JP4831666B2 - Method for producing levulinic acid ester - Google Patents
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- JP4831666B2 JP4831666B2 JP2005359705A JP2005359705A JP4831666B2 JP 4831666 B2 JP4831666 B2 JP 4831666B2 JP 2005359705 A JP2005359705 A JP 2005359705A JP 2005359705 A JP2005359705 A JP 2005359705A JP 4831666 B2 JP4831666 B2 JP 4831666B2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
本発明は、炭水化物、例えば糖、でんぷん、セルロースあるいはそれらを含有する混合物、あるいはバイオマス由来のこれらのもの等とアルコールとを触媒の存在下で反応させてレブリン酸エステルを製造する方法に関する。 The present invention relates to a method for producing a levulinic acid ester by reacting a carbohydrate such as sugar, starch, cellulose or a mixture containing them, or those derived from biomass with an alcohol in the presence of a catalyst.
レブリン酸は高分子可塑剤、生理活性物質などの合成中間体として有用なものであって、糖やでんぷん、グルコースなどの炭水化物を原料として製造され、例えば糖を酸触媒の存在下で加熱分解することによる製造法は古くから知られており、その中に触媒として臭化水素酸や塩酸を用いる方法があるが（非特許文献１参照）、これらの酸は揮発性があり、工業的製法においては装置の防食方法が問題となる。
一方、揮発性の無い硫酸を触媒として用いるレブリン酸製造法も知られているが（特許文献１〜３参照）、硫酸触媒では低温での反応速度が遅く、良好な収率でレブリン酸を得るためには１６０℃以上の高い反応温度が必要である。
Levulinic acid is useful as a synthetic intermediate for polymer plasticizers, physiologically active substances, etc., and is produced from carbohydrates such as sugar, starch and glucose. For example, sugar is decomposed by heating in the presence of an acid catalyst. The production method by this method has been known for a long time, and there is a method using hydrobromic acid or hydrochloric acid as a catalyst (see Non-Patent Document 1), but these acids are volatile and are used in industrial production methods. The problem is the corrosion prevention method of the device.
On the other hand, a levulinic acid production method using non-volatile sulfuric acid as a catalyst is also known (see Patent Documents 1 to 3). However, a sulfuric acid catalyst has a low reaction rate at a low temperature and obtains levulinic acid in a good yield. For this purpose, a high reaction temperature of 160 ° C. or higher is necessary.
本発明の課題は、このような事情の下、炭水化物とアルコールを原料とする触媒反応によりレブリン酸エステルを製造するに当たり、触媒として揮発性が無くかつ温和な条件で触媒活性を示すものを用いる方法を提供することにある。 Under such circumstances, the object of the present invention is to use a non-volatile catalyst that exhibits catalytic activity under mild conditions in producing a levulinic acid ester by a catalytic reaction using carbohydrate and alcohol as raw materials. Is to provide.
本発明者らは、上記の優れた特性を有する、触媒反応によるレブリン酸エステルの製造法における触媒について鋭意研究した結果、ヘテロポリ酸を触媒に用いると温和な条件で効率よくレブリン酸エステルが得られることを見出し、この知見に基づいて本発明をなすに至った。 As a result of intensive research on the catalyst in the method for producing a levulinic acid ester by catalytic reaction having the above-described excellent characteristics, the present inventors can efficiently obtain a levulinic acid ester under mild conditions when a heteropolyacid is used as a catalyst. Based on this finding, the inventors have made the present invention.
すなわち、本発明は、以下のとおりのものである。
（１）炭水化物とアルコールとを触媒の存在下で反応させてレブリン酸エステルを製造する方法において、触媒としてヘテロポリ酸を用いることを特徴とするレブリン酸エステルの製造方法。
（２）ヘテロポリ酸がタングステンをポリ原子とするタングステンヘテロポリ酸である前記（１）記載の製造方法。
（３）タングステンヘテロポリ酸がケイ素をヘテロ原子とするものである前記（２）記載の製造方法。
That is, the present invention is as follows.
