JP2024019582A - Synthesis method of 5-hydroxymethyl-2-furfural and 2,5-diformylfuran - Google Patents
Synthesis method of 5-hydroxymethyl-2-furfural and 2,5-diformylfuran Download PDFInfo
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- JP2024019582A JP2024019582A JP2023212536A JP2023212536A JP2024019582A JP 2024019582 A JP2024019582 A JP 2024019582A JP 2023212536 A JP2023212536 A JP 2023212536A JP 2023212536 A JP2023212536 A JP 2023212536A JP 2024019582 A JP2024019582 A JP 2024019582A
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- hmf
- organic liquid
- water
- diformylfuran
- liquid
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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 179
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 title claims abstract description 14
- QVYAWBLDJPTXHS-UHFFFAOYSA-N 5-Hydroxymethyl-2-furfural Natural products OC1=CC=C(C=O)O1 QVYAWBLDJPTXHS-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000001308 synthesis method Methods 0.000 title description 7
- 239000007788 liquid Substances 0.000 claims abstract description 94
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000002994 raw material Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 29
- 230000003647 oxidation Effects 0.000 claims abstract description 25
- -1 alkali metal salts Chemical class 0.000 claims abstract description 24
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 16
- 239000012043 crude product Substances 0.000 claims abstract description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 229910052784 alkaline earth metal Chemical class 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 78
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 56
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- 238000009835 boiling Methods 0.000 claims description 26
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
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Landscapes
- Saccharide Compounds (AREA)
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、バイオマス由来の原料から５－ヒドロキシメチル－２－フルフラールを合成する方法と、５－ヒドロキシメチル－２－フルフラールから２，５－ジホルミルフランを合成する方法に関する。 The present invention relates to a method for synthesizing 5-hydroxymethyl-2-furfural from biomass-derived raw materials and a method for synthesizing 2,5-diformylfuran from 5-hydroxymethyl-2-furfural.
木、草、藁、竹、もしくは綿などの各種バイオマス、そしてこれらバイオマス由来のチップ、パルプ、糸、またはこれらから得られる紙などの製品を原料として、これらに含まれるセルロースまたはヘミセルロースなどを水熱条件で処理すると、オリゴ糖、グルコマンナン、グルコース、マンノース、キシロース、フルクトースなどの糖類が得られる。これらの糖類をさらに処理すると、炭素数が１個から６個の各種炭化水素の誘導体が得られる。これらの炭化水素の誘導体のうち、２，５－ジホルミルフラン（以下「ＤＦＦ」と記載することがある）は、中間体である５－ヒドロキシメチル－２－フルフラール（以下「ＨＭＦ」と記載することがある）を経由して得られる（下記化学反応式）。ＤＦＦは、ＨＭＦの酸化または脱水素によって得られる。現在、ＤＦＦは、流通量が少ないため、医薬品原料価格ベースで約１万円／ｋｇと高価である。 Using various biomass such as wood, grass, straw, bamboo, or cotton, and products such as chips, pulp, thread, and paper obtained from these biomass as raw materials, the cellulose or hemicellulose contained in these is hydrothermally processed. When processed under these conditions, sugars such as oligosaccharides, glucomannan, glucose, mannose, xylose, and fructose are obtained. Further processing of these saccharides yields various hydrocarbon derivatives having from 1 to 6 carbon atoms. Among these hydrocarbon derivatives, 2,5-diformylfuran (hereinafter sometimes referred to as "DFF") is an intermediate, 5-hydroxymethyl-2-furfural (hereinafter referred to as "HMF"). (chemical reaction formula below). DFF is obtained by oxidation or dehydrogenation of HMF. Currently, DFF is expensive at about 10,000 yen/kg based on the price of pharmaceutical raw materials because the amount of DFF distributed is small.
これらバイオマス等からＨＭＦを合成し、このＨＭＦを酸化してＤＦＦを製造する方法が報告されている（特許文献１～特許文献３および非特許文献１～非特許文献４）。近年では、グルコースまたはフルクトースからＨＭＦを経由して直接ＤＦＦを合成する手法も報告されている（特許文献４および特許文献５）。しかし、バイオマスからＤＦＦの合成と各段階で得られる生成物の精製を考えた場合、ＨＭＦを経由してその酸化によってＤＦＦを合成する方法が確実である。 A method of synthesizing HMF from these biomass and the like and oxidizing this HMF to produce DFF has been reported (Patent Documents 1 to 3 and Non-Patent Documents 1 to 4). In recent years, a method of directly synthesizing DFF from glucose or fructose via HMF has also been reported (Patent Document 4 and Patent Document 5). However, when considering the synthesis of DFF from biomass and the purification of the products obtained at each step, a reliable method is to synthesize DFF by oxidizing HMF via HMF.
近年、ＨＭＦは、バイオマスから得られる重要な化合物の一つで、様々な化合物原料としての利用が期待されている。例えば、ＨＭＦ自体に生理活性があることは既に報告されている。医薬品、機能性食品、化粧品、浴用品、または医薬部外品にＨＭＦを配合することで、安全性が高い新しい抗アレルギー剤および抗炎症剤が容易に製造できる（特許文献６）。また、ＨＭＦから、鋳型造型用粘結剤、バイオプラスチックモノマー、医薬、農薬、殺虫剤、抗菌剤、香料、および高分子材料等を製造できる（特許文献７～特許文献１０）。その他にも、ＨＭＦは、燃料改質剤等としての利用価値もあり、潜在的需要が非常に大きい。 In recent years, HMF is one of the important compounds obtained from biomass, and is expected to be used as a raw material for various compounds. For example, it has already been reported that HMF itself has physiological activity. By incorporating HMF into pharmaceuticals, functional foods, cosmetics, bath products, or quasi-drugs, new highly safe anti-allergic agents and anti-inflammatory agents can be easily produced (Patent Document 6). Furthermore, binders for mold making, bioplastic monomers, medicines, agricultural chemicals, insecticides, antibacterial agents, fragrances, polymeric materials, etc. can be produced from HMF (Patent Documents 7 to 10). In addition, HMF has utility value as a fuel modifier, etc., and has a very large potential demand.
しかし、バイオマスから得られるＨＭＦは、アルデヒド基、ヒドロメチル基、およびフラン環から形成されるため、一般的な芳香族化合物に比べて反応しやすく、容易にオリゴマーとなりフミン質と呼ばれる褐色の不溶物（固形廃棄物）へと変化し、大量製造の実用化の大きな壁となっている。このため、フミン質への変化を抑えたＨＭＦの精製が重要である。ＨＭＦの精製方法として、多種多様な手法が提案されている。ＨＭＦの精製は困難である。 However, since HMF obtained from biomass is formed from aldehyde groups, hydromethyl groups, and furan rings, it is more reactive than general aromatic compounds and easily turns into oligomers, forming brown insoluble substances called humic substances ( (solid waste), which poses a major barrier to the practical implementation of mass production. For this reason, it is important to purify HMF with suppressed changes to humic substances. A wide variety of methods have been proposed as methods for purifying HMF. Purification of HMF is difficult.
例えばＨＭＦの物理的な精製方法である蒸留を行う場合、蒸留可能な温度で長時間ＨＭＦを晒すと、上記の固形廃棄物またはタール状の生成物が生じる。そのため、例えば超高真空下でＨＭＦを蒸留したり、流下薄膜減圧でＨＭＦを精製したり、より低温でＨＭＦを蒸留したりする方法、および蒸留後にさらに再結晶等を行って精製する方法が報告されている（特許文献１１）。これらの精製方法でもＨＭＦの収率低下を抑えることは難しい。 For example, when performing distillation, which is a physical purification method for HMF, exposing HMF for a long time at a temperature that allows distillation produces the above-mentioned solid waste or tar-like products. For this reason, there have been reports of methods such as distilling HMF under ultra-high vacuum, purifying HMF using falling thin film vacuum, distilling HMF at lower temperatures, and purifying HMF by further recrystallization after distillation. (Patent Document 11). Even with these purification methods, it is difficult to suppress a decrease in the yield of HMF.
