JP5013396B2 - Catalyst for dehydration / hydrogenation of polyhydric alcohol having 3 carbon atoms and method for producing hydrocarbon using the same - Google Patents
Catalyst for dehydration / hydrogenation of polyhydric alcohol having 3 carbon atoms and method for producing hydrocarbon using the same Download PDFInfo
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Description
本発明は、炭素数３の多価アルコールを脱水／水素化して対応する同一炭素数（炭素数３）の炭化水素を合成する際に用いられる新規な触媒に関する。 The present invention relates to a novel catalyst used when synthesizing a corresponding hydrocarbon having the same carbon number (3 carbon atoms) by dehydrating / hydrogenating a polyhydric alcohol having 3 carbon atoms.
石油を原料とする化学工業の基幹物質であるプロピレンなどの炭化水素の工業的な製造方法は、１）900°C程度でのナフサのスチーム分解、２）プロパンの脱水素または酸化脱水素、などが代表的なものである。
他方、石油資源の枯渇の懸念と共に、非石油系原料とりわけバイオマス由来アルコールからのプロピレン製造方法の開発が、今後ますます必要になると予想されている。炭素数３の多価アルコール（以下、Ｃ３多価アルコールともいう）の原料としては、発酵法による1,2-プロパンジオール、バイオディーゼル製造の副生物であるグリセリン、などが原料として想定されており、これらC3多価アルコールから対応するプロピレン等のＣ３の炭化水素（以下、Ｃ３炭化水素ともいう）の合成方法が強く求められている。
The industrial production method of hydrocarbons such as propylene, which is a key material of the chemical industry using petroleum as a raw material, is 1) steam decomposition of naphtha at around 900 ° C, 2) propane dehydrogenation or oxidative dehydrogenation, etc. Is a typical one.
On the other hand, it is expected that development of a method for producing propylene from non-petroleum-based raw materials, particularly biomass-derived alcohol, will become more and more necessary in the future due to concerns about the exhaustion of petroleum resources. As raw materials for polyhydric alcohols with 3 carbon atoms (hereinafter also referred to as C3 polyhydric alcohols), 1,2-propanediol by fermentation and glycerin, a byproduct of biodiesel production, are assumed as raw materials. Therefore, a method for synthesizing a corresponding C3 hydrocarbon such as propylene (hereinafter, also referred to as C3 hydrocarbon) from these C3 polyhydric alcohols is strongly demanded.
しかしながら、一価のイソプロパノールの脱水によるプロピレン合成の例は多数知られているものの、Ｃ３多価アルコールからＣ３炭化水素を効率よく製造した例はあまり見あたらない。
最近、Ｃ３の多価アルコールの一つであるグリセリンを原料とし、これをPt/Al2O3触媒の存在下で改質ガス化して水素とCO2を得る方法が提案されている（非特許文献１）が、この反応は炭素−炭素結合を切断して、グリセリンを水素とCO2などのガスに変換するものであり、水素と共に0.7mol%程度(CO2の約1/50)のプロパンが得られることは記載されているとしても、炭素−炭素結合を保持したままで、脱水／水素化を行い、対応するＣ３炭化水素を得るものでなかった。
However, although many examples of propylene synthesis by dehydration of monovalent isopropanol are known, there are not many examples of efficiently producing C3 hydrocarbons from C3 polyhydric alcohols.
Recently, a method has been proposed in which glycerin, which is one of C3 polyhydric alcohols, is used as a raw material, and this is reformed in the presence of a Pt / Al2O3 catalyst to obtain hydrogen and CO2 (Non-patent Document 1). This reaction breaks the carbon-carbon bond and converts glycerin into hydrogen and gas such as CO2, and it is described that about 0.7 mol% (about 1/50 of CO2) propane can be obtained together with hydrogen. Even if it was, dehydration / hydrogenation was carried out while retaining the carbon-carbon bond, and the corresponding C3 hydrocarbon was not obtained.