(1) A method for producing a levulinic acid ester, wherein a heteropoly acid is used as a catalyst in a method for producing a levulinic acid ester by reacting a carbohydrate and an alcohol in the presence of a catalyst.
(2) The production method according to (1), wherein the heteropolyacid is a tungsten heteropolyacid containing tungsten as a poly atom.
(3) The production method according to the above (2), wherein the tungsten heteropolyacid has silicon as a hetero atom.
本発明方法において原料として用いられる炭水化物については特に制限されず、例えば単糖類、二糖類、オリゴ糖類、多糖類、それらの混合物、さらにはバイオマス由来のこれらのものなどが挙げられ、これらのうち、単糖類としては、例えばグルコース、フルクトース等が、また、多糖類としては、例えばでんぷん、セルロース等が挙げられ、好ましくはグルコース、フルクトース等のヘキソース、中でもフルクトースが用いられる。これらの原料は単独で用いてもよいし、また、２種以上を組み合わせて用いてもよく、また、原料自体が混合物の場合にはそれより単離することなく混合物のまま用いてもよい。 The carbohydrate used as a raw material in the method of the present invention is not particularly limited, and examples thereof include monosaccharides, disaccharides, oligosaccharides, polysaccharides, mixtures thereof, and those derived from biomass, among these, Examples of monosaccharides include glucose and fructose, and examples of polysaccharides include starch and cellulose. Preferably, hexoses such as glucose and fructose are used, among which fructose is used. These raw materials may be used alone or in combination of two or more, and when the raw material itself is a mixture, it may be used as it is without being isolated therefrom.
炭水化物とともに反応に供されるアルコールについては、脂肪族あるいは芳香族の１級、２級あるいは３級アルコールのうち、目的とするエステル基に応じて任意のものを用いることができる。融点が反応温度以上のアルコールについては、他の有機溶媒を用いて液化させて用いてもよい。
アルコールは溶媒としても用いることができる。
As the alcohol used for the reaction together with the carbohydrate, any aliphatic or aromatic primary, secondary or tertiary alcohol can be used depending on the target ester group. About alcohol whose melting | fusing point is more than reaction temperature, you may use it liquefying using another organic solvent.
Alcohol can also be used as a solvent.
本発明方法において触媒として用いられるヘテロポリ酸は、一般式
ＨｗＡｘＢｙＯｚ
（式中、Ｂはポリ酸の骨格となるポリ原子、Ａはヘテロ原子、ｗは水素原子の組成比、ｘはヘテロ原子の組成比、ｙはポリ原子の組成比、ｚは酸素原子の組成比を示す）
で表わされる。
ポリ原子Ｂとしてはポリ酸を形成することが知られている原子（例えばＷ、Ｍｏ、Ｖ、Ｎｂなど）の中から任意に選ぶことができる。ポリ原子Ｂは単一原子でもよいし、また、一部を他の原子と置換してもよい。
ヘテロ原子Ａとしては、ヘテロポリ酸を形成することが知られている原子（例えばＳｉ、Ｐ、Ｇｅ、Ｂ、Ａｓなど）の中から任意に選ぶことができる。ヘテロ原子Ａは単一原子でもよいし、また、一部を他の原子と置換してもよい。
ヘテロポリ酸は溶媒に可溶な塩の状態で用いてもよいし、また、溶媒に不溶な塩の状態で用いてもよく、さらにシリカゲルやアルミナなどの担体に固定化した状態で用いてもよい。
ヘテロポリ酸として好ましくは、タングステンをポリ原子とするヘテロポリ酸、例えばＨ３ＰＷ１２Ｏ４０、Ｈ４ＳｉＷ１２Ｏ４０、Ｈ４ＧｅＷ１２Ｏ４０、Ｈ５ＢＷ１２Ｏ４０などが挙げられ、中でも特にＨ４ＳｉＷ１２Ｏ４０が用いられる。
ヘテロポリ酸の使用量は、炭水化物に対して０．１〜１０モル％の範囲とするのが好ましい。
The heteropolyacid used as a catalyst in the method of the present invention is represented by the general formula H w A x B y O z
(In the formula, B is a poly atom serving as a polyacid skeleton, A is a hetero atom, w is a composition ratio of hydrogen atoms, x is a composition ratio of hetero atoms, y is a composition ratio of poly atoms, and z is a composition of oxygen atoms. Indicates the ratio)
It is represented by
The poly atom B can be arbitrarily selected from atoms known to form a polyacid (for example, W, Mo, V, Nb, etc.). The poly atom B may be a single atom or a part thereof may be substituted with another atom.