さらに、ＨＭＦを化学的に精製する方法として、活性なアルデヒド基またはヒドロキシメチル基に保護基を導入し、アセタールまたはエステルに変換してから蒸留した後、保護基を外し、再結晶で精製する方法がよく知られている（非特許文献５～８）。また、酵素を使ってＨＭＦをエステルにしてから精製する方法が報告されている。しかし、これらの精製手法でさえも、エステルからＨＭＦを精製する工程で約２３％のＨＭＦが減少する。このため、精製されたＨＭＦは高価である。 Furthermore, as a method for chemically refining HMF, a method of introducing a protecting group into an active aldehyde group or hydroxymethyl group, converting it to an acetal or ester, distilling it, removing the protecting group, and purifying it by recrystallization. is well known (Non-patent Documents 5 to 8). Furthermore, a method has been reported in which HMF is converted into an ester using an enzyme and then purified. However, even with these purification techniques, approximately 23% of HMF is lost in the process of purifying HMF from ester. For this reason, purified HMF is expensive.
本発明は、このような事情に鑑みてなされたものであり、バイオマス由来の各種原料からＨＭＦを効率的に合成する方法と、ＨＭＦからＤＦＦを効率的に合成する方法を提供することを目的とする。 The present invention has been made in view of these circumstances, and aims to provide a method for efficiently synthesizing HMF from various raw materials derived from biomass, and a method for efficiently synthesizing DFF from HMF. do.
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、安価なアルカリ金属塩またはアルカリ土類金属塩と、塩化鉄などの卑金属塩の混合物を用い、テトラヒドロフランなどの有機液体と水を混合した混合液体中で、各種バイオマス由来のセルロース、六炭糖であるグルコースもしくはフルクトース等、もしくは六炭糖から構成されるオリゴ糖を含有する原料、またはこれらオリゴ糖を含有する原料をさらに糖化して得られたグルコースもしくはフルクトース等の糖類を含む糖液を含有する原料を水熱処理することで、ＨＭＦが高選択的に得られることを見出した。 As a result of intensive research to achieve the above object, the present inventors have discovered that using a mixture of inexpensive alkali metal salts or alkaline earth metal salts and base metal salts such as iron chloride, organic liquids such as tetrahydrofuran and water Cellulose derived from various biomass, hexoses such as glucose or fructose, or raw materials containing oligosaccharides composed of hexoses, or raw materials containing these oligosaccharides are further saccharified in a mixed liquid containing It has been found that HMF can be obtained with high selectivity by hydrothermally treating a raw material containing a sugar solution containing saccharides such as glucose or fructose.
また、得られたＨＭＦは反応液中で不安定で、特に水の存在が安定性に影響を与える。そこで、このＨＭＦを含む反応液を冷却し、反応液中の水を固体（氷）として除去することで、ＨＭＦがフミン質に変化するのを極力抑えたＨＭＦ含有液が得られることを見出した。一方、芳香族化合物を含まずに、グルコースまたはフルクトースを含む糖液を原料として製造したＨＭＦは、反応溶液中で安定であることを見出した。したがって、溶媒中でＨＭＦを取り扱うことで、ＨＭＦのロスが極力抑えられる。 Furthermore, the obtained HMF is unstable in the reaction solution, and the presence of water particularly affects the stability. Therefore, they discovered that by cooling the reaction solution containing HMF and removing the water in the reaction solution as solid (ice), it was possible to obtain an HMF-containing solution that minimized the change of HMF into humic substances. . On the other hand, it has been found that HMF produced from a sugar solution containing glucose or fructose without containing aromatic compounds is stable in the reaction solution. Therefore, by handling HMF in a solvent, loss of HMF can be minimized.
さらに、このＨＭＦ含有液を酸化することでＤＦＦが容易に合成できることと、その後の既報で示された各種簡単な再結晶等の精製操作で純度９５％以上のＤＦＦが得られることを見出した。本発明は、これらの知見に基づいて完成に至ったものである。本発明のＨＭＦの合成方法は、アルカリ金属塩およびアルカリ土類金属塩の一種類以上の塩の存在下、バイオマス由来の炭水化物を含有する原料を、有機液体と水の混合液体を媒体として水熱処理することにより、ＨＭＦを含有する反応液を得る水熱工程を有する。 Furthermore, we found that DFF can be easily synthesized by oxidizing this HMF-containing solution, and that DFF with a purity of 95% or more can be obtained by various simple purification operations such as recrystallization as shown in subsequent reports. The present invention has been completed based on these findings. The HMF synthesis method of the present invention involves hydrothermal treatment of a biomass-derived carbohydrate-containing raw material using a mixed liquid of an organic liquid and water as a medium in the presence of one or more types of alkali metal salts and alkaline earth metal salts. The method includes a hydrothermal step for obtaining a reaction solution containing HMF.
本発明のある態様のＤＦＦの合成方法は、アルカリ金属塩およびアルカリ土類金属塩の一種類以上の塩と、卑金属塩の混合物の存在下、バイオマス由来の炭水化物を含有する原料を、有機液体と水の混合液体を媒体として水熱処理することにより、ＨＭＦを含有する反応液を得る水熱工程と、反応液の有機液体層から水を除去してＨＭＦを含有する粗生成物を効率的に得る水除去工程と、粗生成物中のＨＭＦを酸化してＤＦＦを得る酸化工程を有する。 A method for synthesizing DFF according to an embodiment of the present invention is to combine a biomass-derived carbohydrate-containing raw material with an organic liquid in the presence of a mixture of one or more types of alkali metal salts and alkaline earth metal salts and a base metal salt. A hydrothermal process for obtaining a reaction liquid containing HMF by hydrothermal treatment using a mixed liquid of water as a medium, and a hydrothermal process for obtaining a HMF-containing crude product by removing water from the organic liquid layer of the reaction liquid. The method includes a water removal step and an oxidation step in which HMF in the crude product is oxidized to obtain DFF.
本発明の他の態様のＤＦＦの合成方法は、アルカリ金属塩およびアルカリ土類金属塩の一種類以上の塩の存在下、糖類を含有する原料を、有機液体と水の混合液体を媒体として水熱処理することにより、ＨＭＦを含有する反応液を得る水熱工程と、有機液体および水の沸点より沸点が高い高沸点有機液体を反応液に加えた後、有機液体および水の少なくとも一部を留去して、ＨＭＦを含有する含有液を得る置換工程と、含有液中のＨＭＦを酸化してＤＦＦを得る酸化工程を有する。 A method for synthesizing DFF according to another embodiment of the present invention is to use a raw material containing saccharide in the presence of one or more salts of an alkali metal salt and an alkaline earth metal salt, and water and water using a mixed liquid of an organic liquid and water as a medium. A hydrothermal step for obtaining a reaction solution containing HMF by heat treatment, and a step of adding an organic liquid and a high-boiling organic liquid having a boiling point higher than the boiling point of water to the reaction solution, and then distilling at least a part of the organic liquid and water. The method includes a replacement step in which HMF is removed from the liquid to obtain a liquid containing HMF, and an oxidation step in which HMF in the liquid is oxidized to obtain DFF.
本発明によれば、水に溶解する糖類はもちろん、水に溶けないバイオマスなどを原料とした水熱処理によってＨＭＦが効率的に製造できる。また、得られたＨＭＦを含有する反応液から水を除去することにより、ＨＭＦの安定性が向上し、ＨＭＦを高度に精製せずにこのまま酸化することで、ＤＦＦが効率良く製造できる。さらに、糖類を原料とした水熱処理によって得られたＨＭＦは、有機溶媒中で安定している。このため、ＨＭＦを含有する反応液に高沸点有機液体を加えた後に、有機液体と水の少なくとも一部を留去すれば、ＨＭＦは高沸点有機液体中でそのまま酸化できる。したがって、ＨＭＦのロスを抑えながらＤＦＦが得られる。 According to the present invention, HMF can be efficiently produced by hydrothermal treatment using not only water-soluble saccharides but also water-insoluble biomass and the like as raw materials. Furthermore, by removing water from the obtained HMF-containing reaction solution, the stability of HMF is improved, and by oxidizing HMF as it is without highly purifying it, DFF can be efficiently produced. Furthermore, HMF obtained by hydrothermal treatment using saccharides as a raw material is stable in organic solvents. Therefore, by adding a high-boiling organic liquid to a reaction solution containing HMF and then distilling off at least a portion of the organic liquid and water, HMF can be oxidized as is in the high-boiling organic liquid. Therefore, DFF can be obtained while suppressing HMF loss.