また、ソルビトール(C6H8(OH)6)の脱水/水素化でヘキサン(選択率54mol%)やペンタン(同24mol%)と共に、7mol%のプロパンが副生する報告例(非特許文献２)があるが、この報告例には、Ｃ３の多価アルコールを用いた場合に果たしてどのような反応が生起し如何なる生成物が得られるか否かについて教示するものでなかった。 In addition, there is a report example (Non-patent Document 2) in which 7 mol% of propane is by-produced together with hexane (selectivity 54 mol%) and pentane (24 mol%) in the dehydration / hydrogenation of sorbitol (C6H8 (OH) 6). However, this report does not teach what kind of reaction occurs and what kind of product is obtained when a C3 polyhydric alcohol is used.
本発明は、グリセリンなどの炭素数３の多価アルコールの脱水／水素化により、高められた選択率と空時収率(STY)でプロピレンなどの炭素数３の炭化水素を合成することのできる新規な触媒、及びそれを用いたC3炭化水素の工業的に有利な製造方法を提供することを目的とする。 The present invention can synthesize C3 hydrocarbons such as propylene with increased selectivity and space time yield (STY) by dehydration / hydrogenation of C3 polyhydric alcohols such as glycerin. It is an object of the present invention to provide a novel catalyst and an industrially advantageous method for producing C3 hydrocarbons using the same.
本発明者らは、前記課題を解決すべく種々の触媒群について鋭意研究を重ねた結果、本発明を完成するに至った。
即ち、この出願によれば、以下の発明が提供される。
（１）触媒と、水素及び水の存在下、炭素数３の多価アルコールを脱水及び水素化して対応する炭素数３の炭化水素を合成する際に用いられる炭化水素合成用触媒であって、
白金化合物で修飾されたシリカ又はゼオライトからなることを特徴とする炭化水素合成用触媒。
（２）前記ゼオライトが、シリカ／アルミナ比が小さいゼオライトであることを特徴とする上記（１）の炭化水素合成用触媒。
（３）触媒と、水素及び水の存在下で、炭素数３の多価アルコールを脱水及び水素化して対応する炭素数３の炭化水素を合成する炭化水素の製造方法であって、
前記触媒として、白金化合物で修飾されたシリカ又はゼオライトからなる触媒を用いることを特徴とする炭化水素の製造方法。
（４）前記ゼオライトが、シリカ／アルミナ比が小さいゼオライトであることを特徴とする上記（３）の炭化水素の製造方法。
As a result of intensive studies on various catalyst groups in order to solve the above problems, the present inventors have completed the present invention.
That is, according to this application, the following invention is provided.
(1) A catalyst for hydrocarbon synthesis used in synthesizing a corresponding hydrocarbon having 3 carbon atoms by dehydrating and hydrogenating a C3 polyhydric alcohol in the presence of hydrogen and water,
Hydrocarbon synthesis catalyst, characterized in that it consists of modified silica or zeolite platinum of compounds.
(2) The hydrocarbon synthesis catalyst according to (1), wherein the zeolite is a zeolite having a small silica / alumina ratio.
(3) catalyst and medium, in the presence of hydrogen and water, a process for the preparation of hydrocarbons for synthesizing hydrocarbons with a carbon number of 3 corresponding dehydrated and hydrogenated polyhydric alcohols having 3 carbon atoms,
A method for producing hydrocarbons , wherein a catalyst comprising silica or zeolite modified with a platinum compound is used as the catalyst .
( 4 ) The method for producing a hydrocarbon according to (3), wherein the zeolite is a zeolite having a small silica / alumina ratio.
本発明の触媒を用いれば、水素及び水の存在下で、グリセリンなどの炭素数３の多価アルコールの脱水及び水素化により、高められた選択率と空時収率(STY)でプロピレンなどのC3炭化水素を合成することができる。 With the catalyst of the present invention, propylene and the like can be produced with increased selectivity and space-time yield (STY) by dehydration and hydrogenation of C3-polyhydric alcohols such as glycerin in the presence of hydrogen and water . C3 hydrocarbons can be synthesized.
