JP2010111618A - Method for producing hydrogenolysis product of polyhydric alcohol - Google Patents
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Abstract
Description
本発明は、多価アルコールからその水素化分解物を高収率で製造する方法、及びそれに用いる高活性な水素化分解触媒に関する。 The present invention relates to a method for producing a hydrocracked product from a polyhydric alcohol in high yield, and a highly active hydrocracking catalyst used therefor.
自然界から得られる多価アルコールを触媒を利用して水素化分解し、他の化合物に変換することは、物質の有効利用の観点から重要である。
一方、多価アルコールとして、食品や医療等に使用されているグリセリンは、年々生産量を増やしてきている。その理由として、化石化燃料の供給不安や、地球温暖化問題を背景にして延びてきたバイオディーゼル燃料の普及が挙げられる。植物原料から製造されるバイオディーゼル燃料はその製造過程でグリセリンを生成する。しかしながら、現状ではグリセリンの用途は限られていることから、供給過剰になりつつあり、その有効利用が求められている。その一つとして触媒反応を用いたＣ３アルコール類への変換が世界的に注目されている。
It is important from the viewpoint of effective utilization of a substance that a polyhydric alcohol obtained from nature is hydrocracked using a catalyst and converted to another compound.
On the other hand, the amount of glycerin used as a polyhydric alcohol in foods and medical care has been increasing year by year. Reasons for this include the fear of supplying fossil fuels and the prevalence of biodiesel fuel that has been growing against the background of global warming. Biodiesel fuel produced from plant raw materials produces glycerin during the production process. However, since the use of glycerin is limited at present, the supply is becoming excessive and its effective use is required. As one of them, conversion to C3 alcohols using a catalytic reaction has attracted attention worldwide.
Ｃ３アルコール類は、様々な工業原料等として有用である。Ｃ３アルコール類の中でジオール類としては、１，３−プロパンジオール及び１，２−プロパンジオールがあり、１，３−プロパンジオールは、ポリエステル及びポリウレタン原料等として注目されている。
一方、１，２−プロパンジオールは、例えばポリエステル樹脂、塗料、アルキッド樹脂、各種可塑剤、不凍液、ブレーキオイル等に用いられ、さらには食品保潤剤、果汁粘度増強剤、食品用セロハン柔軟剤、化粧品、医薬品等に有用である。
従来、１，２−プロパンジオールを製造する方法としては、グリセリンの水素化分解法が知られており、これまで種々の方法が提案されている。
C3 alcohols are useful as various industrial raw materials. Among the C3 alcohols, there are 1,3-propanediol and 1,2-propanediol as diols, and 1,3-propanediol is attracting attention as a polyester and polyurethane raw material.
On the other hand, 1,2-propanediol is used in, for example, polyester resins, paints, alkyd resins, various plasticizers, antifreezes, brake oils, and the like, and further includes food humectants, fruit juice viscosity enhancers, cellophane softeners for foods Useful for cosmetics, pharmaceuticals, etc.
Conventionally, glycerol hydrocracking is known as a method for producing 1,2-propanediol, and various methods have been proposed so far.
例えば、触媒として、（１）Ｃｕ−Ｒｅ／Ｃ、Ｃｕ−Ｎｉ／Ｃを用いる方法（例えば、特許文献１参照）、（２）Ｒｕ／Ｃを用いる方法（例えば、特許文献２参照）、（３）Ｃｕ−Ｚｎ／Ａｌ2Ｏ3を用いる方法（例えば、特許文献３参照）、（４）Ｃｕ−ＺｎＯを用いる方法（例えば、特許文献４参照）、（５）Ｃｕ−Ｃｒを用いる方法（例えば、非特許文献１参照）等が知られている。
しかしながら、これらの方法においては、グリセリンの転化率が低かったり、１，２−プロパンジオールの選択率が低かったりなどして、充分に満足し得るものではなかった。
For example, (1) a method using Cu—Re / C and Cu—Ni / C as a catalyst (for example, see Patent Document 1), (2) a method using Ru / C (for example, see Patent Document 2), ( 3) Method using Cu—Zn / Al 2 O 3 (see, for example, Patent Document 3), (4) Method using Cu—ZnO (see, for example, Patent Document 4), (5) Method using Cu—Cr ( For example, see Non-Patent Document 1).
However, these methods are not satisfactory because the conversion rate of glycerin is low and the selectivity of 1,2-propanediol is low.
本発明は、多価アルコールからその水素化分解物を高収率で製造する方法、及びそれに用いる高活性な水素化分解触媒を提供することを課題とする。 An object of the present invention is to provide a method for producing a hydrocracked product from a polyhydric alcohol in a high yield, and a highly active hydrocracking catalyst used therefor.
本発明者らは、多価アルコールの水素化分解触媒として、銅成分及び周期表第８〜１０族の第５〜６周期の元素成分を含む触媒を用いることにより、前記課題を解決し得ることを見出した。
すなわち、本発明は、次の（１）及び（２）を提供する。
（１）銅成分（ａ）、並びに周期表第８〜１０族の第５及び第６周期の元素から選ばれる少なくとも一種の元素成分（ｂ）を含む触媒の存在下に、多価アルコールと水素とを反応させる、多価アルコールの水素化分解物の製造方法。
（２）銅成分（ａ）、並びに周期表第８〜１０族の第５及び第６周期の元素から選ばれる少なくとも一種の元素成分（ｂ）を含む、多価アルコールの水素化分解触媒。
The present inventors can solve the above problems by using a catalyst containing a copper component and an element component of 5th to 6th periods of Groups 8 to 10 of the periodic table as a hydrocracking catalyst for polyhydric alcohol. I found.
That is, the present invention provides the following (1) and (2).
(1) a polyhydric alcohol and hydrogen in the presence of a catalyst comprising a copper component (a) and at least one elemental component (b) selected from the elements of groups 5 and 6 of groups 8 to 10 of the periodic table And a method for producing a hydrocracked product of a polyhydric alcohol.