The heteroatom A can be arbitrarily selected from atoms known to form a heteropolyacid (for example, Si, P, Ge, B, As, etc.). The heteroatom A may be a single atom, or a part thereof may be substituted with another atom.
The heteropolyacid may be used in the form of a salt soluble in the solvent, may be used in the form of a salt insoluble in the solvent, or may be used in a state immobilized on a carrier such as silica gel or alumina. .
The heteropolyacid is preferably a heteropolyacid having tungsten as a poly atom, such as H 3 PW 12 O 40 , H 4 SiW 12 O 40 , H 4 GeW 12 O 40 , H 5 BW 12 O 40, etc. H 4 SiW 12 O 40 is used.
The amount of the heteropolyacid used is preferably in the range of 0.1 to 10 mol% with respect to the carbohydrate.
本発明方法として好ましくは、触媒量のヘテロポリ酸を含むアルコール中に炭水化物を加え、加熱反応させる方法が挙げられ、反応温度は８０℃〜１８０℃、中でも１００℃〜１６０℃の範囲とするのがよい。反応温度がこれより低いと反応速度が遅くなるし、また、これより高いと反応が過剰に進み、黒色の不溶物が生じる。また、反応は一般的には常圧で行われるが、沸点が好ましい反応温度域よりも低いアルコールが用いられる場合には、オートクレーブなどの耐圧反応容器を用い、加圧下で反応させてもよい。
本発明方法においては、溶媒として上記アルコールを併用してもよいし、本発明を損なわない範囲で、必要に応じ他の適当な溶媒、例えば水や、テトラヒドロフラン、ジオキサン、ジエチルエーテル等のエーテルや、ベンゼン、トルエン、キシレン等の芳香族炭化水素、クロロホルム、ジクロロメタン等のハロゲン化炭化水素などを用いてもよい。
Preferably, the method of the present invention includes a method in which a carbohydrate is added to an alcohol containing a catalytic amount of a heteropolyacid and subjected to a heat reaction, and the reaction temperature is in the range of 80 ° C to 180 ° C, particularly 100 ° C to 160 ° C. Good. When the reaction temperature is lower than this, the reaction rate becomes slow, and when the reaction temperature is higher than this, the reaction proceeds excessively and black insoluble matter is generated. The reaction is generally carried out at normal pressure, but when an alcohol having a boiling point lower than the preferred reaction temperature range is used, the reaction may be carried out under pressure using a pressure-resistant reaction vessel such as an autoclave.
In the method of the present invention, the above-mentioned alcohol may be used in combination as a solvent, and other suitable solvents such as water, ethers such as tetrahydrofuran, dioxane, diethyl ether, and the like, as long as the present invention is not impaired. Aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as chloroform and dichloromethane may be used.
本発明方法によれば、糖、でんぷん、セルロース等の炭水化物を原料として、従来の触媒よりも温和な条件で効率よくレブリン酸エステルを製造することができる。 According to the method of the present invention, a levulinic acid ester can be efficiently produced using carbohydrates such as sugar, starch and cellulose as raw materials under conditions milder than those of conventional catalysts.