本発明は、グリセリンなどのＣ３の多価アルコールを脱水／水素化して、プロピレンなどのC3の炭化水素を合成する際に用いられる触媒として、白金族金属を含む化合物で修飾された固体酸化物を用いたことを特徴としている。 The present invention relates to a solid oxide modified with a compound containing a platinum group metal as a catalyst used when dehydrating / hydrogenating a C3 polyhydric alcohol such as glycerin to synthesize a C3 hydrocarbon such as propylene. It is characterized by the use.
固体酸化物としては、白金族金属を含む化合物と共存、またはその表面に白金等の化合物を担持できるものであればいかなる酸化物も含まれるが、一般に触媒担体として知られている金属酸化物（非多孔性であっても多孔性であってもよい）や多孔性酸化物を用いることが好ましい。 The solid oxide includes any oxide as long as it can coexist with a compound containing a platinum group metal or can carry a compound such as platinum on the surface thereof, but is generally a metal oxide known as a catalyst support ( It may be non-porous or porous) and a porous oxide is preferably used.
金属酸化物としては、たとえば、シリカ、アルミナ、ジルコニア、チタニア、セリアなどの通常用いられる金属酸化物が挙げられる。またシリカ−アルミナなどの複合酸化物を用いることも可能である。 Examples of the metal oxide include commonly used metal oxides such as silica, alumina, zirconia, titania, and ceria. It is also possible to use a composite oxide such as silica-alumina.
多孔性酸化物としては、ゼオライト化合物などが挙げられる。
ゼオライト化合物としては、Y-型、L-型、モルデナイト、フェリエライト、ベータ型、H-ZSM-5などを挙げることができる。またゼオライト化合物以外の多孔性酸化物としては、TS-1、MCM-41、MCM-22、MCM-48、ガロシリケート、などの結晶性メタロシリケート、大口径シリカ化合物などを挙げることができる。
Examples of the porous oxide include zeolite compounds.
Examples of the zeolite compound include Y-type, L-type, mordenite, ferrierite, beta-type, and H-ZSM-5. Examples of the porous oxide other than the zeolite compound include crystalline metallosilicates such as TS-1, MCM-41, MCM-22, MCM-48, and gallosilicate, and large-diameter silica compounds.
またこれらの多孔性酸化物にはチタン、アルミニウム、バナジウム、ニオブ、タンタル、ホウ素、ジルコニウムなどの元素を含有するものや非晶質多孔性シリカ化合物も含まれる。 These porous oxides include those containing elements such as titanium, aluminum, vanadium, niobium, tantalum, boron, zirconium, and amorphous porous silica compounds.
これらの固体酸化物は、塩酸、硝酸、硫酸などにより表面処理してから用いることもできる。なお、本発明でとりわけ好ましく使用される固体酸化物は、グリセリン等をその細孔の中に包含でき、またグリセリンのOH基にプロトンを供給して脱水を促すことができる、シリカ／アルミナ比が小さなゼオライト化合物などを挙げることが出来る。 These solid oxides can be used after surface treatment with hydrochloric acid, nitric acid, sulfuric acid or the like. The solid oxide particularly preferably used in the present invention can include glycerin and the like in its pores, and can supply a proton to the OH group of glycerin to promote dehydration, and has a silica / alumina ratio. Small zeolite compounds can be mentioned.
本発明で用いる固体酸化物はその使用に当たって、白金族金属を含む化合物で修飾しておくことが必要である。修飾法としては、固体酸化物に白金等の化合物を含有させ、空気中で焼成する方法等が採られる。
ここで、白金族金属を含む化合物（以下、白金等の化合物ともいう）とは、白金、パラジウム、ルテニウム、ロジウム、オスミニウムおよびイリジウムの少なくとも一種を含む化合物を意味する。
The solid oxide used in the present invention must be modified with a compound containing a platinum group metal before use. As the modification method, a method of containing a compound such as platinum in a solid oxide and firing in air is adopted.
Here, the compound containing a platinum group metal (hereinafter also referred to as a compound such as platinum) means a compound containing at least one of platinum, palladium, ruthenium, rhodium, osmium and iridium.