(2) A polyhydric alcohol hydrocracking catalyst comprising a copper component (a) and at least one elemental component (b) selected from elements of groups 5 and 6 of Groups 8 to 10 of the periodic table.
本発明によれば、多価アルコールからその水素化分解物、特にグリセリンから１，２−プロパンジオールを高収率で製造する方法、及びそれに用いる高活性な水素化分解触媒を提供することができる。 According to the present invention, it is possible to provide a method for producing a hydrocracked product from a polyhydric alcohol, particularly 1,2-propanediol from glycerin in a high yield, and a highly active hydrocracking catalyst used therefor. .
本発明の多価アルコールの水素化分解物の製造方法においては、水素化分解触媒の存在下に、多価アルコールと水素とを反応させて、該多価アルコールを水素化分解する。
水素化分解の対象となる多価アルコールとしては、反応性の観点から、融点が１８０℃以下の化合物が好ましい。具体的には、水酸基数が２〜２０、好ましくは２〜１２、より好ましくは２〜６であって、かつ炭素数が３〜２０、好ましくは３〜１２、より好ましくは３〜６の脂肪族多価アルコール又は脂環式多価アルコールが挙げられる。これらの多価アルコールのうち、最も分子量の小さい化合物としては１，３−プロパンジオールが挙げられ、最も分子量の大きい化合物としては糖類が挙げられる。
In the method for producing a hydrocracked product of a polyhydric alcohol according to the present invention, the polyhydric alcohol is reacted with hydrogen in the presence of a hydrocracking catalyst to hydrocrack the polyhydric alcohol.
As the polyhydric alcohol to be hydrocracked, a compound having a melting point of 180 ° C. or lower is preferable from the viewpoint of reactivity. Specifically, the number of hydroxyl groups is 2-20, preferably 2-12, more preferably 2-6, and the carbon number is 3-20, preferably 3-12, more preferably 3-6. Group polyhydric alcohol or alicyclic polyhydric alcohol. Among these polyhydric alcohols, the compound having the smallest molecular weight includes 1,3-propanediol, and the compound having the largest molecular weight includes saccharides.
多価アルコールの置換基の位置関係としては、多価アルコールの主たる水酸基が結合している炭素原子から数えてγ位の炭素原子に、酸素原子を有する置換基が存在する場合が好ましい。酸素原子を有する置換基としては水酸基やエーテル基が好ましく、水酸基がさらに好ましい。
一方、酸素原子を有する置換基が、主たる水酸基が結合している炭素原子から数えてβ位にある場合やγ位より離れている場合は、該水酸基は反応しづらくなる。例えば、グリセリンや１，３−プロパンジオールは水素化分解され易いが、エチレングリコール、１，２−プロパンジオール、１，４−ブタンジオール等の反応性は低い。従って、発明に用いる多価アルコールとしては、特定の水酸基が結合している炭素原子から数えてγ位にある炭素原子に別の酸素原子を有する置換基を有する多価アルコールが好ましい。
As the positional relationship of the substituent of the polyhydric alcohol, a case where a substituent having an oxygen atom is present at the γ-position carbon atom counting from the carbon atom to which the main hydroxyl group of the polyhydric alcohol is bonded is preferable. The substituent having an oxygen atom is preferably a hydroxyl group or an ether group, more preferably a hydroxyl group.
On the other hand, when the substituent having an oxygen atom is in the β-position or away from the γ-position when counted from the carbon atom to which the main hydroxyl group is bonded, the hydroxyl group is difficult to react. For example, glycerin and 1,3-propanediol are easily hydrocracked, but the reactivity of ethylene glycol, 1,2-propanediol, 1,4-butanediol, etc. is low. Therefore, the polyhydric alcohol used in the invention is preferably a polyhydric alcohol having a substituent having another oxygen atom at the carbon atom at the γ-position counting from the carbon atom to which a specific hydroxyl group is bonded.
多価アルコールの好適例としては、１，３−プロパンジオール、ビス（３−ヒドロキシプロピル）エーテル、ビス（３−ヒドロキシブチル）エーテル、１，３−ブタンジオール、ペンタンジオール、ペンタントリオール、ヘキサンジオール、ヘキサントリオール、グリセリン、ジグリセリン、トリグリセリン、シクロヘキサンジオール、シクロヘキサントリオール、ペンタエリスリトール、トリメチロールプロパン、リボース、グルコース、スクロース、ソルビトールやマンニトールが挙げられる。これらの中では、グリセリン、ソルビトール、グルコースが好ましく、工業的観点から、特にグリセリンが好ましい。 Preferred examples of the polyhydric alcohol include 1,3-propanediol, bis (3-hydroxypropyl) ether, bis (3-hydroxybutyl) ether, 1,3-butanediol, pentanediol, pentanetriol, hexanediol, Examples include hexanetriol, glycerin, diglycerin, triglycerin, cyclohexanediol, cyclohexanetriol, pentaerythritol, trimethylolpropane, ribose, glucose, sucrose, sorbitol, and mannitol. In these, glycerol, sorbitol, and glucose are preferable, and glycerol is especially preferable from an industrial viewpoint.
また、本発明における多価アルコールの水素化分解物とは、多価アルコールに水素を作用させて、C−O結合を分解させて得られたものであり、少なくとも１つ以上の水酸基を残す程度に分解させて得られる化合物を意味する。例えば、グリセリン（分子内の水酸基数：３つ）の水素化分解物は、Ｃ３ジオール（分子内の水酸基：２つ）、Ｃ３モノオール（分子内の水酸基数：１つ）である。 In addition, the hydrocracked product of polyhydric alcohol in the present invention is obtained by causing hydrogen to act on polyhydric alcohol to decompose the C—O bond, and leaving at least one or more hydroxyl groups. Means a compound obtained by decomposition into For example, hydrogenolysis products of glycerin (number of hydroxyl groups in the molecule: 3) are C3 diol (hydroxyl groups in the molecule: 2) and C3 monool (number of hydroxyl groups in the molecule: 1).