次に、実施例により本発明を実施するための最良の形態をさらに詳細に説明するが、本発明はこれらにより何ら限定されるものではない。 Next, the best mode for carrying out the present invention will be described in more detail by way of examples, but the present invention is not limited to these at all.
内容積２５ｍｌのナス型フラスコにブタノール８．０ｍｌ、フルクトース２．５ｍｍｏｌおよびＨ４ＳｉＷ１２Ｏ４０・２６Ｈ２Ｏのヘテロポリ酸触媒０．０５ｍｍｏｌを加え、還流下５時間加熱反応させた。反応後室温まで冷却し、反応溶液をガスクロマトグラフにより分析した結果、レブリン酸ブチルが収率６０モル％で得られていることが確認された。 To an eggplant-shaped flask having an internal volume of 25 ml, 8.0 ml of butanol, 2.5 mmol of fructose and 0.05 mmol of H 4 SiW 12 O 40 · 26H 2 O heteropolyacid catalyst were added, and the mixture was heated and reacted for 5 hours under reflux. After the reaction, the reaction solution was cooled to room temperature, and the reaction solution was analyzed by gas chromatography. As a result, it was confirmed that butyl levulinate was obtained in a yield of 60 mol%.
ヘテロポリ酸触媒をＨ４ＧｅＷ１２Ｏ４０・７Ｈ２Ｏに代えた以外は実施例１と同様にして反応させ分析した結果、レブリン酸ブチルが収率５５モル％で得られていることが確認された。 As a result of analyzing and analyzing in the same manner as in Example 1 except that the heteropolyacid catalyst was replaced with H 4 GeW 12 O 40 · 7H 2 O, it was confirmed that butyl levulinate was obtained in a yield of 55 mol%. It was.
ヘテロポリ酸触媒をＨ３ＰＷ１２Ｏ４０・４Ｈ２Ｏに代えた以外は実施例１と同様にして反応させ分析した結果、レブリン酸ブチルが収率５１モル％で得られていることが確認された。 As a result of analyzing and analyzing in the same manner as in Example 1 except that the heteropolyacid catalyst was replaced with H 3 PW 12 O 40 · 4H 2 O, it was confirmed that butyl levulinate was obtained in a yield of 51 mol%. It was.
ヘテロポリ酸触媒をＨ５ＢＷ１２Ｏ４０・３３Ｈ２Ｏに代えた以外は実施例１と同様にして反応させ分析した結果、レブリン酸ブチルが収率４３モル％で得られていることが確認された。 As a result of analyzing and analyzing in the same manner as in Example 1 except that the heteropolyacid catalyst was replaced with H 5 BW 12 O 40 · 33H 2 O, it was confirmed that butyl levulinate was obtained in a yield of 43 mol%. It was.
ヘテロポリ酸触媒をＨ３ＰＭｏ１２Ｏ４０・４Ｈ２Ｏに代えた以外は実施例１と同様にして反応させ分析した結果、レブリン酸ブチルが収率３９モル％で得られていることが確認された。 As a result of performing the reaction and analysis in the same manner as in Example 1 except that the heteropolyacid catalyst was replaced with H 3 PMo 12 O 40 · 4H 2 O, it was confirmed that butyl levulinate was obtained in a yield of 39 mol%. It was.