本発明の実施形態に係るＨＭＦの合成方法は水熱工程を備えている。水熱工程では、塩の存在下、原料を水熱処理して、ＨＭＦを含有する反応液を得る。本実施形態で用いる塩は、アルカリ金属塩およびアルカリ土類金属塩の一種類以上である。この塩の存在によって、ＨＭＦの反応収率が向上する。塩は、リチウム塩、ナトリウム塩、またはカルシウム塩であることが好ましい。塩のアニオンとしては、Ｆ－、Ｃｌ－、Ｂｒ－、Ｉ－、ＨＳＯ４ －、ＳＯ４ ２－、ＣＦ３ＳＯ３ －、ＮＯ３ －、（ＣＦ３ＳＯ２）２Ｎ－、ＢＦ４ －、ＰＦ６ －、ＣＨ３ＣＯＯ－、ＣＦ３ＣＯＯ－、ＨＰＯ４ －、およびＰＯ４ ２－などが挙げられる。 The HMF synthesis method according to the embodiment of the present invention includes a hydrothermal step. In the hydrothermal step, the raw material is hydrothermally treated in the presence of a salt to obtain a reaction solution containing HMF. The salt used in this embodiment is one or more types of alkali metal salts and alkaline earth metal salts. The presence of this salt improves the reaction yield of HMF. Preferably, the salt is a lithium, sodium or calcium salt. Salt anions include F − , Cl − , Br − , I − , HSO 4 − , SO 4 2− , CF 3 SO 3 − , NO 3 − , (CF 3 SO 2 ) 2 N − , BF 4 − , PF 6 − , CH 3 COO − , CF 3 COO − , HPO 4 − , and PO 4 2− .
アルカリ金属塩およびアルカリ土類金属塩の一種類以上の塩と、アルカリ金属塩およびアルカリ土類金属塩以外であって、塩化鉄および塩化亜鉛などの卑金属塩の存在下で水熱処理することで、ＨＭＦの反応収率がさらに向上する。卑金属塩のカチオンとしては、鉄、鉄鋼、銅、アルミニウム、鉛、亜鉛、すず、タングステン、インジウム、モリブデン、クロム、ゲルマニウム、タンタル、マグネシウム、コバルト、カドミウム、チタン、ジルコニウム、バナジウム、ガリウム、アンチモン、マンガン、ニッケル、ハフニウム、ニオブ、ビスマス、レニウム、およびタリウムなどが挙げられる。卑金属塩のアニオンとしては、Ｆ－、Ｃｌ－、Ｂｒ－、Ｉ－、ＨＳＯ４ －、ＳＯ４ ２－、ＣＦ３ＳＯ３ －、ＮＯ３ －、（ＣＦ３ＳＯ２）２Ｎ－、ＢＦ４ －、ＰＯ４ ３－、ＰＦ６ －、ＣＨ３ＣＯＯ－、ＣＦ３ＣＯＯ－、ＨＰＯ４ －、およびＰＯ４ ２－などが挙げられる。 By hydrothermal treatment in the presence of one or more salts of alkali metal salts and alkaline earth metal salts and base metal salts other than alkali metal salts and alkaline earth metal salts, such as iron chloride and zinc chloride, The reaction yield of HMF is further improved. Cations of base metal salts include iron, steel, copper, aluminum, lead, zinc, tin, tungsten, indium, molybdenum, chromium, germanium, tantalum, magnesium, cobalt, cadmium, titanium, zirconium, vanadium, gallium, antimony, and manganese. , nickel, hafnium, niobium, bismuth, rhenium, and thallium. Examples of anions of base metal salts include F − , Cl − , Br − , I − , HSO 4 − , SO 4 2− , CF 3 SO 3 − , NO 3 − , (CF 3 SO 2 ) 2 N − , BF 4 - , PO 4 3- , PF 6 - , CH 3 COO - , CF 3 COO - , HPO 4 - , PO 4 2- , and the like.
原料は、バイオマス由来の炭水化物を含有する。より具体的には、この原料は、例えば、稲わらまたはスギチップ等の草木系バイオマス、これらのバイオマス由来のパルプ、紙および再生紙、これらを糖化して得られたセルロース、ならびにこれらを糖化して得られた六炭糖および六炭糖から構成されるオリゴ糖を含む糖液を含有する。また、原料としては、水に溶解するグルコースまたはフルクトース等の六炭糖およびこれらの六炭糖からなるオリゴ糖等の糖類はもちろん、ソーダパルプ、クラフトパルプ、サルファイトパルプ、ケミグランドパルプ、リファイナーグランドパルプ、サーモメカニカルパルプ、および蒸解パルプなどの各種パルプ、水に溶けないセルロースを含むバイオマス、ならびに段ボール、新聞、紙容器、および再生紙などの紙が挙げられる。 The raw material contains carbohydrates derived from biomass. More specifically, this raw material includes, for example, vegetable biomass such as rice straw or cedar chips, pulp derived from these biomass, paper and recycled paper, cellulose obtained by saccharifying these, and cellulose obtained by saccharifying these. It contains a sugar solution containing the obtained hexose and an oligosaccharide composed of the hexose. In addition, raw materials include saccharides such as hexoses such as glucose or fructose that dissolve in water and oligosaccharides made of these hexoses, as well as soda pulp, kraft pulp, sulfite pulp, chemical ground pulp, and refiner ground. These include various types of pulp such as pulp, thermomechanical pulp, and digested pulp, biomass containing cellulose that is not soluble in water, and paper such as cardboard, newspaper, paper containers, and recycled paper.
水に溶けないセルロースを含むバイオマスとしては、例えば松、杉、ブナ、楓、およびユーカリなどの木材、稲わら、麦わら、もみがら、およびバガスなどの草、ならびに綿、麻、亜麻、椰子の果皮、および竹などの非木材が挙げられる。
原料に含まれる炭水化物としては、セルロース、グルコースまたはフルトースなど六炭糖、および六炭糖から構成されるオリゴ糖、ならびにバイオマス由来の物質に含まれるセルロースを糖化した糖類の一種類以上が挙げられる。
Biomass containing cellulose that is insoluble in water includes, for example, wood such as pine, cedar, beech, maple, and eucalyptus, grass such as rice straw, wheat straw, rice husk, and bagasse, and cotton, hemp, flax, and palm peel. , and non-wood materials such as bamboo.
The carbohydrates contained in the raw materials include cellulose, hexoses such as glucose or frutose, oligosaccharides composed of hexoses, and one or more types of saccharides obtained by saccharifying cellulose contained in biomass-derived substances.
原料に含まれる炭水化物の元となるバイオマスは特に制限はされず、じゃがいもまたはサトウキビのデンプンなどを含む食料となるバイオマスも使用できる。しかし、近年の食糧事情等から鑑みるに、食料に影響を及ぼさないまたは影響が小さい稲わら、麦わら、もみがら、椰子の果皮、バガス、トウモロコシの芯などの残渣、および野草などの草本系バイオマス由来の原料、ユーカリ、竹、杉、クヌギ、アカシデ、松などの薪、チップ、ペレット、ブリケット、木くず、製材端材などの木質系バイオマス由来の原料、ならびにこれらを糖化した糖類を含む糖液などを用いることが好ましい。 There are no particular restrictions on the biomass that is the source of the carbohydrates contained in the raw materials, and biomass that can be used as food, such as potato or sugarcane starch, can also be used. However, in view of the recent food situation, rice straw, wheat straw, rice husk, palm peel, bagasse, corn cob residue, etc., which have no or small impact on food, and herbaceous biomass such as wildflowers raw materials derived from wood biomass such as eucalyptus, bamboo, cedar, oak, red hornbeam, and pine firewood, chips, pellets, briquettes, wood chips, and lumber scraps, as well as sugar solutions containing sugars obtained by saccharifying these materials. It is preferable to use
これらの中でも原料は、ユーカリ、竹、および杉由来のチップ、ならびにこれらから得られる各種パルプ、そしてさらに各種パルプを糖化した糖類を含む糖液が好ましく、ユーカリ、竹、および杉由来のチップ、ならびにこれらから得られた蒸解パルプ、さらに杉またはユーカリのパルプを糖化した糖類を含む糖液がより好ましい。バイオマスを原料として直接用いる以外にも、近年はセルロース、六炭糖、および六炭糖から構成されるオリゴ糖を含む古紙なども原料として用いることができる。また、汎用的に流通しているグルコース、フルクトース、果糖、でんぷん、およびセルロースなどの炭水化物を含む物質も、原料として当然用いることができる。 Among these, the raw materials are preferably chips derived from eucalyptus, bamboo, and cedar, various pulps obtained from these, and sugar solutions containing saccharides obtained by saccharifying various pulps. Chips derived from eucalyptus, bamboo, and cedar, and More preferred are digested pulps obtained from these materials, as well as sugar solutions containing saccharides obtained by saccharifying cedar or eucalyptus pulp. In addition to directly using biomass as a raw material, in recent years, cellulose, hexose, and waste paper containing oligosaccharides composed of hexose can also be used as a raw material. Moreover, substances containing carbohydrates, such as glucose, fructose, fructose, starch, and cellulose, which are commonly distributed, can naturally be used as raw materials.