前記水素化分解触媒としては、銅成分（ａ）、並びに周期表第８〜１０族の第５及び第６周期の元素から選ばれる少なくとも一種の元素成分（ｂ）を含む触媒が用いられる。周期表第８〜１０族の第５及び第６周期の元素としては、ルテニウム（Ｒｕ）、ロジウム（Ｒｈ）、パラジウム（Ｐｄ）、オスミウム（Ｏｓ）、イリジウム（Ｉｒ）、白金（Ｐｔ）が挙げられ、白金（Ｐｔ）、パラジウム（Ｐｄ）及びルテニウム（Ｒｕ）が好ましく、白金（Ｐｔ）が特に好ましい。
前記水素化分解触媒としては、銅成分（ａ）、並びに周期表第８〜１０族の第５及び第６周期の元素から選ばれる少なくとも一種の元素成分（ｂ）を担体に担持させた触媒を用いることができる。担体としては、シリカ、アルミナ、チタニア、ジルコニア、カーボン等が挙げられ、特にシリカが好ましい。
As the hydrocracking catalyst, a catalyst containing a copper component (a) and at least one elemental component (b) selected from the elements of the fifth and sixth periods of Groups 8 to 10 of the periodic table is used. Examples of the elements of the fifth and sixth periods of Groups 8 to 10 of the periodic table include ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt). Platinum (Pt), palladium (Pd) and ruthenium (Ru) are preferable, and platinum (Pt) is particularly preferable.
Examples of the hydrocracking catalyst include a catalyst in which a support is loaded with a copper component (a) and at least one elemental component (b) selected from the elements of the fifth and sixth periods of Groups 8 to 10 of the periodic table. Can be used. Examples of the carrier include silica, alumina, titania, zirconia, carbon and the like, and silica is particularly preferable.
本発明の水素化分解触媒中における銅成分（ａ）及び元素成分（ｂ）の含有割合は、触媒活性（多価アルコールの転化率及び水素化分解物の選択性）の観点から、以下のとおりである。
触媒中の銅成分（ａ）の含有量は、銅元素換算で、好ましくは０．１〜７０質量％、より好ましくは１〜６５質量％、更に好ましくは５〜６０質量％、特に好ましくは１０〜６０質量％である。
触媒中の元素成分（ｂ）の含有量は、該元素換算で、好ましくは０．００５〜１０質量％、より好ましくは０．０1〜８質量％、更に好ましくは０．０２〜５質量％である。
触媒中の〔銅成分（ａ）／元素成分（ｂ）〕の元素換算による質量比は、好ましくは１００／〔０．０１〜１０．０〕、より好ましくは１００／〔０．０５〜５．０〕である。
触媒の使用量は、原料である多価アルコール１００質量部に対して、好ましくは０．０１〜３０質量部、より好ましくは０．１〜２０質量部、更に好ましくは０．３〜１５質量部である。
The content ratio of the copper component (a) and the element component (b) in the hydrocracking catalyst of the present invention is as follows from the viewpoint of catalytic activity (conversion rate of polyhydric alcohol and selectivity of hydrocracked product). It is.
The content of the copper component (a) in the catalyst is preferably 0.1 to 70% by mass, more preferably 1 to 65% by mass, still more preferably 5 to 60% by mass, and particularly preferably 10 in terms of copper element. -60 mass%.
The content of the elemental component (b) in the catalyst is preferably 0.005 to 10% by mass, more preferably 0.01 to 8% by mass, and still more preferably 0.02 to 5% by mass in terms of the element. is there.
The mass ratio in terms of element of [copper component (a) / element component (b)] in the catalyst is preferably 100 / [0.01-10.0], more preferably 100 / [0.05-5. 0].
The amount of the catalyst used is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and still more preferably 0.3 to 15 parts by mass with respect to 100 parts by mass of the polyhydric alcohol as a raw material. It is.
触媒の調製方法としては特に制限はなく、従来公知の方法、例えば沈殿法、アルコキシド法、イオン交換法、蒸発乾固法、噴霧乾燥法、混練法等を採用することができる。
触媒調製に用いる銅成分（ａ）を含む化合物としては、水溶性銅塩が好ましく挙げられる。水溶性銅塩としては、硝酸銅、硫酸銅、酢酸銅、銅塩化物等が挙げられ、これらの中では硫酸第二銅、硝酸第二銅、塩化第二銅、及びそれらの混合物がより好ましい。
元素成分（ｂ）を含む化合物としては、水溶性化合物が好ましく挙げられる。
水溶性白金化合物としては、Ｐｔ（ＮＨ3）4（ＮＯ3）2、Ｐｔ（ＮＨ3）4Ｃｌ2、Ｈ2ＰｔＣｌ6等が挙げられ、水溶性パラジウム化合物としては、Ｐｄ（ＮＨ3）4（ＮＯ3）2、Ｐｄ（ＮＨ3）4Ｃｌ2、ＰｄＣｌ2、Ｐｄ（ＮＯ3）2等が挙げられ、水溶性ルテニウム化合物としては、Ｒｕ（ＮＯ）（ＮＯ3）ｘ（ＯＨ）ｙ（Ｘ＋Ｙ＝３）、ＲｕＣｌ3・ｘＨ2Ｏ、Ｒｕ（ＮＨ3）6Ｃｌ3等が挙げられる。
これらの中では、テトラアンミン白金（II）硝酸塩［Ｐｔ（ＮＨ3）4（ＮＯ3）2］、硝酸パラジウム［Ｐｄ（ＮＯ3）2］、水溶性ルテニウム化合物［Ｒｕ（ＮＯ）（ＮＯ3）ｘ（ＯＨ）ｙ（Ｘ＋Ｙ＝３）］水溶液等がより好ましい。
The method for preparing the catalyst is not particularly limited, and conventionally known methods such as precipitation, alkoxide, ion exchange, evaporation to dryness, spray drying, kneading and the like can be employed.