固体酸化物に白金等の化合物を含有させる方法としては、物理混合法や，含浸法、沈殿法、混練法、インシピエントウェットネス法等の従来公知の方法を採用することが出来る。 As a method of incorporating a compound such as platinum into the solid oxide, a conventionally known method such as a physical mixing method, an impregnation method, a precipitation method, a kneading method, or an incipient wetness method can be employed.
白金等の化合物としては、代表的には、白金化合物、パラジウム化合物などが挙げられ、白金化合物としては、塩化白金酸、塩化第一白金アンモニウム、塩化第２白金ナトリウム、シアン化第一白金カリウム、ジクロロテトラアンミン白金、テトラミン硝酸白金、ビス−アセチルアセトナト白金、テトラキストリフェニルフォスフィン白金等が挙げられる。パラジウム化合物としては、酢酸パラジウム、ビス−アセチルアセトナトパラジウム、塩化パラジウム、四塩化パラジウムアンモニウム、六塩化パラジウムナトリウム、ジアミノ亜硝酸パラジウム、テトラキストリフェニルフォスフィンパラジウム、硝酸パラジウム、硫酸パラジウム等が挙げられる。 As a compound such as platinum, typically, a platinum compound, a palladium compound, and the like can be given. Examples of the platinum compound include chloroplatinic acid, ammonium platinum chloride, sodium platinum chloride, potassium potassium cyanide, Examples include dichlorotetraammine platinum, tetramine platinum nitrate, bis-acetylacetonatoplatinum, tetrakistriphenylphosphine platinum, and the like. Examples of the palladium compound include palladium acetate, bis-acetylacetonato palladium, palladium chloride, ammonium ammonium tetrachloride, sodium palladium hexachloride, palladium diaminonitrite, tetrakistriphenylphosphine palladium, palladium nitrate, and palladium sulfate.
これらの白金等の化合物は、通常、水溶液として固体酸化物に担持される。またアセトン、イソプロパノール、ベンゼンなどの有機溶媒も用いられる。白金等の化合物を含有させたシリカやゼオライト酸化物等の焼成温度は、300〜900℃，好ましくは500〜700℃程度である。白金等の担持量は、白金金属として、担体酸化物100g当たり、0.001〜10g、好ましくは0.1〜10gである。 These compounds such as platinum are usually supported on a solid oxide as an aqueous solution. Organic solvents such as acetone, isopropanol, and benzene are also used. The firing temperature of silica or zeolite oxide containing a compound such as platinum is about 300 to 900 ° C, preferably about 500 to 700 ° C. The supported amount of platinum or the like is 0.001 to 10 g, preferably 0.1 to 10 g, per 100 g of the carrier oxide as platinum metal.
本発明に用いる炭素数３の多価アルコールとしては、グリセリン、1,2-プロパンジオール、1,3-プロパンジオールを挙げることが出来る。 Examples of the polyhydric alcohol having 3 carbon atoms used in the present invention include glycerin, 1,2-propanediol, and 1,3-propanediol.
本達明による炭化水素の合成は、前記した触媒と、水素及び水の存在下で、グリセリン等を脱水及び水素化することにより、対応する同一炭素数の飽和または不飽和炭化水素に変換することにより実施される。
本発明の合成反応はグリセリンを例にとると以下の反応式で示すことができる。
すなわち、この合成反応は、脱水/水素化反応(下式(1))及び水蒸気改質(同(2)式)が通常併発し、全体では、グリセリンからC3炭化水素(プロピレン＋プロパン)、CO2及び水が生成していると考えられる(同(3)式)。
（化１）
7/2C3H5(OH)3 ＋7H2 → 7/2C3H6＋ 21/2H2O (1)
C3H5(OH)3 ＋3H2O → 3CO2 ＋ 7H2 (2)
9C3H5(OH)3 → 7C3H6 ＋6CO2 ＋ 15H2O (3)
Synthesis of hydrocarbons according to our Ming, the catalyst described above, in the presence of hydrogen and water, by dehydrating and hydrogenating glycerin, be converted to saturated or unsaturated hydrocarbons of the corresponding same carbon number Is implemented.
