JP5224751B2 - Process for producing 5-hydroxymethylfurfural - Google Patents
Process for producing 5-hydroxymethylfurfural Download PDFInfo
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Description
本発明は、ヘキソースの脱水反応により５−ヒドロキシメチルフルフラールを製造する方法に関する。 The present invention relates to a method for producing 5-hydroxymethylfurfural by dehydration reaction of hexose.
５−ヒドロキシメチルフルフラール（以下５−ＨＭＦと略す）は、各種医薬品、香料、農薬等の合成中間体として知られており、また、各種ポリマーの材料として期待されている。 5-Hydroxymethylfurfural (hereinafter abbreviated as 5-HMF) is known as a synthetic intermediate for various pharmaceuticals, fragrances, agricultural chemicals and the like, and is also expected as a material for various polymers.
糖類からの５−ＨＭＦの製法としては、水溶液中で、強酸触媒を用いて脱水反応を行う方法が知られている（非特許文献１乃至３参照）。しかし、この方法では、生成した５−ＨＭＦの重合、分解が起こりやすく、これを防ぐ為に高温、高圧下で瞬間的に反応させる必要がある。そのため、工業的方法としては、操作性や経済性の点から不利である。 As a method for producing 5-HMF from saccharides, a method of performing a dehydration reaction in an aqueous solution using a strong acid catalyst is known (see Non-Patent Documents 1 to 3). However, in this method, the produced 5-HMF is likely to be polymerized and decomposed, and in order to prevent this, it is necessary to react instantaneously under high temperature and high pressure. Therefore, it is disadvantageous from the viewpoint of operability and economy as an industrial method.
また、ジメチルスルホキシドなどの極性溶媒中で無触媒もしくは酸触媒存在下で脱水反応を行う方法（非特許文献１、２及び４、特許文献１及び２参照）もあるが、生成した５−ＨＭＦからの溶媒除去には、カラムクロマトグラフィーなどを行う必要があるため、工業的方法として考えた場合、経済性の面から不利である。 There is also a method of performing a dehydration reaction in a polar solvent such as dimethyl sulfoxide in the absence of a catalyst or in the presence of an acid catalyst (see Non-Patent Documents 1, 2, and 4, Patent Documents 1 and 2). Removal of the solvent requires column chromatography or the like, which is disadvantageous in terms of economy when considered as an industrial method.
さらに、水と極性溶媒の混合溶媒中で脱水反応を行う方法（非特許文献５参照）も知られているが、反応系にジメチルスルホキシドを添加している為、上記と同様に５−ＨＭＦとの分離の面で不利である。
水溶液中で強酸触媒を用いて糖類の脱水反応を行う５−ＨＭＦの製造方法では、高温、高圧下で瞬間的に反応させる必要があるため、工業的方法としては、操作性や経済性の点から不利である。 In the manufacturing method of 5-HMF which performs dehydration reaction of saccharides using a strong acid catalyst in an aqueous solution, since it is necessary to react instantaneously under high temperature and high pressure, as an industrial method, the point of operativity and economical efficiency Is disadvantageous.
また、ＤＭＳＯなどの非プロトン性の極性溶媒中で糖類の脱水反応を行い、５−ＨＭＦを製造する方法では、高収率で５−ＨＭＦが得られるが、上記のように反応後の溶媒除去に時間や手間がかかり、経済的に不利である。 Further, in the method of producing 5-HMF by dehydrating saccharides in an aprotic polar solvent such as DMSO, 5-HMF is obtained in a high yield. As described above, removal of the solvent after the reaction is performed. Is time consuming and laborious and is economically disadvantageous.
したがって、合成からその後の精製まで含めて、高温高圧条件を必要とせずに、溶媒除去が容易な５−ＨＭＦの製造方法が求められている。 Accordingly, there is a need for a process for producing 5-HMF that allows easy removal of the solvent without requiring high-temperature and high-pressure conditions from synthesis to subsequent purification.