本実施形態では、有機液体と水の混合液体を媒体として原料を水熱処理する。水熱処理は、バッチ式、フロー式、またはパーコレート式で行える。また、水熱処理は温度１００℃以上２５０℃以下で行える。また、水熱処理は、バッチ式の場合は１時間以上６０時間以下で、フロー式およびパーコレート式の場合は１０分以上の滞在時間で行える。また、水熱処理は圧力０．１ＭＰａ以上２０ＭＰａ以下で行える。水熱処理の媒体としては、有機液体と水の混合液体が使用できる。セルロース、グルコース、およびフルクトースが反応しやすいからである。有機液体は、温度１００℃以上２５０℃以下、圧力０．１ＭＰａ以上２０ＭＰａ以下で、セルロース、グルコース、およびフルクトースと反応せず、かつ分解しないものから選択できる。 In this embodiment, raw materials are hydrothermally treated using a mixed liquid of an organic liquid and water as a medium. Hydrothermal treatment can be performed in a batch, flow, or percolate manner. Further, the hydrothermal treatment can be performed at a temperature of 100°C or more and 250°C or less. Further, the hydrothermal treatment can be carried out for a residence time of 1 hour or more and 60 hours or less in the case of a batch type, and for a residence time of 10 minutes or more in the case of a flow type or percolation type. Further, the hydrothermal treatment can be performed at a pressure of 0.1 MPa or more and 20 MPa or less. As a medium for hydrothermal treatment, a mixed liquid of an organic liquid and water can be used. This is because cellulose, glucose, and fructose react easily. The organic liquid can be selected from those that do not react with cellulose, glucose, and fructose, and do not decompose at a temperature of 100° C. or more and 250° C. or less and a pressure of 0.1 MPa or more and 20 MPa or less.
このような有機液体としては、テトラヒドロフラン、メチルテトラヒドロフラン、１，４－ジオキサン、ジエチルエーテル、ジメチルエーテル、ジメチルイミダゾリジノン、アセトニトリル、メタノール、エタノール、ブタノール、メチルイソブチルケトン、ヘキサフルオロイソプロパノール、酢酸エチル、ヘキサン、ジメチルホルムアミド、ジメチルスルフィド、アセトン、メチルエチルケトン、アセトンなどが挙げられる。これらの中で、有機液体としては、水に少しだけ溶け、かつ水と相分離できるテトラヒドロフラン、ジオキサン、ブタノール、メチルイソブチルケトン、酢酸エチル、ジメチルホルムアミド、ジメチルスルフィド、メチルエチルケトンなどが好ましい。 Such organic liquids include tetrahydrofuran, methyltetrahydrofuran, 1,4-dioxane, diethyl ether, dimethyl ether, dimethylimidazolidinone, acetonitrile, methanol, ethanol, butanol, methyl isobutyl ketone, hexafluoroisopropanol, ethyl acetate, hexane, Examples include dimethylformamide, dimethyl sulfide, acetone, methyl ethyl ketone, and acetone. Among these, preferred organic liquids include tetrahydrofuran, dioxane, butanol, methyl isobutyl ketone, ethyl acetate, dimethylformamide, dimethyl sulfide, and methyl ethyl ketone, which are slightly soluble in water and phase-separable from water.
なお、反応容器の耐圧性の事情などで高圧での水熱処理ができない場合、有機液体の一部を、より高沸点の有機液体に置換することで、目的のＨＭＦが得られる。例えば、有機液体であるテトラヒドロフランの約７５質量％を、より高沸点の有機液体であるトルエンなどの芳香族炭化水素で置換すれば、ＨＭＦの収率の低下を抑えつつ、圧力１ＭＰａ以下で水熱反応を行える。 Note that if hydrothermal treatment at high pressure is not possible due to the pressure resistance of the reaction vessel, the desired HMF can be obtained by replacing a portion of the organic liquid with an organic liquid having a higher boiling point. For example, if approximately 75% by mass of tetrahydrofuran, an organic liquid, is replaced with an aromatic hydrocarbon such as toluene, which is an organic liquid with a higher boiling point, hydrothermal heating at a pressure of 1 MPa or less can be achieved while suppressing a decrease in HMF yield. Can perform reactions.
原料の形態には特に制限がないが、混合液体中に均一に溶解または均一に分散していることが好ましい。原料からＨＭＦへの選択率が向上するからである。糖類を含む糖液が原料である場合は、混合液体中に原料が溶解するので、糖液を混合液体中に溶かした溶液をそのまま水熱処理できる。一方、木質系バイオマスまたは草本系バイオマスなどの水を含む各種媒体に難溶性のセルロースを含む原料は、予め粉砕して、混合液体に均一に分散させた分散液を水熱処理するのが好ましい。反応時に、混合液体中の原料に含まれる炭水化物の量は、０．１質量％以上であることが好ましく、１質量％以上であることがより好ましく、１０質量％以上であることがさらに好ましく、２５質量％以上であることが最も好ましい。 There is no particular restriction on the form of the raw material, but it is preferable that it is uniformly dissolved or uniformly dispersed in the mixed liquid. This is because the selectivity from raw materials to HMF is improved. When the raw material is a sugar solution containing saccharides, the raw material is dissolved in the mixed liquid, so the solution obtained by dissolving the sugar solution in the mixed liquid can be directly subjected to hydrothermal treatment. On the other hand, raw materials containing cellulose that are poorly soluble in various media containing water, such as woody biomass or herbaceous biomass, are preferably pulverized in advance, and a dispersion liquid that is uniformly dispersed in a mixed liquid is subjected to hydrothermal treatment. During the reaction, the amount of carbohydrates contained in the raw materials in the mixed liquid is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 10% by mass or more, Most preferably, it is 25% by mass or more.
バッチ式での水熱処理では、この原料の粉砕後の粒径が水熱処理に影響しないため、原料の粉砕後の粒径は、特に限定されない。しかし、フロー式で水熱処理を行う場合は、原料の粉砕後の粒径を１００μｍ以下にすることが好ましく、５０μｍ以下にすることがより好ましく、３０μｍ以下にすることがさらに好ましく、２０μｍ以下にすることが最も好ましい。原料が分散した混合液体の分散液が安定するからである。 In batch-type hydrothermal treatment, the particle size of the raw material after pulverization does not affect the hydrothermal treatment, so the particle size of the raw material after pulverization is not particularly limited. However, when hydrothermal treatment is performed using a flow method, the particle size of the raw material after pulverization is preferably 100 μm or less, more preferably 50 μm or less, even more preferably 30 μm or less, and 20 μm or less. is most preferable. This is because the dispersion of the mixed liquid in which the raw materials are dispersed becomes stable.
本発明の実施形態に係るＤＦＦの合成方法は、水熱工程と、水除去工程と、酸化工程を備えている。水熱工程では、本実施形態のＨＭＦの合成方法の水熱工程と同様に、ＨＭＦを含有する反応液を得る。必要に応じた濾過によって残った原料を取り除いたこの反応液を放置すると、水層と有機液体層に分離する。生成したＨＭＦは有機液体層により多く溶解している。 The DFF synthesis method according to the embodiment of the present invention includes a hydrothermal step, a water removal step, and an oxidation step. In the hydrothermal step, a reaction solution containing HMF is obtained similarly to the hydrothermal step of the HMF synthesis method of this embodiment. When this reaction solution, which has been filtered as necessary to remove remaining raw materials, is left to stand, it separates into an aqueous layer and an organic liquid layer. The generated HMF is more dissolved in the organic liquid layer.
そこで、反応液から有機液体層を採取して、次の酸化工程に用いる。有機液体層に含まれるＨＭＦを酸化してＤＦＦを生成させるためには、水を含む有機液体層から、できるだけ多くの水を除去する必要がある。水除去工程では、反応液の有機液体層から水を除去して、ＨＭＦを含有する粗生成物を得る。 Therefore, an organic liquid layer is collected from the reaction solution and used in the next oxidation step. In order to oxidize HMF contained in the organic liquid layer to generate DFF, it is necessary to remove as much water as possible from the water-containing organic liquid layer. In the water removal step, water is removed from the organic liquid layer of the reaction solution to obtain a crude product containing HMF.