The synthesis reaction of the present invention can be represented by the following reaction formula when glycerin is taken as an example.
That is, in this synthesis reaction, a dehydration / hydrogenation reaction (the following formula (1)) and a steam reforming (the same formula (2)) are usually combined, and as a whole, glycerin is converted to C3 hydrocarbon (propylene + propane), CO2 In addition, it is considered that water is generated (formula (3)).
(Chemical formula 1)
7 / 2C 3 H 5 (OH) 3 + 7H 2 → 7 / 2C 3 H 6 + 21 / 2H 2 O (1)
C 3 H 5 (OH) 3 + 3H 2 O → 3CO 2 + 7H 2 (2)
9C 3 H 5 (OH) 3 → 7C 3 H 6 + 6CO 2 + 15H 2 O (3)
本発明の合成反応方法は気相及び液相のいずれで行うこともできるが、概して高沸点原料を対象としているため、液相がより好ましい。この場合の反応温度は、50〜500℃、好ましくは150〜300℃の条件下であり、また反応圧力は任意であるが加圧が好ましく、0.01Mpa〜100Mpa、好ましくは0.5MPa〜10MPaである。
雰囲気ガスには、反応として水素化を含むため、水素が用いられる。水素の使用割合は、多価アルコール１モル当たり、0.05〜50モル、好ましくは0.1〜5モルの割合である。また水素は、窒素、ヘリウム、アルゴンガス等の不活性ガスで希釈して用いることができる。
Although the synthetic reaction method of the present invention can be carried out in either a gas phase or a liquid phase, the liquid phase is more preferable because it generally targets high-boiling-point raw materials. In this case, the reaction temperature is 50 to 500 ° C., preferably 150 to 300 ° C., and the reaction pressure is arbitrary, but pressurization is preferable, and 0.01 MPa to 100 MPa, preferably 0.5 MPa to 10 MPa. .
The atmospheric gas, for containing hydrogen as reaction, hydrogen is used. The use ratio of hydrogen is 0.05 to 50 moles, preferably 0.1 to 5 moles per mole of polyhydric alcohol. Hydrogen can be diluted with an inert gas such as nitrogen, helium, or argon gas.
本発明では溶媒として水を共存させる。この場合の水の使用割合は、多価アルコール１モル当たり、0.05〜500モル、好ましくは0.5〜50モルの割合である。多価アルコールと水などの溶媒との相溶性は概して良いので、相分離することは少ないが、混合比によってはまれに２層に分離することも考えられるが、反応の進行上何ら影響はない。 In the present invention, water is allowed to coexist as a solvent . The proportion of water used in this case is 0.05 to 500 mol, preferably 0.5 to 50 mol, per mol of polyhydric alcohol. Since the compatibility between polyhydric alcohols and solvents such as water is generally good, phase separation is rare, but depending on the mixing ratio, it may be rarely separated into two layers, but there is no effect on the progress of the reaction. .
次に本発明を実施例によりさらに詳細に説明する。 Next, the present invention will be described in more detail with reference to examples.