そこで、発明者らは上記課題を解決すべく鋭意検討したところ、溶媒として有機酸を用いてヘキソースの脱水反応を行うことにより、穏和な条件で５−ＨＭＦを生成することができ、かつ溶媒の除去が容易であることがわかった。 Therefore, the inventors have intensively studied to solve the above-mentioned problems. As a result, 5-HMF can be generated under mild conditions by performing dehydration reaction of hexose using an organic acid as a solvent, and It was found that removal was easy.
したがって、本発明に係る５−ＨＭＦの製造方法は、
ヘキソースを含む原料を溶媒中で加熱して５−ＨＭＦを製造する方法において、
前記溶媒として有機酸を使用することを特徴とする。
Therefore, the method for producing 5-HMF according to the present invention is as follows.
In a method for producing 5-HMF by heating a raw material containing hexose in a solvent,
An organic acid is used as the solvent.
前記ヘキソースを含む原料としては、加水分解によりヘキソースを生成する糖類を用いることも可能であり、又、この加水分解は系中で行ってもよく、その場合は、前記溶媒中に少量の水が含まれていることが好ましい。 As the raw material containing hexose, saccharides that generate hexose by hydrolysis can be used, and this hydrolysis may be carried out in the system, in which case a small amount of water is contained in the solvent. It is preferably included.
前記ヘキソースはフルクトースであることが好ましい。 The hexose is preferably fructose.
前記溶媒中に酸触媒を添加して反応を行うことが好ましい。 It is preferable to carry out the reaction by adding an acid catalyst to the solvent.
前記酸触媒はスルホン酸型のイオン交換樹脂であることが好ましい。 The acid catalyst is preferably a sulfonic acid type ion exchange resin.
前記有機酸は、１気圧における沸点が１５０℃以下であることが好ましい。 The organic acid preferably has a boiling point of 150 ° C. or less at 1 atmosphere.
前記有機酸は、酢酸若しくはギ酸又はこれらの混合液であることが好ましい。 The organic acid is preferably acetic acid or formic acid or a mixture thereof.
本発明に係る製造方法により、ヘキソースから、穏和な条件で５−ＨＭＦを製造することができる。また、有機酸の沸点が低い為、反応溶液から蒸留等の方法により容易に溶媒を除去できる。 By the production method according to the present invention, 5-HMF can be produced from hexose under mild conditions. Moreover, since the boiling point of the organic acid is low, the solvent can be easily removed from the reaction solution by a method such as distillation.
本発明は、ヘキソースを含む原料を溶媒中で加熱して５−ＨＭＦを製造する方法において、前記溶媒として有機酸を使用することを特徴とする５−ＨＭＦの製造方法である。以下、本発明の製造方法について詳細に説明する。 The present invention is a method for producing 5-HMF, wherein an organic acid is used as the solvent in a method for producing 5-HMF by heating a raw material containing hexose in a solvent. Hereinafter, the production method of the present invention will be described in detail.
本発明による５−ＨＭＦ合成では、まず、容器内で有機酸とヘキソースを含む原料とを混合し、ヘキソースを溶解させる。その後、該反応溶液を加熱し、５−ＨＭＦを生成する。なお、該反応溶液には、酸触媒を添加してもよい。 In the 5-HMF synthesis according to the present invention, first, an organic acid and a raw material containing hexose are mixed in a container to dissolve the hexose. Thereafter, the reaction solution is heated to produce 5-HMF. An acid catalyst may be added to the reaction solution.
本発明において溶媒として用いる有機酸は、特に限定されるものではないが、１気圧における沸点が１５０℃以下のものが好ましい。また、溶媒としては、異なる有機酸同士の混合液を用いることもできる。本発明に用いる有機酸としては、溶媒除去の観点から、沸点が１５０℃以下の有機酸として、例えば、プロピオン酸、酢酸又はギ酸が挙げられる。 The organic acid used as a solvent in the present invention is not particularly limited, but preferably has a boiling point at 1 atm of 150 ° C. or less. Moreover, as a solvent, the liquid mixture of different organic acids can also be used. As an organic acid used for this invention, a propionic acid, an acetic acid, or a formic acid is mentioned as an organic acid whose boiling point is 150 degrees C or less from a viewpoint of solvent removal, for example.