しかし、このＨＭＦを含有する反応液を加熱すると、ＨＭＦは、フミン質からなる不溶性固体であって、ＨＭＦへの再生が不可能な物質に容易に変換されてしまう。このため、蒸留などの加熱が必要な方法で、この反応液の有機液体層から水分を除去することは好ましくない。そこで、この反応液を冷却して、有機液体層中の水分を凍らせた後に氷を濾過することによって、有機液体層中の水を除去でき、ＨＭＦを含有する粗生成物が得られる。このときの反応液の冷却温度は、有機液体の凝固点以上０℃以下が好ましい。例えば、有機液体がテトラヒドロフラン（以下「ＴＨＦ」と記載することがある）のとき、反応液を－１０８℃以上０℃以下に冷却すれば、好適に反応液中の水を氷として除去できる。 However, when a reaction solution containing this HMF is heated, HMF is easily converted into a substance that is an insoluble solid composed of humic substances and cannot be regenerated into HMF. For this reason, it is not preferable to remove water from the organic liquid layer of the reaction solution by a method that requires heating, such as distillation. Therefore, by cooling the reaction solution to freeze the water in the organic liquid layer and then filtering the ice, the water in the organic liquid layer can be removed and a crude product containing HMF can be obtained. The cooling temperature of the reaction liquid at this time is preferably above the freezing point of the organic liquid and below 0°C. For example, when the organic liquid is tetrahydrofuran (hereinafter sometimes referred to as "THF"), water in the reaction solution can be suitably removed as ice by cooling the reaction solution to -108°C or higher and 0°C or lower.
なお、次の酸化工程の前に、ＨＭＦを含有する反応液の有機液体を、酸化工程で用いる他の有機液体に置換する場合、従来は、反応液から有機液体を除去した後に、この他の有機液体を添加していた。この従来の方法では、有機液体の除去時に濃縮されたＨＭＦと微量に残る水分などが要因となって、ＨＭＦがフミン質に変わる現象が著しかった。このため、ＨＭＦの大幅なロスを招き、最終的生成物であるＤＦＦの収率の低下をもたらした。 In addition, when replacing the organic liquid in the reaction solution containing HMF with another organic liquid used in the oxidation step before the next oxidation step, conventionally, after removing the organic liquid from the reaction solution, this other organic liquid is replaced. Added organic liquid. In this conventional method, there was a significant phenomenon in which HMF was converted into humic substances due to concentrated HMF and trace amounts of moisture remaining during removal of the organic liquid. This resulted in a large loss of HMF, resulting in a decrease in the yield of the final product, DFF.
しかし、リグニン成分などの芳香族化合物を含まず、グルコースまたはフルクトースを含む糖類を原料とした場合、水熱工程で得られた反応液中で、ＨＭＦが長時間安定していた。このため、反応液中の水を氷として除去しなくても、液・液分離による水分除去のみで、次の酸化工程が行える。さらに、水熱工程で得られた反応液中の有機液体および水の沸点より沸点が高く、酸化工程で用いる高沸点有機液体を反応液に加えた後、有機液体を留去しつつ、共沸現象を利用して有機液体に含まれる水を留去すれば、溶液状態のままで有機媒体を置換でき、ＨＭＦを含有する含有液が得られる。 However, when saccharides containing glucose or fructose without containing aromatic compounds such as lignin components were used as raw materials, HMF was stable for a long time in the reaction solution obtained in the hydrothermal process. Therefore, the next oxidation step can be performed only by removing water by liquid-liquid separation without removing water in the reaction solution as ice. Furthermore, after adding to the reaction liquid a high boiling point organic liquid that has a boiling point higher than the organic liquid in the reaction liquid obtained in the hydrothermal process and water and is used in the oxidation process, an azeotropic distillation process is performed while distilling off the organic liquid. If water contained in an organic liquid is distilled off using this phenomenon, the organic medium can be replaced while the organic liquid remains in a solution state, and a liquid containing HMF can be obtained.
すなわち、糖類を含有する原料を水熱工程に用いる場合、本実施形態の水除去工程に代えて置換工程が適用できる。なお、本願の「糖類」は、単糖類と二糖類だけでなく、オリゴ糖などの少糖類、およびでんぷんなどの多糖類も含む。この置換工程では、有機液体および水の沸点より沸点が高い高沸点有機液体を反応液に加えた後、有機液体を留去しつつ、共沸現象を利用して有機液体に含まれる水の少なくとも一部を留去して、ＨＭＦを含有する含有液を得る。留去する有機液体および水の量は多いほど好ましい。酸化工程に適した高沸点有機液体の含有量を限りなく多くできるとともに、ＨＭＦの不安定化の原因の一つとなる水を少なくできるからである。不可避的に含まれる有機液体および水以外は、高沸点有機液体に置換することが最も好ましい。 That is, when a raw material containing saccharides is used in a hydrothermal process, a substitution process can be applied instead of the water removal process of this embodiment. Note that "saccharides" in the present application include not only monosaccharides and disaccharides, but also oligosaccharides such as oligosaccharides, and polysaccharides such as starch. In this substitution process, an organic liquid and a high-boiling organic liquid with a boiling point higher than that of water are added to the reaction liquid, and then the organic liquid is distilled off, and at least the water contained in the organic liquid is removed using an azeotropic phenomenon. A portion is distilled off to obtain a liquid containing HMF. It is preferable that the amount of organic liquid and water to be distilled off is as large as possible. This is because the content of a high boiling point organic liquid suitable for the oxidation process can be increased as much as possible, and the amount of water, which is one of the causes of destabilization of HMF, can be reduced. It is most preferable to replace the unavoidably contained organic liquid and water with a high boiling point organic liquid.
有機液体がＴＨＦのとき、酸化工程で用いる高沸点有機液体としては、常圧での沸点が６６℃以上の有機媒体が挙げられる。このような有機媒体としては、ヘキサン、酢酸エチル、アセトニトリル、ジメチルホルムアミド、ジメチルスルホキシド、またはトリクロロベンゼンなどの脂肪族系溶媒、およびトルエン、エチルベンゼン、クメン、キシレン、アニソール、ベンズアルデヒド、アセトフェノン、ベンゾフェノン、またはピリジンなどの芳香族系溶媒が挙げられる。これらの中でも、酸素または空気を酸化剤とする触媒反応でＨＭＦからＤＦＦを合成するのに適したトルエン、エチルベンゼン、クメン、キシレン、またはアニソールが好ましい。さらに、トルエンまたはアニソールが好ましい。水熱工程で用いたＴＨＦを容易に置換できると同時に、これらの有機媒体は水と共沸するため、有機媒体に溶解している水も除去できるからである。 When the organic liquid is THF, the high boiling point organic liquid used in the oxidation step includes an organic medium having a boiling point of 66° C. or higher at normal pressure. Such organic media include aliphatic solvents such as hexane, ethyl acetate, acetonitrile, dimethylformamide, dimethylsulfoxide, or trichlorobenzene, and toluene, ethylbenzene, cumene, xylene, anisole, benzaldehyde, acetophenone, benzophenone, or pyridine. Examples include aromatic solvents such as. Among these, toluene, ethylbenzene, cumene, xylene, or anisole, which are suitable for synthesizing DFF from HMF by a catalytic reaction using oxygen or air as an oxidizing agent, are preferred. Furthermore, toluene or anisole is preferred. This is because THF used in the hydrothermal process can be easily replaced, and at the same time, since these organic media are azeotropic with water, water dissolved in the organic media can also be removed.
酸化工程では、水除去工程で得られた粗生成物中のＨＭＦを酸化してＤＦＦを得る。より具体的には、例えば、ＨＭＦを含有する粗生成物から有機液体を除去した後、酸化反応に用いる溶媒にこのＨＭＦを溶かして酸化反応を行う。ＨＭＦの酸化方法には特に制限がない。しかし、粗生成物中には数十質量％のバイオマス由来の不純物が含まれており、ＨＭＦの酸化に固体触媒などを用いると、触媒被毒が起こりやすく、酸化反応を効率的に進ませることができない。 In the oxidation step, HMF in the crude product obtained in the water removal step is oxidized to obtain DFF. More specifically, for example, after removing the organic liquid from a crude product containing HMF, the HMF is dissolved in a solvent used for the oxidation reaction to perform the oxidation reaction. There are no particular restrictions on the method of oxidizing HMF. However, the crude product contains several tens of mass % of impurities derived from biomass, and when a solid catalyst is used to oxidize HMF, catalyst poisoning tends to occur, making it difficult to efficiently proceed with the oxidation reaction. I can't.