As a compound containing the copper component (a) used for catalyst preparation, water-soluble copper salt is mentioned preferably. Examples of water-soluble copper salts include copper nitrate, copper sulfate, copper acetate, copper chloride, etc. Among these, cupric sulfate, cupric nitrate, cupric chloride, and mixtures thereof are more preferable. .
Preferred examples of the compound containing the element component (b) include water-soluble compounds.
Examples of water-soluble platinum compounds include Pt (NH 3 ) 4 (NO 3 ) 2 , Pt (NH 3 ) 4 Cl 2 , H 2 PtCl 6 , and examples of water-soluble palladium compounds include Pd (NH 3 ) 4. (NO 3 ) 2 , Pd (NH 3 ) 4 Cl 2 , PdCl 2 , Pd (NO 3 ) 2 and the like can be mentioned. As the water-soluble ruthenium compound, Ru (NO) (NO 3 ) x (OH) y ( X + Y = 3), RuCl 3 .xH 2 O, Ru (NH 3 ) 6 Cl 3 and the like.
Among these, tetraammineplatinum (II) nitrate [Pt (NH 3 ) 4 (NO 3 ) 2 ], palladium nitrate [Pd (NO 3 ) 2 ], water-soluble ruthenium compound [Ru (NO) (NO 3 ) x (OH) y (X + Y = 3)] aqueous solution and the like are more preferable.
触媒を沈殿法又はアルコキシド法で調製する場合、例えば以下に示す方法を用いることができる。
沈殿法では、シリカ等の担体を分散させたアルカリ性水溶液に、水溶性銅塩を滴下し、銅水酸化物の沈殿を生成させ、固液分離した後、分離された沈殿を充分に水洗後、乾燥処理し、さらに１００〜１２００℃程度、好ましくは３００〜９００℃の温度で焼成処理する。得られた粉末状の触媒は、必要に応じ、従来公知の方法により、粒状化し、メジアン径が０．１〜５００μｍ程度、好ましくは０．４〜２００μｍの粒状物としてもよい。
また、アルコキシド法では、水溶性銅塩と多価アルコール（例えば、エチレングリコールやプロピレングリコール等）からなるスラリーにテトラアルコキシシラン（例えば、テトラエトキシシラン、テトラメトキシシラン等）を滴下攪拌し、その後、水により加水分解し沈殿させ、固液を分離した後、乾燥処理し、さらに１００〜１２００℃程度、好ましくは３００〜９００℃の温度で焼成処理する。得られた粉末状の触媒は、必要に応じ、従来公知の方法により、粒状化し、メジアン径が０．１〜５００μｍ程度、好ましくは０．４〜２００μｍの粒状物としてもよい。
触媒に含有又は担持された酸化銅の平均一次粒子径は、好ましくは１〜１００ｎｍ、より好ましくは５〜８０ｎｍ、更に好ましくは１０〜６０ｎｍである。
When preparing a catalyst by a precipitation method or an alkoxide method, the method shown below can be used, for example.
In the precipitation method, a water-soluble copper salt is dropped into an alkaline aqueous solution in which a carrier such as silica is dispersed to form a copper hydroxide precipitate, and after solid-liquid separation, the separated precipitate is sufficiently washed with water, It is dried and further baked at a temperature of about 100 to 1200 ° C., preferably 300 to 900 ° C. The obtained powdery catalyst may be granulated by a conventionally known method, if necessary, and may be a granular material having a median diameter of about 0.1 to 500 μm, preferably 0.4 to 200 μm.
In the alkoxide method, tetraalkoxysilane (for example, tetraethoxysilane, tetramethoxysilane, etc.) is dropped and stirred into a slurry composed of a water-soluble copper salt and a polyhydric alcohol (for example, ethylene glycol or propylene glycol), and then After hydrolyzing and precipitating with water and separating the solid and liquid, it is dried and further baked at a temperature of about 100 to 1200 ° C., preferably 300 to 900 ° C. The obtained powdery catalyst may be granulated by a conventionally known method, if necessary, and may be a granular material having a median diameter of about 0.1 to 500 μm, preferably 0.4 to 200 μm.
The average primary particle size of the copper oxide contained or supported on the catalyst is preferably 1 to 100 nm, more preferably 5 to 80 nm, and still more preferably 10 to 60 nm.
本発明においては、上記の調製法にて得られた銅／担体触媒に元素成分（ｂ）を含む水溶性化合物の水溶液を添加し、乾燥した後、例えば２００〜６００℃で焼成し、目的の触媒を得ることができる。
また、本発明の触媒を沈殿法で調製する場合に、シリカ等の担体を分散させたアルカリ性水溶液に、水溶性銅塩と、水溶性白金化合物や水溶性パラジウム化合物等を滴下し、それらの金属の水酸化物の沈殿を生成させ、以下、前記の沈殿法と同様の操作を行って調製することもできる。
さらに、本発明の触媒をアルコキシド法で調製する場合に、水溶性銅塩と、水溶性白金化合物や水溶性パラジウム化合物等と、多価アルコールとからなるスラリーにテトラアルコキシシランを滴下攪拌し、以下、前記のアルコキシド法と同様の操作を行って調製することもできる。
In the present invention, an aqueous solution of a water-soluble compound containing the element component (b) is added to the copper / support catalyst obtained by the above preparation method, dried, and calcined at, for example, 200 to 600 ° C. A catalyst can be obtained.
Further, when the catalyst of the present invention is prepared by a precipitation method, a water-soluble copper salt, a water-soluble platinum compound, a water-soluble palladium compound, or the like is dropped into an alkaline aqueous solution in which a carrier such as silica is dispersed, and these metals are added. It can also be prepared by generating a hydroxide precipitate and performing the same operation as the precipitation method described above.