また、溶媒中には水が存在しない方が望ましいが、少量の水が存在しても有機酸が溶媒としての機能を損なう程の量でなければ、本発明による５−ＨＭＦの製造は可能である。さらに、本発明における溶媒には、有機酸以外にも、本発明の効果を妨げるものでなければ他の溶媒が含まれていてもよく、溶媒としては、例えば、アセトン、メチルイソブチルケトンのようなケトン類、酢酸エチルのようなエステル類、ジエチルエーテルのようなエーテル類などが挙げられる。 In addition, it is desirable that no water is present in the solvent. However, even if a small amount of water is present, 5-HMF can be produced according to the present invention unless the amount of the organic acid impairs the function as a solvent. is there. Furthermore, the solvent in the present invention may contain other solvents besides the organic acid as long as they do not interfere with the effects of the present invention. Examples of the solvent include acetone and methyl isobutyl ketone. Examples include ketones, esters such as ethyl acetate, ethers such as diethyl ether, and the like.
本発明における原料としては、ヘキソースを用いることができる。ヘキソース、つまり炭素数６の単糖としては、特に限定されるものではないが、例えば、グルコース、フルクトース、ガラクトース、マンノース又はソルビトースを挙げることができ、特にフルクトースが望ましい。また、原料としては、これらの単糖類の混合物を用いることもできる。公知のようにヘキソースは加熱脱水反応を受けて５−ＨＭＦを生成する。 As a raw material in the present invention, hexose can be used. The hexose, that is, a monosaccharide having 6 carbon atoms is not particularly limited, and examples thereof include glucose, fructose, galactose, mannose, and sorbitol, and fructose is particularly desirable. Moreover, a mixture of these monosaccharides can also be used as a raw material. As is known, hexose undergoes a heat dehydration reaction to produce 5-HMF.
さらに、溶媒中に本発明の効果を妨げない程度に少量の水が含まれている場合は、本発明における原料としては、加水分解によりヘキソースを生成する糖類を用い、反応系中でヘキソースを生成させることができる。加水分解性を有する糖類が含有されている場合であっても、それらの糖類が加水分解されてヘキソースを生成した後、該ヘキソースが加熱脱水され、５−ＨＭＦを生成することができるからである。加水分解によりヘキソースを生成する糖類としては、例えば、オリゴ糖や多糖類が挙げられる。オリゴ糖としては、例えば、スクロースやマルトース等が挙げられる。多糖類としては、セルロース、デンプン又はイヌリンなどが挙げられる。なお、少量の水とは、本発明の効果を妨げない程度の量であって、加水分解によりヘキソースを生成する糖類を反応系において加水分解できる量のことをいう。 Furthermore, when the solvent contains a small amount of water to the extent that the effects of the present invention are not hindered, saccharides that generate hexose by hydrolysis are used as raw materials in the present invention, and hexose is generated in the reaction system. Can be made. This is because even when saccharides having hydrolyzability are contained, after the saccharides are hydrolyzed to produce hexose, the hexose can be dehydrated by heating to produce 5-HMF. . Examples of saccharides that generate hexose by hydrolysis include oligosaccharides and polysaccharides. Examples of oligosaccharides include sucrose and maltose. Examples of the polysaccharide include cellulose, starch, and inulin. The small amount of water means an amount that does not interfere with the effects of the present invention and can hydrolyze a saccharide that generates hexose by hydrolysis in the reaction system.
本発明における反応温度は、５０℃以上溶媒の沸点以下であればよいが、用いる原料や溶媒等に応じて適宜調整することができる。特に制限されるものではないが、６０℃以上溶媒の沸点以下が好ましく、８０℃以上溶媒の沸点以下がより好ましい。 Although the reaction temperature in this invention should just be 50 degreeC or more and the boiling point of a solvent, it can adjust suitably according to the raw material, solvent, etc. to be used. Although it does not restrict | limit in particular, 60 degreeC or more and the boiling point of a solvent or less are preferable, and 80 degreeC or more and the boiling point or less of a solvent are more preferable.