このため、酸化工程では、均一系の酸化触媒または強い酸化剤などを用いることが好ましいが、酸化マンガンなど不均一系の酸化剤等も好ましい。酸化触媒としては、塩化銅、ヨウ化銅、ニトロキシラジカル（Ｒ２Ｎ－Ｏ・）、およびバナジウム錯体などが挙げられ、酸化剤としては、酸化マンガン、過マンガン酸、クロム酸、二クロム酸、酸化クロム、硝酸、塩素酸、次亜塩素酸、ハロゲン、オゾン、酸素、過酸化水素、過酸化物、および酸素などが挙げられる。酸化工程では、これらの酸化剤と前述の各種酸化触媒とを組み合わせた酸化も行うことができる。また、酸化工程では、置換工程で得られたＨＭＦ含有液中のＨＭＦを酸化してＤＦＦを得てもよい。 Therefore, in the oxidation step, it is preferable to use a homogeneous oxidation catalyst or a strong oxidizing agent, but a heterogeneous oxidizing agent such as manganese oxide is also preferable. Examples of oxidation catalysts include copper chloride, copper iodide, nitroxy radicals (R 2 N-O.), and vanadium complexes, and examples of oxidizing agents include manganese oxide, permanganic acid, chromic acid, and dichromic acid. , chromium oxide, nitric acid, chloric acid, hypochlorous acid, halogen, ozone, oxygen, hydrogen peroxide, peroxide, and oxygen. In the oxidation step, oxidation can also be performed using a combination of these oxidizing agents and the various oxidation catalysts described above. Further, in the oxidation step, DFF may be obtained by oxidizing HMF in the HMF-containing liquid obtained in the substitution step.
以下、実施例に基づいて、本発明のＨＭＦの合成方法およびＤＦＦの合成方法を具体的に説明するが、本発明は、以下の実施例によって何ら限定されるものではない。 EXAMPLES Hereinafter, the HMF synthesis method and DFF synthesis method of the present invention will be specifically explained based on Examples, but the present invention is not limited by the following Examples.
ＨＭＦの収率は、原料中のユーカリチップ、杉チップ、孟宗竹チップ、パルプ、セルロース、または糖液に含まれるグルコース相当の物質量（いわゆるモル量）に対する得られたＨＭＦの物質量を百分率（原料％）で表した。ＤＦＦの収率は、用いたＨＭＦの物質量に対する得られたＤＦＦの物質量を百分率（ＨＭＦ％）で表したか、原料中のユーカリチップ、杉チップ、孟宗竹チップ、パルプ、セルロース、または糖液に含まれるグルコース相当の物質量に対する得られたＤＦＦの物質量を百分率（原料％）で表した。転化率は、原料中のグルコース相当の物質量または質量に対する反応した原料の物質量または質量を百分率（％）で表した。 The yield of HMF is calculated by calculating the amount of the obtained HMF as a percentage (raw material %). The yield of DFF is expressed as a percentage (HMF%) of the amount of DFF obtained relative to the amount of HMF used, or the amount of eucalyptus chips, cedar chips, moso bamboo chips, pulp, cellulose, or sugar solution in the raw materials. The amount of the obtained DFF substance relative to the amount of substance equivalent to glucose contained in the sample was expressed as a percentage (raw material %). The conversion rate was expressed as a percentage (%) of the amount or mass of a reacted raw material relative to the amount or mass of a substance equivalent to glucose in the raw material.
（実施例１：糖液からＨＭＦの合成）
グルコース７．８４ｇとキシロース１．３５ｇを含む糖液３５ｇに、塩である塩化リチウム１０．５ｇ（０．２４ｍｏｌ）と、卑金属塩である塩化鉄６水和物６．７ｇ（０．０２４ｍｏｌ）を入れ、よくかき混ぜて完全に溶解させてから、容積３００ｍＬのオートクレーブに充填した。オートクレーブにＴＨＦ２００ｍＬをさらに入れた後、オートクレーブを密閉し、窒素置換を行った。その後、加熱炉でオートクレーブを加熱し、反応温度１５０℃になってから反応開始とし、その後２０時間反応を行った。反応時のオートクレーブ内の圧力は４ＭＰａであった。その後、反応液を室温まで冷やした。冷却後、得られた反応液の有機層（ＴＨＦ層）と水層をそれぞれ別々に採取した。有機層および水層に含まれるＨＭＦの糖液からの収率は４６原料％であった。
(Example 1: Synthesis of HMF from sugar solution)
To 35 g of sugar solution containing 7.84 g of glucose and 1.35 g of xylose, 10.5 g (0.24 mol) of lithium chloride, which is a salt, and 6.7 g (0.024 mol) of iron chloride hexahydrate, which is a base metal salt, were added. After stirring well to completely dissolve, the mixture was charged into an autoclave having a volume of 300 mL. After 200 mL of THF was further added to the autoclave, the autoclave was sealed and replaced with nitrogen. Thereafter, the autoclave was heated in a heating furnace, and the reaction was started when the reaction temperature reached 150° C., and the reaction was then continued for 20 hours. The pressure inside the autoclave during the reaction was 4 MPa. Thereafter, the reaction solution was cooled to room temperature. After cooling, the organic layer (THF layer) and aqueous layer of the resulting reaction solution were collected separately. The yield of HMF contained in the organic layer and the aqueous layer from the sugar solution was 46% based on the raw material.
（実施例２：ＨＭＦからＤＦＦの合成）
実施例１で得られた反応液から分取した有機層を－３０℃に冷却した後、析出した氷を濾過し、有機層から水分を除去した。なお、濾液（有機層）の水分が十分に除去されなかった場合は、必要に応じて、冷却温度をさらに下げて、または再度冷却して氷を除去するなどの操作を繰り返すことで、濾液に含まれる水分をできる限り除去した。得られた濾液（ＨＭＦを含むＴＨＦ溶液）を６０℃以下の低温で減圧留去した。得られたＨＭＦを含む粘性の高い反応物に、酸化反応で用いる溶媒のジクロロメタン１００ｍＬを加えた。ジクロロメタンに不溶な固体を濾過して除去した。必要に応じて、アルミナを用いてフミン質およびその他の不純物を取り除いた。
(Example 2: Synthesis of DFF from HMF)
After cooling the organic layer separated from the reaction solution obtained in Example 1 to -30°C, the precipitated ice was filtered to remove water from the organic layer. In addition, if the water in the filtrate (organic layer) is not sufficiently removed, if necessary, lower the cooling temperature further or repeat the operation such as cooling again to remove ice. Removed as much moisture as possible. The obtained filtrate (THF solution containing HMF) was distilled off under reduced pressure at a low temperature of 60° C. or lower. 100 mL of dichloromethane, a solvent used in the oxidation reaction, was added to the obtained highly viscous reaction product containing HMF. Solids insoluble in dichloromethane were removed by filtration. If necessary, alumina was used to remove humic substances and other impurities.
得られたＨＭＦのジクロロメタン溶液に、酸化剤である二酸化マンガン２０ｍｇ～３０ｍｇ程度を数回に分けて添加し、室温で反応を行った。反応中、ガスクロマトグラフィーを用いてＨＭＦの残量を確認し、ＨＭＦが残っている場合は二酸化マンガンをさらに加えて反応を進めた。ＨＭＦがほぼ消失したことを確認した後、二酸化マンガンを濾過して回収した。使用した二酸化マンガンは、硫酸で洗浄して再利用した。得られた濾液にアルミナを加えて不純物を吸着させて濾過した。得られた濾液は減圧下で溶媒を留去した。その後、ジクロロメタンとヘキサンを適切な比で混合した溶液を加えて再結晶を行い、目的の物質であるＤＦＦ２．５０ｇ（糖液からの収率４６原料％）を得た。 About 20 mg to 30 mg of manganese dioxide, which is an oxidizing agent, was added in several portions to the obtained dichloromethane solution of HMF, and the reaction was carried out at room temperature. During the reaction, the remaining amount of HMF was confirmed using gas chromatography, and if HMF remained, manganese dioxide was further added to advance the reaction. After confirming that HMF had almost disappeared, manganese dioxide was collected by filtration. The used manganese dioxide was washed with sulfuric acid and reused. Alumina was added to the obtained filtrate to adsorb impurities, and the mixture was filtered. The solvent of the obtained filtrate was distilled off under reduced pressure. Thereafter, a solution of dichloromethane and hexane mixed in an appropriate ratio was added to perform recrystallization to obtain 2.50 g of DFF (yield from sugar solution: 46% raw material), which was the target substance.