Furthermore, when the catalyst of the present invention is prepared by the alkoxide method, tetraalkoxysilane is added dropwise to a slurry comprising a water-soluble copper salt, a water-soluble platinum compound or a water-soluble palladium compound, and a polyhydric alcohol. It can also be prepared by performing the same operation as in the alkoxide method.
本発明の多価アルコールの水素化分解物の製造方法においては、製造工程を簡略化する観点から、反応溶媒を用いないことが好ましいが、反応溶媒を用いて、多価アルコールの水素化分解を行うこともできる。
反応溶媒としては、プロトン性溶媒が好ましく、例えば、水、メタノール、エタノール、１−プロパノール、２−プロパノール、ｎ−ブタノール、イソブタノール、１，２−プロパンジオール、エチレングリコール等の群から選ばれる少なくとも１種を用いることができる。これらの中では、反応性の観点から、水を含有するものが好ましい。
反応溶媒の使用量は、多価アルコールの含有量が１質量％以上の溶液になるように選択することが好ましく、１０質量％以上の溶液となるように選択ことがより好ましい。
本発明の方法において、原料となる水素ガスは、そのまま又は窒素、アルゴン、ヘリウム等の不活性ガスで希釈して用いることができる。
また、反応溶媒以外の添加剤、例えば、酸や塩基等を用いて反応することも可能であるが、製造工程の簡略化の観点から、特に本反応系では添加剤を用いないことが好ましい。
In the method for producing a hydrocracked product of a polyhydric alcohol of the present invention, it is preferable not to use a reaction solvent from the viewpoint of simplifying the production process, but hydrogenation of a polyhydric alcohol is performed using a reaction solvent. It can also be done.
The reaction solvent is preferably a protic solvent, for example, at least selected from the group of water, methanol, ethanol, 1-propanol, 2-propanol, n-butanol, isobutanol, 1,2-propanediol, ethylene glycol and the like. One type can be used. In these, the thing containing water is preferable from a reactive viewpoint.
The amount of the reaction solvent used is preferably selected so that the polyhydric alcohol content is 1% by mass or more, and more preferably 10% by mass or more.
In the method of the present invention, the hydrogen gas used as a raw material can be used as it is or diluted with an inert gas such as nitrogen, argon or helium.
Moreover, although it is possible to react using additives other than a reaction solvent, for example, an acid, a base, etc., it is preferable not to use an additive especially in this reaction system from a viewpoint of simplification of a manufacturing process.
反応条件については特に制限はなく、使用する多価アルコールや触媒の種類等に応じて適宣選定される。水素圧は、通常、３０ＭＰａ以下が好ましく、０．１〜１０ＭＰａがより好ましく、０．５〜３ＭＰａが更に好ましい。反応温度は、通常８０℃以上で水素化分解を実施することができるが、多価アルコールの水素化分解による転化率及び分解生成物の選択性等の観点から、１３０〜３５０℃が好ましく、１５０〜２５０℃がより好ましく、特にＰＧの選択性及びＥＧ副生量の観点から１６０〜２００℃がより好ましく、１７０℃〜１９０℃が更に好ましい。
水素化分解反応は、回分式及び連続式のいずれも採用することができるが、回分式がより好ましい。また、水素密閉系及び水素流通系のいずれも採用することができるが、水素流通系がより好ましい。
反応装置としては特に制限はなく、オートクレーブ等の加圧可能な装置や、固定床流通式の装置等を用いることができる。
There are no particular restrictions on the reaction conditions, and the reaction conditions are appropriately selected according to the type of polyhydric alcohol and catalyst used. The hydrogen pressure is usually preferably 30 MPa or less, more preferably 0.1 to 10 MPa, and still more preferably 0.5 to 3 MPa. The reaction temperature can usually be hydrocracked at 80 ° C. or higher, but is preferably 130 to 350 ° C. from the viewpoint of the conversion rate of the polyhydric alcohol by hydrocracking, the selectivity of the cracked product, and the like. -250 degreeC is more preferable, 160-200 degreeC is more preferable from a viewpoint of the selectivity of PG and the amount of EG by-products, and 170 degreeC-190 degreeC is still more preferable.
As the hydrocracking reaction, either a batch system or a continuous system can be adopted, but a batch system is more preferable. Moreover, although both a hydrogen sealing system and a hydrogen circulation system can be adopted, a hydrogen circulation system is more preferable.
There is no restriction | limiting in particular as a reaction apparatus, The apparatus which can be pressurized, such as an autoclave, a fixed bed flow-type apparatus, etc. can be used.
本発明の多価アルコールの水素化分解物の製造方法においては、多価アルコールとしてグリセリンを用いることが好ましい。このグリセリンを用いることにより、水素化分解物として、１，２−プロパンジオールを高収率で製造することができる。
本発明は、また、銅成分（ａ）、並びに周期表第８、９及び１０族の第５及び第６周期の元素から選ばれた少なくとも一種の元素成分（ｂ）を含む、多価アルコールの水素化分解触媒をも提供する。
In the method for producing a hydrogenolysis product of a polyhydric alcohol of the present invention, glycerin is preferably used as the polyhydric alcohol. By using this glycerin, 1,2-propanediol can be produced in high yield as a hydrocracked product.
The present invention also provides a polyhydric alcohol comprising a copper component (a) and at least one elemental component (b) selected from the elements of the fifth and sixth periods of Groups 8, 9 and 10 of the periodic table. A hydrocracking catalyst is also provided.