本発明における方法では、特に触媒を用いなくても５−ＨＭＦを製造可能であるが、生成効率を向上する観点から、酸触媒を用いることが好ましい。酸触媒としては、スルホン酸型のイオン交換樹脂を使用することができ、例としては、Ａｍｂｅｒｌｙｓｔ １５ Ｄｒｙ（登録商標、オルガノ株式会社製）、ＭＴ−Ｋ−１０２２（登録商標、ムロマチテクノス株式会社製）等を挙げることができる。反応に酸触媒を用いる場合、反応後の分離の観点から、強酸性イオン交換樹脂などの不溶性の触媒が望ましい。 In the method of the present invention, 5-HMF can be produced without using a catalyst, but an acid catalyst is preferably used from the viewpoint of improving production efficiency. As the acid catalyst, a sulfonic acid type ion exchange resin can be used, and examples thereof include Amberlyst 15 Dry (registered trademark, manufactured by Organo Corporation), MT-K-1022 (registered trademark, manufactured by Muromachi Technos Co., Ltd.). And the like. When an acid catalyst is used for the reaction, an insoluble catalyst such as a strongly acidic ion exchange resin is desirable from the viewpoint of separation after the reaction.
また、最適な反応時間は、原料、溶媒、反応温度又は触媒の種類若しくは量等によって異なるが、例えば、反応温度を１１８℃とし、触媒にＡｍｂｅｒｌｙｓｔ１５ Ｄｒｙ ２．５ｇを使用した場合は、０．５〜５時間程度が望ましい。また、反応温度を１００℃とし、触媒にＡｍｂｅｒｌｙｓｔ１５ Ｄｒｙ ２００ｍｇを使用した場合には、２０〜４０時間程度が望ましい。反応温度を上げるほど、また触媒量を増やすほど、最適な反応時間は短くなる。 The optimum reaction time varies depending on the raw material, solvent, reaction temperature, or the type or amount of the catalyst. For example, when the reaction temperature is 118 ° C. and Amberlyst 15 Dry 2.5 g is used as the catalyst, 0.5% About 5 hours is desirable. In addition, when the reaction temperature is 100 ° C. and 200 mg of Amberlyst 15 Dry is used as the catalyst, about 20 to 40 hours is desirable. As the reaction temperature is increased and the amount of catalyst is increased, the optimum reaction time is shortened.
溶媒量は、特に限定されるものではないが、原料が全て溶媒に溶解する量であることが好ましい。例えば、原料をフルクトースとした場合、溶媒の量は、フルクトース１重量部に対して５〜１０００重量部であることが望ましく、９〜１００重量部であることがより望ましい。低温で長時間反応させる場合であれば、さらにフルクトースの量を増やすことも可能である。 The amount of the solvent is not particularly limited, but is preferably an amount in which all raw materials are dissolved in the solvent. For example, when the raw material is fructose, the amount of the solvent is preferably 5 to 1000 parts by weight and more preferably 9 to 100 parts by weight with respect to 1 part by weight of fructose. If the reaction is performed at a low temperature for a long time, the amount of fructose can be further increased.
なお、反応中、反応溶液内に不溶性の固体成分が析出する場合があるが、この析出はフルクトース濃度、反応温度、反応時間に依存し、糖類の濃度が高い程、反応温度が高い程、反応時間が長い程起こりやすくなる。例えば、原料をフルクトース、溶媒を氷酢酸として、フルクトース濃度を９．５重量部、反応温度を１１８℃で行った場合、２０時間後には析出が見られる。 During the reaction, insoluble solid components may precipitate in the reaction solution. This precipitation depends on the fructose concentration, reaction temperature, and reaction time. The higher the saccharide concentration, the higher the reaction temperature, The longer the time, the more likely it will happen. For example, when the raw material is fructose, the solvent is glacial acetic acid, the fructose concentration is 9.5 parts by weight, and the reaction temperature is 118 ° C., precipitation is observed after 20 hours.