（実施例３：各種塩を用いた糖液からＨＭＦの合成）
下記の表１に示す塩を用い、反応時間を２時間にし、塩化鉄を用いずに、実施例１と同様にして糖液からＨＭＦを合成した。その結果を表１に示す。転化率に対する収率の比（収率／転化率）は、塩化リチウムを塩として用いたときが最も大きかった。
(Example 3: Synthesis of HMF from sugar solution using various salts)
HMF was synthesized from a sugar solution in the same manner as in Example 1, using the salts shown in Table 1 below, for a reaction time of 2 hours, and without using iron chloride. The results are shown in Table 1. The ratio of yield to conversion (yield/conversion) was highest when lithium chloride was used as the salt.
（実施例４：各種条件での糖液からＨＭＦの合成）
下記の表２に示す条件で、塩化リチウムのみ、または表中の物質量比で塩化リチウムと塩化鉄を用いて、実施例１と同様の方法で糖液からＨＭＦを合成した。その結果を表２に示す。さらに塩化鉄を用いることで、転化率と収率が上がることがわかった。また、塩化リチウムの物質量に対する塩化鉄の物質量の比が０．１以上であるときに、転化率と収率の上昇効果があることがわかった。さらに、反応時間が長くなるものの、反応温度を１５０℃に下げることで、副生成物の生成を極力抑え、高収率でＨＭＦが得られることがわかった。
(Example 4: Synthesis of HMF from sugar solution under various conditions)
HMF was synthesized from a sugar solution in the same manner as in Example 1 under the conditions shown in Table 2 below, using lithium chloride alone or lithium chloride and iron chloride in the amount ratios shown in the table. The results are shown in Table 2. Furthermore, it was found that the use of iron chloride increased the conversion rate and yield. It has also been found that when the ratio of the amount of iron chloride to the amount of lithium chloride is 0.1 or more, there is an effect of increasing the conversion rate and yield. Furthermore, although the reaction time was longer, it was found that by lowering the reaction temperature to 150° C., the formation of by-products could be suppressed as much as possible and HMF could be obtained in high yield.
（実施例５：各種条件での糖液からＨＭＦの合成）
下記の表３に示す条件で、塩化リチウムより安価で入手容易な塩化カルシウムのみ、または表中の物質量比で塩化カルシウムと塩化鉄を用いて、実施例１と同様の方法で糖液からＨＭＦを合成した。その結果を表３に示す。塩化カルシウムと塩化鉄を用いると、塩化カルシウムのみを用いたときと比べて、転化率は同等であるものの、収率が上がることがわかった。
(Example 5: Synthesis of HMF from sugar solution under various conditions)
HMF was extracted from the sugar solution in the same manner as in Example 1 under the conditions shown in Table 3 below, using only calcium chloride, which is cheaper and easier to obtain than lithium chloride, or using calcium chloride and iron chloride in the substance amount ratios shown in the table. was synthesized. The results are shown in Table 3. It was found that when calcium chloride and iron chloride were used, the yield was higher than when only calcium chloride was used, although the conversion rate was the same.
また、反応温度１９０℃のとき、オートクレーブ内の圧力は３ＭＰａ程度であったが、反応温度を１５０℃に下げることで、オートクレーブ内の圧力が１ＭＰａ程度となり、より汎用的な反応装置を用いてＨＭＦが製造できることがわかった。さらに、反応温度１３０℃～１６０℃でＨＭＦの製造を行ったところ、反応温度１４５℃～１５５℃のときに、転化率と収率がおおむね同等であった。すなわち、反応温度のむらが生じるような環境であっても、反応温度１４５℃～１５５℃で反応を行うことができれば、安定した収率でＨＭＦが得られることがわかった。 In addition, when the reaction temperature was 190°C, the pressure inside the autoclave was about 3 MPa, but by lowering the reaction temperature to 150°C, the pressure inside the autoclave became about 1 MPa, and HMF It turns out that it can be manufactured. Furthermore, when HMF was produced at a reaction temperature of 130°C to 160°C, the conversion rate and yield were approximately the same when the reaction temperature was 145°C to 155°C. In other words, it was found that even in an environment where the reaction temperature is uneven, if the reaction can be carried out at a reaction temperature of 145° C. to 155° C., HMF can be obtained in a stable yield.
（実施例６：溶媒の一部を置換したＨＭＦの合成）
反応圧力を低下させる目的で、有機液体であるＴＨＦの一部を、ＴＨＦの沸点より高沸点の有機液体であるトルエンに置き換えて、実施例５と同様の方法で糖液からＨＭＦを合成した。容積３０ｍＬのオートクレーブに、塩である塩化カルシウム１．２ｇと卑金属塩である塩化鉄０．１２ｇを入れ、糖液２．０ｇと水３．０ｇをさらに加え、下記の表４に示す量でＴＨＦとトルエンをさらに加え、反応温度１５０℃で２４時間反応を行った。
(Example 6: Synthesis of HMF with partial substitution of solvent)
HMF was synthesized from a sugar solution in the same manner as in Example 5, except that part of the organic liquid THF was replaced with toluene, an organic liquid with a boiling point higher than that of THF, for the purpose of lowering the reaction pressure. Into a 30 mL autoclave, put 1.2 g of calcium chloride as a salt and 0.12 g of iron chloride as a base metal salt, add 2.0 g of sugar solution and 3.0 g of water, and add THF in the amounts shown in Table 4 below. and toluene were further added, and the reaction was carried out at a reaction temperature of 150° C. for 24 hours.
反応後、液体クロマトグラフィーで生成物の分析を行い、有機相と水相にそれぞれ含まれる成分を調べ、転化率と収率を求めた。反応時のオートクレーブ内の圧力と、ＨＭＦの転化率および収率を表４に示す。その結果、トルエンの置換量が増加すると、収率が１０％程度減少するものの、反応圧力を下げられることがわかった。これによって、耐圧性が低い反応容器を用いて、ＨＭＦが合成できることが証明された。 After the reaction, the product was analyzed by liquid chromatography to determine the components contained in the organic phase and the aqueous phase, and the conversion rate and yield were determined. Table 4 shows the pressure inside the autoclave during the reaction, the conversion rate and yield of HMF. As a result, it was found that when the amount of toluene substituted increased, the reaction pressure could be lowered, although the yield decreased by about 10%. This proved that HMF can be synthesized using a reaction vessel with low pressure resistance.
（実施例７：杉由来パルプからＨＭＦの合成）
下記の表５に示す条件で、原料として杉由来のパルプ０．５ｇを用いて、実施例１と同様の方法でＨＭＦの合成を行った。その結果を表５に示す。原料としてパルプを用いてもＨＭＦを合成できることがわかった。塩化リチウムのみを用いた場合は、収率が１９％であったが（Ｎｏ．１）、塩化リチウムに塩化鉄を加えることで、転化率と収率が向上した（Ｎｏ．２の６８％と４０％）。
(Example 7: Synthesis of HMF from cedar-derived pulp)
HMF was synthesized in the same manner as in Example 1 under the conditions shown in Table 5 below, using 0.5 g of cedar-derived pulp as a raw material. The results are shown in Table 5. It was found that HMF can also be synthesized using pulp as a raw material. When only lithium chloride was used, the yield was 19% (No. 1), but by adding iron chloride to lithium chloride, the conversion rate and yield improved (68% for No. 2). 40%).
塩化亜鉛のみを用いた場合、塩化リチウムのみまたは塩化鉄のみを用いた場合と比べてパルプの溶解度が向上し、ＨＭＦの収率が２８％と上昇することもわかった（Ｎｏ．４）。また、塩化リチウムに塩化亜鉛を加えることで転化率と収率が改善された（Ｎｏ．５の８４％と４５％）。さらに、塩化リチウムと塩化鉄または塩化亜鉛（Ｎｏ．２とＮｏ．５）の代わりに、塩化カルシウムと塩化鉄または塩化亜鉛（Ｎｏ．６とＮｏ．７）を用いた場合、転化率と収率の若干の低下が見られるが、おおむね良好な結果を得た。 It was also found that when only zinc chloride was used, the solubility of the pulp was improved compared to when only lithium chloride or only iron chloride was used, and the yield of HMF increased to 28% (No. 4). Furthermore, the conversion rate and yield were improved by adding zinc chloride to lithium chloride (84% and 45% for No. 5). Furthermore, when calcium chloride and iron chloride or zinc chloride (No. 6 and No. 7) are used instead of lithium chloride and iron chloride or zinc chloride (No. 2 and No. 5), the conversion rate and yield are Although there was a slight decrease in the results, generally good results were obtained.
