytic oxidation of c1-c3 alkanes |
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| JP4016121B2 (en) * | 1997-09-05 | 2007-12-05 | 独立行政法人産業技術総合研究所 | Hydrocarbon partial oxidation catalyst and method for producing oxygen-containing organic compound |
| KR100704141B1 (en) * | 1999-04-08 | 2007-04-09 | 다우 글로벌 테크놀로지스 인크. | Process for the hydro-oxidation of olefins to olefin oxides using oxidized gold catalyst and a composition comprising oxidized gold on a titanium-containing support |
| JP2005053808A (en) * | 2003-08-01 | 2005-03-03 | Kansai Tlo Kk | Method for producing organic compound with metallosilicate photocatalyst |
| JP4526907B2 (en) * | 2004-09-15 | 2010-08-18 | エヌ・イーケムキャット株式会社 | Titania-based oxidation catalyst for exhaust gas purification, catalyst structure for exhaust gas purification, and exhaust gas purification method |
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