これらの実施例より、同じポリ酸で比較すると、ケイ素をヘテロ元素とするヘテロポリ酸が好ましく（実施例１〜４参照）、同じヘテロ元素で比較すると、タングステン酸が好ましい（実施例３，５参照）ことが分る。 From these examples, when compared with the same polyacid, a heteropolyacid containing silicon as a heteroelement is preferable (see Examples 1 to 4), and when compared with the same heteroelement, tungstic acid is preferable (see Examples 3 and 5). )
内容積５０ｍｌのステンレス製オートクレーブにメタノール８．０ｍｌ、フルクトース２．５ｍｍｏｌおよびＨ４ＳｉＷ１２Ｏ４０・２６Ｈ２Ｏのヘテロポリ酸触媒０．０５ｍｍｏｌを加え、アルゴンで１ＭＰａに加圧し、１４０℃で１５時間加熱反応させた。反応後室温まで冷却し、反応溶液をガスクロマトグラフにより分析した結果、レブリン酸メチルが収率８０モル％で得られていることが確認された。 To a stainless steel autoclave with an internal volume of 50 ml, 8.0 ml of methanol, 2.5 mmol of fructose and 0.05 mmol of H 4 SiW 12 O 40 · 26H 2 O heteropolyacid catalyst were added, pressurized to 1 MPa with argon, and 140 ° C. for 15 hours. The reaction was heated. After the reaction, the reaction solution was cooled to room temperature, and the reaction solution was analyzed by gas chromatography. As a result, it was confirmed that methyl levulinate was obtained in a yield of 80 mol%.
反応時間を５時間、反応温度を１２０℃に代えた以外は実施例６と同様にして反応させ分析した結果、レブリン酸メチルが収率７８モル％で得られていることが確認された。 As a result of analyzing and analyzing in the same manner as in Example 6 except that the reaction time was changed to 5 hours and the reaction temperature was changed to 120 ° C., it was confirmed that methyl levulinate was obtained in a yield of 78 mol%.
フルクトースに代えてグルコースを用いた以外は実施例６と同様にして反応させ分析した結果、レブリン酸メチルが収率６０モル％で得られていることが確認された。 As a result of performing reaction and analysis in the same manner as in Example 6 except that glucose was used instead of fructose, it was confirmed that methyl levulinate was obtained in a yield of 60 mol%.
フルクトースに代えてでんぷん（とうもろこし由来、純正化学社製）を用いた以外は実施例６と同様にして反応させ分析した結果、レブリン酸メチルが収率４０モル％で得られていることが確認された。 As a result of analyzing and analyzing in the same manner as in Example 6 except that starch (derived from corn, manufactured by Junsei Chemical Co., Ltd.) was used instead of fructose, it was confirmed that methyl levulinate was obtained in a yield of 40 mol%. It was.
フルクトースに代えてセルロース（ナカライタスク社製）を用いた以外は実施例６と同様にして反応させ分析した結果、レブリン酸メチルが収率４０モル％で得られていることが確認された。 As a result of performing the reaction and analysis in the same manner as in Example 6 except that cellulose (manufactured by Nacalai Task Co.) was used instead of fructose, it was confirmed that methyl levulinate was obtained in a yield of 40 mol%.
比較例１
ヘテロポリ酸触媒を市販の濃硫酸（９７質量％濃度）に代えた以外は実施例１と同様にして反応させ分析した結果、レブリン酸ブチルが収率３４モル％で得られていることが確認された。
Comparative Example 1
As a result of performing the reaction and analysis in the same manner as in Example 1 except that the heteropolyacid catalyst was replaced with commercially available concentrated sulfuric acid (97 mass% concentration), it was confirmed that butyl levulinate was obtained in a yield of 34 mol%. It was.
比較例２
ヘテロポリ酸触媒をＨ２ＷＯ４に代えた以外は実施例１と同様にして反応させ分析した結果、レブリン酸ブチルは収率０モル％で全く得られていないことが確認された。
Comparative Example 2
As a result of analyzing the reaction in the same manner as in Example 1 except that the heteropolyacid catalyst was replaced with H 2 WO 4 , it was confirmed that butyl levulinate was not obtained at a yield of 0 mol%.
これら比較例より、従来用いられている硫酸触媒では収率が低く、またヘテロ元素を持たないイソポリ酸では反応が進行しないことが分る。 From these comparative examples, it can be seen that the conventionally used sulfuric acid catalyst has a low yield, and that the reaction does not proceed with an isopolyacid having no hetero element.