反応終了後、反応溶液から溶媒を除去するためには、従来の方法を用いることができ、例えば、蒸留により容易に溶媒を除去することができる。 In order to remove the solvent from the reaction solution after completion of the reaction, a conventional method can be used. For example, the solvent can be easily removed by distillation.
（実施例１）
５ｇフルクトース（キシダ化学株式会社製）、５０ｍｌ氷酢酸（キシダ化学株式会社製）およびマグネティックスターラーを丸底フラスコに添加し、フラスコの上部にモレキュラーシーブを充填した管を、さらにその上部に冷却管を装着した。
Example 1
Add 5 g fructose (manufactured by Kishida Chemical Co., Ltd.), 50 ml of glacial acetic acid (manufactured by Kishida Chemical Co., Ltd.) and a magnetic stirrer to the round bottom flask. Installed.
その後、上記フラスコの内容物を、電磁撹拌装置で撹拌しながら高温槽中で７０℃まで昇温し、フルクトースを溶解させた。フルクトースが溶解した後、上記フラスコに２．５ｇのＡｍｂｅｒｌｙｓｔ１５ Ｄｒｙを添加し、内容物を撹拌しながら３０分以内の間に反応温度である１１８℃まで昇温した。１１８℃に達してから３時間、保温・撹拌を続けながら反応を行った後、試料を採取し、純水で希釈して液体クロマトグラフィーで測定した。示唆屈折法およびＵＶ検出法（吸収波長：２８４ｎｍ）で得られたクロマトグラムにおける５−ＨＭＦのピーク面積を測定し、あらかじめ作成しておいた５−ＨＭＦの濃度−面積の関係図を用いて試料中の５−ＨＭＦ濃度を計算した。その結果、仕込みフルクトース基準で３５．４モル％の収率で５−ＨＭＦの生成が確認された。 Thereafter, the contents of the flask were heated to 70 ° C. in a high-temperature bath while stirring with an electromagnetic stirrer to dissolve fructose. After the fructose was dissolved, 2.5 g of Amberlyst15 Dry was added to the flask, and the content was heated to 118 ° C. as the reaction temperature within 30 minutes while stirring the contents. After the reaction was continued for 3 hours while maintaining the temperature and stirring after reaching 118 ° C., a sample was taken, diluted with pure water, and measured by liquid chromatography. The peak area of 5-HMF in the chromatogram obtained by the suggested refraction method and the UV detection method (absorption wavelength: 284 nm) was measured, and the sample was prepared using the 5-HMF concentration-area relationship diagram prepared in advance. The medium 5-HMF concentration was calculated. As a result, it was confirmed that 5-HMF was produced in a yield of 35.4 mol% based on the charged fructose.
（実施例２）
実施例１において、上記反応温度を１００℃、反応時間を２８時間、Ａｍｂｅｒｌｙｓｔ１５ Ｄｒｙの量を２００ｍｇに設定し、それ以外の条件は同じにして反応を行ったところ、仕込みフルクトース基準で２９．６モル％の収率で５−ＨＭＦの生成が確認された。
(Example 2)
In Example 1, the reaction temperature was set to 100 ° C., the reaction time was set to 28 hours, the amount of Amberlyst15 Dry was set to 200 mg, and the reaction was carried out under the same conditions except for 29.6 mol based on the charged fructose. The production of 5-HMF was confirmed with a yield of%.
（実施例３）
実施例１において、上記反応温度を８０℃に、反応時間を３０時間に設定し、それ以外の条件を同じにして反応を行ったところ、仕込みフルクトース基準で１９．９モル％の収率で５−ＨＭＦの生成が確認された。
(Example 3)
In Example 1, the reaction temperature was set to 80 ° C., the reaction time was set to 30 hours, and the other conditions were the same. The reaction was carried out at a yield of 19.9 mol% on the basis of the charged fructose. -Production of HMF was confirmed.