以下の実施例及び比較例において、特記しない限り「％」は「質量％」を意味する。
実施例１
（１）銅−白金／シリカ触媒の調製
還流冷却器を有する反応器に、エチレングリコール（２００ｇ）、硝酸第二銅三水和物（７６ｇ）を加え、８０℃で２時間加熱攪拌後、テトラエトキシシラン（５２ｇ）を滴下し８０℃で２時間加熱攪拌した。その後、水（１８ｇ）を滴下し８０℃で３時間加熱攪拌し沈澱物を得た。生成した沈殿物を約１２０℃で乾燥させ、４００℃で２時間、空気中で焼成し、銅／シリカ触媒（銅含有量５０％）を得た。
得られた銅／シリカ触媒（３ｇ）に、テトラアンミン白金（II）硝酸塩［Ｐｔ（ＮＨ3）4（ＮＯ3）2］（２９．８ｍｇ）の水溶液を添加し、ロータリーエバポレーターで乾燥乾固させた。得られた固体を１２０℃で乾燥させ、４００℃で２時間、空気中で焼成し、銅−白金／シリカ触媒（Ｃｕ／Ｐｔ／Ｓｉ＝５０／０．５／１７）（銅含有量５０％）を得た。
得られた触媒の酸化銅の平均一次粒子径は４４ｎｍであった。
なお、一次粒子径の測定は、Ｘ線回折装置（理学電機株式会社製、型式：ＵＬＴＲＡ Ｘ １８ＶＢ２−３、Ｘ線源ＣｕＫ α線、電圧４０ｋＶ、電流１２０ｍＡ）で測定を行い、解析ソフト（ＭＤＪ ＪＡＤＥ ＶＥＲＳＩＯＮ ５）を用い、平均一次粒子径を算出した。
（２）水素化分解物の製造
攪拌機付きの５００ｍＬの鉄製オートクレーブに、上記の方法で得られた銅−白金／シリカ触媒２ｇ、及びグリセリン２００ｇを加え、水素置換した。その後、水素を液中に導入し、オートクレーブ内の圧力を２ＭＰａに維持したまま、５Ｌ／ｍｉｎ．（２５℃、Ｈ２）で流通させつつ、加熱し、２３０℃にて７時間反応させた。
反応終了液はろ過後、ガスクロマトグラフィー[カラム：Ultra-alloy キャピラリーカラム １５．０ｍ×２５０μｍ×０．１５μｍ（Frontier Laboratories 社製）、検出器：ＦＩＤ、インジェクション温度：３００℃、ディテクター温度：３５０℃、Ｈｅ流量：４．６ｍＬ／ｍｉｎ．]にて分析し、生成物を定量した。また、経時的に測定した残存グリセリン量より一次反応速度定数ｋ（５ｈ→７ｈ）を算出し、これを活性の目安とした。これらの結果を表１に示す。
In the following examples and comparative examples, “%” means “mass%” unless otherwise specified.
Example 1
(1) Preparation of copper-platinum / silica catalyst To a reactor having a reflux condenser, ethylene glycol (200 g) and cupric nitrate trihydrate (76 g) were added, and the mixture was heated and stirred at 80 ° C. for 2 hours. Ethoxysilane (52 g) was added dropwise and stirred with heating at 80 ° C. for 2 hours. Thereafter, water (18 g) was added dropwise, and the mixture was heated and stirred at 80 ° C. for 3 hours to obtain a precipitate. The produced precipitate was dried at about 120 ° C. and calcined in air at 400 ° C. for 2 hours to obtain a copper / silica catalyst (copper content 50%).
An aqueous solution of tetraammineplatinum (II) nitrate [Pt (NH 3 ) 4 (NO 3 ) 2 ] (29.8 mg) was added to the obtained copper / silica catalyst (3 g), and dried and dried on a rotary evaporator. . The obtained solid was dried at 120 ° C., calcined in air at 400 ° C. for 2 hours, and copper-platinum / silica catalyst (Cu / Pt / Si = 50 / 0.5 / 17) (copper content 50% )
The average primary particle diameter of copper oxide of the obtained catalyst was 44 nm.
The primary particle size is measured with an X-ray diffractometer (manufactured by Rigaku Corporation, model: ULTRA X 18VB2-3, X-ray source CuK α ray, voltage 40 kV, current 120 mA), and analysis software (MDJ The average primary particle size was calculated using JADE VERSION 5).
(2) Production of hydrocracked product To a 500 mL iron autoclave equipped with a stirrer, 2 g of the copper-platinum / silica catalyst obtained by the above method and 200 g of glycerin were added and replaced with hydrogen. Thereafter, hydrogen was introduced into the liquid, and the pressure in the autoclave was maintained at 2 MPa, and 5 L / min. The mixture was heated while being circulated at (25 ° C., H 2) and reacted at 230 ° C. for 7 hours.
After completion of the reaction, the reaction solution was filtered and then subjected to gas chromatography [column: Ultra-alloy capillary column 15.0 m × 250 μm × 0.15 μm (manufactured by Frontier Laboratories), detector: FID, injection temperature: 300 ° C., detector temperature: 350 ° C., He flow rate: 4.6 mL / min. The product was quantified. Also, a first-order rate constant k (5h → 7h) was calculated from the amount of residual glycerin measured over time, and this was used as a standard for activity. These results are shown in Table 1.
実施例２
実施例１のＰｔ（ＮＨ3）4（ＮＯ3）2の量を５９．５ｍｇに変えた他は実施例１と同様にして、銅−白金／シリカ触媒（Ｃｕ／Ｐｔ／Ｓｉ＝５０／１／１７）を得た。得られた触媒の酸化銅の平均一次粒子径は４５ｎｍであった。
この銅−白金／シリカ触媒を用いて、実施例１（２）と同様に反応させた。結果を表１に示す。
実施例３
実施例１のＰｔ（ＮＨ3）4（ＮＯ3）2の量を１２５．１ｍｇに変えた他は実施例１と同様にして、銅−白金／シリカ触媒（Ｃｕ／Ｐｔ／Ｓｉ＝４９／２．１／１７）を得た。得られた触媒の酸化銅の平均一次粒子径は４６ｎｍであった。
この銅−白金／シリカ触媒を用いて、実施例１（２）と同様に反応させた。結果を表１に示す。
Example 2
A copper-platinum / silica catalyst (Cu / Pt / Si = 50/1) in the same manner as in Example 1 except that the amount of Pt (NH 3 ) 4 (NO 3 ) 2 in Example 1 was changed to 59.5 mg. / 17) was obtained. The average primary particle diameter of copper oxide of the obtained catalyst was 45 nm.