実施例１
富士シリシア製シリカ(Cariact G-10)にジクロロテトラアンミン白金(白金換算で5wt%)を含浸させ、333Kで一晩乾燥、さらに373Kで3時間乾燥後、873Kで５時間空気焼成した。こうして得られた5%Pt/SiO2を１ｇ、グリセリン／水＝100mmol/220mmolを100mlのオートクレーブに入れ、水素と窒素の混合ガス(体積比(水素/窒素=84.3/15.7))を全圧2.0MPaにて導入して、523Kで12時間反応させた。反応後の生成物をガスクロマトグラフにより分析したところ，グリセリン転化率5.13%，C3炭化水素選択率20.3%、C3炭化水素空時収率85.8mmol/kg-cat/hにてC3炭化水素が生成した(表１)。副生物として，メタン、C2炭化水素、CO2の他(表１)、アセトン、1-プロパノール、ジエチルエーテルなどの含酸素化合物が少量検出された。
Example 1
Silica manufactured by Fuji Silysia (Cariact G-10) was impregnated with dichlorotetraammine platinum (5 wt% in terms of platinum), dried at 333 K overnight, further dried at 373 K for 3 hours, and then air calcined at 873 K for 5 hours. 1 g of 5% Pt / SiO2 thus obtained and glycerin / water = 100 mmol / 220 mmol were put into a 100 ml autoclave, and a mixed gas of hydrogen and nitrogen (volume ratio (hydrogen / nitrogen = 84.3 / 15.7)) was supplied at a total pressure of 2.0 MPa. And reacted at 523K for 12 hours. Analysis of the product after the reaction by gas chromatography revealed that C3 hydrocarbons were produced at a glycerol conversion of 5.13%, C3 hydrocarbon selectivity of 20.3%, and C3 hydrocarbon space time yield of 85.8 mmol / kg-cat / h. (Table 1). As by-products, a small amount of oxygen-containing compounds such as acetone, 1-propanol and diethyl ether were detected in addition to methane, C2 hydrocarbons and CO2 (Table 1).
グリセリン転化率，Cｎ炭化水素及びCOx選択率，C3空時収率は便宜的に以下のように計算した。
(1)グリセリン転化率= (ΣCn*n (n=1-4)+CO+CO2)/(GLY初期導入量) X 100.
ここでCnは炭素数ｎの炭化水素モル数(n=1-4)。
(2)Cｎ選択率 = （Cn*n）/((ΣCn*n: n=1-4)+CO+CO2)x100
COx選択率= (CO+CO2)/((ΣCn*n: n=1-4)+CO+CO2).
*は積を表す。
(3)C3空時収率 = C3 (mmol)/触媒量(1g)/反応時間(12h)
The glycerin conversion, Cn hydrocarbon and COx selectivity, and C3 space time yield were calculated as follows for convenience.
(1) Glycerin conversion rate = (ΣCn * n (n = 1-4) + CO + CO 2 ) / (GLY initial introduction amount) X 100.
Here, Cn is the number of moles of hydrocarbons having n carbon atoms (n = 1-4).
(2) Cn selectivity = (Cn * n) / ((ΣCn * n: n = 1-4) + CO + CO 2 ) x100
COx selectivity = (CO + CO2) / ((ΣCn * n: n = 1-4) + CO + CO 2 ).
* Represents a product.
(3) C3 space time yield = C3 (mmol) / amount of catalyst (1 g) / reaction time (12 h)
実施例２
Cariact G-10の代わりにH-モルデナイト(MOR)(シリカ/アルミナ比=240)を用い、同様に白金換算で5.0wt%担持／焼成することにより調製した5.0wt%Pt/H-MORを１ｇ用いた以外は実施例１と同様にして反応させたところ、グリセリン転化率1.16%，C3炭化水素選択率13.5%、C3炭化水素空時収率12.9mmol/kg-cat/hにてC3炭化水素が生成した(表１)。
Example 2
1 g of 5.0 wt% Pt / H-MOR prepared by loading / burning 5.0 wt% in the same manner as platinum using H-mordenite (MOR) (silica / alumina ratio = 240) instead of Cariact G-10 The reaction was carried out in the same manner as in Example 1 except that the glycerin conversion was 1.16%, the C3 hydrocarbon selectivity was 13.5%, and the C3 hydrocarbon space-time yield was 12.9 mmol / kg-cat / h. (Table 1).
比較例１
白金を使用せず、H-MOR担体のみを用いた以外、実施例２と同様にして反応させたところ、グリセリン転化率0.83%，C3炭化水素選択率4.71%、C3炭化水素空時収率3.21mmol/kg-cat/hとなり、実施例２に比べ、C3炭化水素選択率は1/3に、またC3空時収率は1/4に低下していることがわかる（表１）。
Comparative Example 1
The reaction was carried out in the same manner as in Example 2 except that only H-MOR carrier was used without using platinum. As a result, the glycerol conversion was 0.83%, the C3 hydrocarbon selectivity was 4.71%, and the C3 hydrocarbon space-time yield was 3.21. It becomes mmol / kg-cat / h, and it can be seen that the C3 hydrocarbon selectivity is reduced to 1/3 and the C3 space time yield is reduced to 1/4 compared to Example 2 (Table 1).