（実施例４）
実施例１において、酢酸の代わりにギ酸（キシダ化学株式会社製）を用い、Ａｍｂｅｒｌｙｓｔ１５ Ｄｒｙを添加せず、温度を１００℃、反応時間を２３時間に設定し、それ以外の条件を同じにして反応を行ったところ、仕込みフルクトース基準で２２．１モル％の収率で５−ＨＭＦの生成が確認された。
Example 4
In Example 1, formic acid (manufactured by Kishida Chemical Co., Ltd.) was used in place of acetic acid, Amberlyst15 Dry was not added, the temperature was set to 100 ° C., the reaction time was set to 23 hours, and the other conditions were the same. As a result, it was confirmed that 5-HMF was produced in a yield of 22.1 mol% based on the charged fructose.
（比較例１）
実施例１において溶媒に、溶媒の除去が容易な純水を用い、反応時間を２４時間に設定し、それ以外の条件を同じにして反応を行ったところ、仕込みフルクトース基準で７．０モル％の低い収率で、５−ＨＭＦの生成が確認された。
(Comparative Example 1)
In Example 1, pure water that can be easily removed was used as the solvent, the reaction time was set to 24 hours, and the reaction was carried out under the same conditions as above. The result was 7.0 mol% based on the charged fructose. The production of 5-HMF was confirmed with a low yield of.
（実施例５）
５重量％の５−ＨＭＦを含む酢酸溶液９ｍｌをナス型フラスコに入れ、エバポレーターに装着した。このフラスコを１８０ｒｐｍで回転させながら、４０〜６０℃、１３３〜２６６Ｐａで、留分が出なくなるまで（約４０分間）減圧蒸留を行い、酢酸を留去した。その後、フラスコに残った試料を採取し、純水で希釈して液体クロマトグラフィーで測定した。示唆屈折法およびＵＶ検出法（吸収波長：２８４ｎｍ）で得られたクロマトグラムにおける５−ＨＭＦおよび酢酸のピーク面積を測定し、あらかじめ作成しておいた濃度−面積の関係図を用いて試料中の５−ＨＭＦおよび酢酸の濃度を計算した。その結果、蒸留前と比較して８６．３モル％の５−ＨＭＦを回収することができた。また、酢酸は除去され、検出されなかった。
(Example 5)
9 ml of an acetic acid solution containing 5% by weight of 5-HMF was placed in an eggplant-shaped flask and attached to an evaporator. While rotating the flask at 180 rpm, vacuum distillation was performed at 40 to 60 ° C. and 133 to 266 Pa until no fraction was obtained (about 40 minutes), and acetic acid was distilled off. Thereafter, the sample remaining in the flask was collected, diluted with pure water, and measured by liquid chromatography. The peak areas of 5-HMF and acetic acid in the chromatogram obtained by the suggested refraction method and the UV detection method (absorption wavelength: 284 nm) are measured, and the concentration-area relationship diagram prepared in advance is used. The concentrations of 5-HMF and acetic acid were calculated. As a result, it was possible to recover 86.3 mol% of 5-HMF compared to before distillation. Also, acetic acid was removed and not detected.
（比較例２）
実施例５において、溶媒にジメチルスルホキシド（極性溶媒、沸点１８９℃）を用い、その他は同じ条件で減圧蒸留を行った。その結果、減圧蒸留の時間は約１時間かかり、蒸留前と比較してほぼ１００モル％の５−ＨＭＦが確認できた。しかし、ジメチルスルホキシドは、蒸留前と比較して２０．９モル％残留していた。
(Comparative Example 2)
In Example 5, dimethyl sulfoxide (polar solvent, boiling point 189 ° C.) was used as a solvent, and vacuum distillation was performed under the same conditions. As a result, it took about 1 hour for distillation under reduced pressure, and almost 100 mol% of 5-HMF was confirmed compared with that before distillation. However, dimethyl sulfoxide remained 20.9 mol% compared to before distillation.
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