Using this copper-platinum / silica catalyst, the reaction was carried out in the same manner as in Example 1 (2). The results are shown in Table 1.
Example 3
A copper-platinum / silica catalyst (Cu / Pt / Si = 49/2) was prepared in the same manner as in Example 1 except that the amount of Pt (NH 3 ) 4 (NO 3 ) 2 in Example 1 was changed to 125.1 mg. 1/17). The average primary particle diameter of copper oxide of the obtained catalyst was 46 nm.
Using this copper-platinum / silica catalyst, the reaction was carried out in the same manner as in Example 1 (2). The results are shown in Table 1.
実施例４
実施例１のＰｔ（ＮＨ3）4（ＮＯ3）2の量を１１．９ｍｇに変えた他は実施例１と同様にして、銅−白金／シリカ触媒（Ｃｕ／Ｐｔ／Ｓｉ＝５０／０．２／１７）を得た。得られた触媒の酸化銅の平均一次粒子径は４４ｎｍであった。
この銅−白金／シリカ触媒を用いて、実施例１（２）と同様に反応させた。結果を表１に示す。
実施例５
実施例１のＰｔ（ＮＨ3）4（ＮＯ3）2の量を３ｍｇに変えた他は実施例１と同様にして、銅−白金／シリカ触媒（Ｃｕ／Ｐｔ／Ｓｉ＝５０／０．０５／１７）を得た。得られた触媒の酸化銅の平均一次粒子径は４３ｎｍであった。
この銅−白金／シリカ触媒を用いて、実施例１（２）と同様に反応させた。結果を表１に示す。
Example 4
A copper-platinum / silica catalyst (Cu / Pt / Si = 50/0) was obtained in the same manner as in Example 1 except that the amount of Pt (NH 3 ) 4 (NO 3 ) 2 in Example 1 was changed to 11.9 mg. 2/17). The average primary particle diameter of copper oxide of the obtained catalyst was 44 nm.
Using this copper-platinum / silica catalyst, the reaction was carried out in the same manner as in Example 1 (2). The results are shown in Table 1.
Example 5
A copper-platinum / silica catalyst (Cu / Pt / Si = 50 / 0.05) was obtained in the same manner as in Example 1 except that the amount of Pt (NH 3 ) 4 (NO 3 ) 2 in Example 1 was changed to 3 mg. / 17) was obtained. The average primary particle diameter of copper oxide of the obtained catalyst was 43 nm.
Using this copper-platinum / silica catalyst, the reaction was carried out in the same manner as in Example 1 (2). The results are shown in Table 1.
実施例６
実施例１のＰｔ（ＮＨ3）4（ＮＯ3）2（２９．８ｍｇ）をＰｄ（ＮＯ3）2（３２．５ｍｇ）に変えた他は実施例１と同様にして、銅−パラジウム／シリカ触媒（Ｃｕ／Ｐｄ／Ｓｉ＝５０／０．５／１７）を得た。得られた触媒の酸化銅の平均一次粒子径は４４ｎｍであった。
この銅−パラジウム／シリカ触媒を用いて、実施例１（２）と同様に反応させた。結果を表１に示す。
実施例７
実施例１のＰｔ（ＮＨ3）4（ＮＯ3）2（２９．８ｍｇ）をＲｕ（ＮＯ）（ＮＯ3）ｘ（ＯＨ）ｙ（Ｘ＋Ｙ＝３）水溶液（Ｒｕ：１．５％、１．０ｇ）に変えた他は実施例１と同様にして、銅−ルテニウム／シリカ触媒（Ｃｕ／Ｒｕ／Ｓｉ＝５０／０．５／１７）を得た。得られた触媒の酸化銅の平均一次粒子径は４４ｎｍであった。
この銅−ルテニウム／シリカ触媒を用いて、実施例１（２）と同様に反応させた。結果を表１に示す。
Example 6
Copper-palladium / silica was obtained in the same manner as in Example 1 except that Pt (NH 3 ) 4 (NO 3 ) 2 (29.8 mg) in Example 1 was changed to Pd (NO 3 ) 2 (32.5 mg). A catalyst (Cu / Pd / Si = 50 / 0.5 / 17) was obtained. The average primary particle diameter of copper oxide of the obtained catalyst was 44 nm.
Using this copper-palladium / silica catalyst, the reaction was carried out in the same manner as in Example 1 (2). The results are shown in Table 1.
Example 7
Pt (NH 3 ) 4 (NO 3 ) 2 (29.8 mg) of Example 1 was replaced with an aqueous Ru (NO) (NO 3 ) x (OH) y (X + Y = 3) solution (Ru: 1.5%, 1. The copper-ruthenium / silica catalyst (Cu / Ru / Si = 50 / 0.5 / 17) was obtained in the same manner as in Example 1 except that the amount was changed to 0 g). The average primary particle diameter of copper oxide of the obtained catalyst was 44 nm.
Using this copper-ruthenium / silica catalyst, the reaction was carried out in the same manner as in Example 1 (2). The results are shown in Table 1.