実施例３
ジクロロテトラアンミン白金の代わりにテトラミン硝酸白金を用い、担持率を0.5wt%、反応温度を498Kとした以外は実施例２と同様にして反応させたところ、グリセリン転化率1.77%，C3炭化水素選択率19.1%、C3炭化水素空時収率27.8mmol/kg-cat/hにてC3炭化水素が生成した(表１)。
Example 3
The reaction was conducted in the same manner as in Example 2 except that tetramine platinum nitrate was used in place of dichlorotetraammine platinum, the loading rate was 0.5 wt%, and the reaction temperature was 498 K. The glycerin conversion rate was 1.77% and the C3 hydrocarbon selectivity. C3 hydrocarbons were produced at 19.1%, C3 hydrocarbon space time yield of 27.8 mmol / kg-cat / h (Table 1).
実施例４
ジクロロテトラアンミン白金の担持率を1wt%、担体をH-ZSM-5(シリカ/アルミナ比=1900)、グリセリン／水のモル比を= 0.016mol/ 0.500molとした以外は実施例２と同様にして反応させたところ、グリセリン転化率1.95%，C3炭化水素選択率49.1%、C3炭化水素空時収率13.5mmol/kg-cat/h、と高められた選択率にてC3炭化水素が生成した(表１)。
Example 4
The same procedure as in Example 2 except that the loading ratio of dichlorotetraammine platinum was 1 wt%, the carrier was H-ZSM-5 (silica / alumina ratio = 1900), and the molar ratio of glycerol / water was 0.016 mol / 0.500 mol. As a result of the reaction, C3 hydrocarbons were produced with increased selectivity such as glycerol conversion 1.95%, C3 hydrocarbon selectivity 49.1%, C3 hydrocarbon space time yield 13.5 mmol / kg-cat / h ( Table 1).
実施例５
担体をH-モルデナイト(MOR)(シリカ/アルミナ比=18.3)を用い、グリセリン／水のモル比を= 0.016mol/ 0.500molとし、反応温度を270°Cとした以外は実施例２と同様にして反応させたところ、グリセリン転化率79.6%，C3炭化水素選択率30.4%、C3炭化水素空時収率367mmol/kg-cat/h、と圧倒的に高められたグリセリン転化率とC3空時収率にてC3炭化水素が生成した(表１)。
Example 5
The same procedure as in Example 2 was conducted except that H-mordenite (MOR) (silica / alumina ratio = 18.3) was used as the carrier, the molar ratio of glycerin / water was 0.016 mol / 0.500 mol, and the reaction temperature was 270 ° C. The glycerol conversion rate was 79.6%, the C3 hydrocarbon selectivity was 30.4%, and the C3 hydrocarbon space-time yield was 367 mmol / kg-cat / h. C3 hydrocarbons were produced at a rate (Table 1).
Claims (4)
白金化合物で修飾されたシリカ又はゼオライトからなることを特徴とする炭化水素合成用触媒。 A catalyst for synthesizing hydrocarbons used in synthesizing corresponding hydrocarbons having 3 carbon atoms by dehydrating and hydrogenating polyhydric alcohols having 3 carbon atoms in the presence of hydrogen and water,
Hydrocarbon synthesis catalyst, characterized in that it consists of modified silica or zeolite platinum of compounds.
前記触媒として、白金化合物で修飾されたシリカ又はゼオライトからなる触媒を用いることを特徴とする炭化水素の製造方法。 And catalyze, in the presence of hydrogen and water, a process for the preparation of hydrocarbons for synthesizing hydrocarbons with a carbon number of 3 corresponding dehydrated and hydrogenated polyhydric alcohols having 3 carbon atoms,
A method for producing hydrocarbons , wherein a catalyst comprising silica or zeolite modified with a platinum compound is used as the catalyst .
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