本発明は、糖、でんぷん、セルロース等の炭水化物を原料として、従来の触媒よりも温和な条件で効率よくレブリン酸エステルを製造するのに有用であり、原料となる炭水化物としては資源作物から得られる糖やでんぷんの他に、廃棄物から得られる糖やでんぷん、セルロースの利用も可能であるし、また、得られたレブリン酸エステルは、香料、高分子可塑剤、生理活性物質など従来の用途のほかに生分解性高分子モノマーや医薬品中間体としての利用も可能であることから、化学産業の化石資源への依存性を低減させるのに資する。
INDUSTRIAL APPLICABILITY The present invention is useful for efficiently producing a levulinic acid ester using carbohydrates such as sugar, starch and cellulose as raw materials under milder conditions than conventional catalysts, and the carbohydrates used as raw materials are obtained from resource crops. In addition to sugar and starch, sugar, starch, and cellulose obtained from waste can be used, and the obtained levulinic acid ester is used for conventional applications such as fragrances, polymer plasticizers, and physiologically active substances. In addition, it can be used as biodegradable polymer monomers and pharmaceutical intermediates, which contributes to reducing the dependence of the chemical industry on fossil resources.
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| CN102399144A (en) * | 2011-09-26 | 2012-04-04 | 华南理工大学 | Method for preparing methyl levulinate through clean conversion of biomass sugar and separating methyl levulinate |
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| JP4877045B2 (en) | 2007-04-25 | 2012-02-15 | トヨタ自動車株式会社 | Method for decomposing plant fiber materials |
| JP4240138B1 (en) * | 2007-09-05 | 2009-03-18 | トヨタ自動車株式会社 | Method for separating saccharification of plant fiber material |
| JP5114298B2 (en) | 2008-06-03 | 2013-01-09 | トヨタ自動車株式会社 | Method for separating saccharification of plant fiber material |
| JP5060397B2 (en) | 2008-06-03 | 2012-10-31 | トヨタ自動車株式会社 | Method for separating saccharification of plant fiber material |
| JP4609526B2 (en) | 2008-06-03 | 2011-01-12 | トヨタ自動車株式会社 | Method for separating saccharification of plant fiber material |
| JP5366128B2 (en) * | 2008-12-19 | 2013-12-11 | 独立行政法人産業技術総合研究所 | Method for producing levulinic acid ester |
| NL2005928C2 (en) * | 2010-12-28 | 2012-07-02 | Furanix Technologies Bv | Process for the conversion of a carbohydrate-containing feedstock. |
| WO2013078391A1 (en) | 2011-11-23 | 2013-05-30 | Segetis, Inc. | Process to prepare levulinic acid |
| US9073841B2 (en) | 2012-11-05 | 2015-07-07 | Segetis, Inc. | Process to prepare levulinic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5587741A (en) * | 1978-12-27 | 1980-07-02 | Noguchi Kenkyusho | Preparation of levulinic acid |
| JPS577439A (en) * | 1980-06-13 | 1982-01-14 | Asahi Chem Ind Co Ltd | Production of levulinic acid or its ester |
| FR2640263B1 (en) * | 1988-12-09 | 1991-06-14 | Organo Synthese Ste Fse | PREPARATION OF LEVULINIC ACID |
| WO2003085071A1 (en) * | 2002-04-01 | 2003-10-16 | E.I. Du Pont De Nemours And Company | Preparation of levulinic acid esters and formic acid esters from biomass and olefins |
| JP4025866B2 (en) * | 2002-08-27 | 2007-12-26 | 独立行政法人森林総合研究所 | Effective use of lignocellulose |
| JP4633339B2 (en) * | 2003-05-26 | 2011-02-16 | 三洋化成工業株式会社 | Method for producing carboxylic acid ester |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102399144A (en) * | 2011-09-26 | 2012-04-04 | 华南理工大学 | Method for preparing methyl levulinate through clean conversion of biomass sugar and separating methyl levulinate |
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