比較例１
還流冷却器を有する反応器に、エチレングリコール（２００ｇ）、硝酸第二銅三水和物（７６ｇ）を加え、８０℃で２時間加熱攪拌後、テトラエトキシシラン（５２ｇ）を滴下し８０℃で２時間加熱攪拌した。その後、水（１８ｇ）を滴下し８０℃で３時間加熱攪拌し沈澱物を得た。生成した沈殿物を約１２０℃で乾燥させ、４００℃で２時間、空気中で焼成し、銅／シリカ触媒（Ｃｕ／Ｓｉ＝５０／１７）を得た。得られた触媒の酸化銅の平均一次粒子径は４４ｎｍであった。
この銅／シリカ触媒を用いて、実施例１（２）と同様に反応させた。結果を表１に示す。
Comparative Example 1
Ethylene glycol (200 g) and cupric nitrate trihydrate (76 g) are added to a reactor having a reflux condenser, and after stirring with heating at 80 ° C. for 2 hours, tetraethoxysilane (52 g) is added dropwise at 80 ° C. The mixture was heated and stirred for 2 hours. Thereafter, water (18 g) was added dropwise, and the mixture was heated and stirred at 80 ° C. for 3 hours to obtain a precipitate. The produced precipitate was dried at about 120 ° C. and calcined in air at 400 ° C. for 2 hours to obtain a copper / silica catalyst (Cu / Si = 50/17). The average primary particle diameter of copper oxide of the obtained catalyst was 44 nm.
Using this copper / silica catalyst, the reaction was carried out in the same manner as in Example 1 (2). The results are shown in Table 1.
表１に示すように、実施例１〜７の触媒は比較例１の触媒に比べ活性が高く、かつ１,２−プロパンジオールの収率も高いことが分かる。 As shown in Table 1, it can be seen that the catalysts of Examples 1 to 7 are more active than the catalyst of Comparative Example 1, and the yield of 1,2-propanediol is also high.
実施例８
実施例１で得られた銅−白金／シリカ触媒（Ｃｕ／Ｐｔ／Ｓｉ＝５０／０．５／１７）を１０ｇ用いて、１８０℃にて３時間反応を行った以外は、実施例１（２）と同様に反応させた。結果を表２に示す。
比較例２
比較例１で得られた銅／シリカ触媒（Ｃｕ／Ｓｉ＝５０／１７）を１０ｇ用いて、１８０℃にて３時間反応を行った以外は、実施例１（２）と同様に反応させた。結果を表２に示す。
Example 8
Example 1 (except that the reaction was carried out at 180 ° C. for 3 hours using 10 g of the copper-platinum / silica catalyst (Cu / Pt / Si = 50 / 0.5 / 17) obtained in Example 1. The reaction was conducted in the same manner as in 2). The results are shown in Table 2.
Comparative Example 2
The reaction was conducted in the same manner as in Example 1 (2) except that 10 g of the copper / silica catalyst (Cu / Si = 50/17) obtained in Comparative Example 1 was used and the reaction was performed at 180 ° C. for 3 hours. . The results are shown in Table 2.
表２に示すように、実施例８の触媒は比較例２の触媒に比べ、活性が高く、かつ１，２−プロパンジオールの選択率、収率も高いことが分かる。さらに、実施例８の触媒を用いて反応を続けた結果、２３時間でグリセリン転化率９９．７ｍｏｌ％、１，２−プロパンジオールの選択性９７．８ｍｏｌ％（収率：９７．５ｍｏｌ％）、エチレングリコール選択率０．４ｍｏｌ％で反応が進行した。この結果を表１と対比すると、２３０℃に比べて１８０℃の方がエチレングリコール副生量は少ないことが分かる。 As shown in Table 2, the catalyst of Example 8 is higher in activity than the catalyst of Comparative Example 2, and the selectivity and yield of 1,2-propanediol are also high. Furthermore, as a result of continuing the reaction using the catalyst of Example 8, the glycerol conversion rate was 99.7 mol% in 23 hours, the selectivity of 1,2-propanediol was 97.8 mol% (yield: 97.5 mol%), The reaction proceeded with an ethylene glycol selectivity of 0.4 mol%. When this result is compared with Table 1, it can be seen that the amount of ethylene glycol by-product is smaller at 180 ° C. than at 230 ° C.
本発明の多価アルコールの水素化分解生成物の製造方法は、多価アルコールからその水素化分解物、特にグリセリンから１，２−プロパンジオールを高収率で製造することができる。 The method for producing a hydrocracked product of a polyhydric alcohol according to the present invention can produce a hydrocracked product from a polyhydric alcohol, particularly 1,2-propanediol from glycerin in a high yield.
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| WO2014104341A1 (en) | 2012-12-28 | 2014-07-03 | 三菱瓦斯化学株式会社 | Polyether diol and production method therefor |
| US9447011B2 (en) | 2012-11-21 | 2016-09-20 | University Of Tennessee Research Foundation | Methods, systems and devices for simultaneous production of lactic acid and propylene glycol from glycerol |
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| US5326912A (en) * | 1992-01-31 | 1994-07-05 | Montecatini Technologie S.R.L. | Hydrogenation catalyst, and a method for its preparation and use, in particular for hydrogenation and/or hydrogenolysis of carbohydrates and polyhydric alcohols |
| WO2008069120A1 (en) * | 2006-12-05 | 2008-06-12 | Kao Corporation | Process for producing product of hydrogenolysis of polyhydric alcohol |
| WO2008069830A2 (en) * | 2006-05-08 | 2008-06-12 | Virent Energy Systems, Inc. | Methods and systems for generating polyols |
| WO2008129933A1 (en) * | 2007-04-17 | 2008-10-30 | Kao Corporation | Process for producing hydrogenolysis products of polyhydric alcohols |
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| WO2008069830A2 (en) * | 2006-05-08 | 2008-06-12 | Virent Energy Systems, Inc. | Methods and systems for generating polyols |
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| US9447011B2 (en) | 2012-11-21 | 2016-09-20 | University Of Tennessee Research Foundation | Methods, systems and devices for simultaneous production of lactic acid and propylene glycol from glycerol |
| WO2014104341A1 (en) | 2012-12-28 | 2014-07-03 | 三菱瓦斯化学株式会社 | Polyether diol and production method therefor |
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