（実施例８：ＨＭＦからＤＦＦの合成）
下記の表６に示す酸化触媒と酸化剤と、パルプから得たＨＭＦ溶液を用いて、実施例２と同様にしてＤＦＦを合成した。その結果を表６に示す。パルプから得られるＨＭＦを含む反応液には、水分とＴＨＦに不要な固形分が除去されているものの、リグニン由来の成分等が少量含まれている。このため、ＤＦＦの合成に固体触媒（Ｎｏ．１～Ｎｏ．４）を用いることは難しい傾向にある。逆に均一系のバナジウム触媒（Ｎｏ．５）は、収率が高い傾向にあった。
(Example 8: Synthesis of DFF from HMF)
DFF was synthesized in the same manner as in Example 2 using the oxidation catalyst and oxidizing agent shown in Table 6 below and the HMF solution obtained from the pulp. The results are shown in Table 6. The reaction solution containing HMF obtained from the pulp contains a small amount of components derived from lignin, etc., although moisture and THF have been removed from unnecessary solid content. For this reason, it tends to be difficult to use solid catalysts (No. 1 to No. 4) in the synthesis of DFF. On the contrary, the homogeneous vanadium catalyst (No. 5) tended to have a high yield.
（実施例９：杉由来パルプからＤＦＦの合成）
原料として杉由来のパルプ１．１６ｇを用いた点を除いて、実施例２と同様にしてＨＭＦを経由してＤＦＦを合成した。ＤＦＦの収量は３６．２ｍｇで、ＤＦＦの収率は、パルプに含まれるセルロース換算で１７．９原料％であった。
(Example 9: Synthesis of DFF from cedar-derived pulp)
DFF was synthesized via HMF in the same manner as in Example 2, except that 1.16 g of cedar-derived pulp was used as the raw material. The yield of DFF was 36.2 mg, and the yield of DFF was 17.9% of the raw material in terms of cellulose contained in the pulp.
（実施例１０：ユーカリ由来パルプからＤＦＦの合成）
原料としてユーカリ由来のパルプ１．０６ｇを用いた点を除いて、実施例２と同様にしてＨＭＦを経由したＤＦＦの合成を行った。ＤＦＦの収量は４５．４ｍｇで、ＤＦＦの収率はパルプに含まれるセルロース換算で７．４７％であった。
(Example 10: Synthesis of DFF from eucalyptus-derived pulp)
DFF was synthesized via HMF in the same manner as in Example 2, except that 1.06 g of eucalyptus-derived pulp was used as the raw material. The yield of DFF was 45.4 mg, which was 7.47% in terms of cellulose contained in the pulp.
（実施例１１：孟宗竹チップからのＤＦＦの合成）
原料として孟宗竹チップ１．５ｇを用いた点を除いて、実施例２と同様にしてＨＭＦを経由してＤＦＦを合成した。ＤＦＦの収量は６０．２ｍｇで、ＤＦＦの収率は、チップに含まれるセルロース換算で、１０．７原料％であった。
(Example 11: Synthesis of DFF from Moso bamboo chips)
DFF was synthesized via HMF in the same manner as in Example 2, except that 1.5 g of Moso bamboo chips were used as the raw material. The yield of DFF was 60.2 mg, and the yield of DFF was 10.7% of the raw material in terms of cellulose contained in the chip.
（実施例１２：試薬のセルロース、グルコース、フルクトースを使用したＤＦＦの合成）
原料として、試薬で購入した純度９５％以上のセルロース（アビセル）１．０ｇ、グルコース１．０ｇ、およびフルクトース１．０ｇをそれぞれ用いて、実施例１および実施例２と同様にしてＨＭＦを経由してＤＦＦを合成した。ＤＦＦの収量（収率）は、それぞれ１２１．５ｍｇ（１５．８％）、２１５．１ｍｇ（３１．２％）、３０６．４ｍｇ（４４．５％）であった。
(Example 12: Synthesis of DFF using reagents cellulose, glucose, and fructose)
As raw materials, 1.0 g of cellulose (Avicel) with a purity of 95% or more purchased as a reagent, 1.0 g of glucose, and 1.0 g of fructose were used as the raw materials, and the mixture was passed through HMF in the same manner as in Examples 1 and 2. DFF was synthesized. The yields of DFF were 121.5 mg (15.8%), 215.1 mg (31.2%), and 306.4 mg (44.5%), respectively.
（実施例１３：二酸化マンガンの再利用）
実施例８から実施例１２で用いた二酸化マンガンを回収し、室温で濃硫酸を加えて撹拌後、濾過、水で洗浄し、６０℃のオーブンで１日乾燥させて再生した。得られた二酸化マンガンを２０ｇ～３０ｇ程度に数回に分けて実施例８のＨＭＦ溶液に添加し、室温でＤＦＦの合成を行った。反応中、ガスクロマトグラフィーを用いてＨＭＦの残量を確認し、残っている場合はさらに二酸化マンガンを加えて反応を進めた。
(Example 13: Reuse of manganese dioxide)
The manganese dioxide used in Example 12 was recovered from Example 8, stirred with concentrated sulfuric acid added at room temperature, filtered, washed with water, and dried in an oven at 60° C. for one day to regenerate. The obtained manganese dioxide was added in several portions of about 20 g to 30 g to the HMF solution of Example 8, and DFF was synthesized at room temperature. During the reaction, the remaining amount of HMF was confirmed using gas chromatography, and if any remained, manganese dioxide was further added to proceed with the reaction.
ＨＭＦがほぼ消失したことを確認後、濾過して二酸化マンガンを回収した。なお、使用した二酸化マンガンは、さらに硫酸で洗浄して再々利用した。得られた濾液にアルミナを加えて不純物を吸着させてさらに濾過した。減圧下で得られた濾液の溶媒を留去した。その後、ジクロロメタン－ヘキサンを適当な比で混合した溶液を加えて再結晶を行い、目的の物質ＤＦＦ（２．５０ｇ、糖液からの収率４６原料％）を得た。 After confirming that HMF had almost disappeared, it was filtered to recover manganese dioxide. The manganese dioxide used was further washed with sulfuric acid and reused. Alumina was added to the obtained filtrate to adsorb impurities, and the mixture was further filtered. The solvent of the obtained filtrate was distilled off under reduced pressure. Thereafter, a solution of dichloromethane and hexane mixed in an appropriate ratio was added to perform recrystallization to obtain the target substance DFF (2.50 g, yield from sugar solution 46% raw material).
（実施例１４：糖液からＨＭＦの合成２）
容量３０ｍＬのオートクレーブに、実施例１で用いた糖液２ｇ（グルコース含有量０．８２ｇ）、塩である塩化カルシウム１．２ｇ、卑金属塩である塩化鉄０．１２ｇ、水２ｍＬ、およびＴＨＦ２０ｍＬを加え、反応温度１５０℃で２４時間反応させた。反応後、生成物を液体クロマトグラフィーで分析したところ、ＨＭＦの収率は６２％であった。分液ロートでＴＨＦ相のみを採取し、不溶物を濾過除去した。
(Example 14: Synthesis of HMF from sugar solution 2)
In an autoclave with a capacity of 30 mL, add 2 g of the sugar solution used in Example 1 (glucose content 0.82 g), 1.2 g of calcium chloride as a salt, 0.12 g of iron chloride as a base metal salt, 2 mL of water, and 20 mL of THF. , the reaction was carried out at a reaction temperature of 150° C. for 24 hours. After the reaction, the product was analyzed by liquid chromatography, and the yield of HMF was 62%. Only the THF phase was collected using a separatory funnel, and insoluble materials were removed by filtration.
このＨＭＦを含むＴＨＦ溶液の一部を採取して、常温常圧で１５日間放置した。採取した直後のＨＭＦ含有量に対する時間経過後のＨＭＦ含有量の比（時間経過後のＨＭＦ含有量／採取直後のＨＭＦ含有量（以下「ＨＭＦ含有量比」と記載することがある））は、１日経過後が０．９８で、４日経過後が１．１０で、５日経過後が０．９５で、６日経過後が１．０２で、１５日経過後が１．０１であった。ＨＭＦを含むＴＨＦ溶液の採取から１５日経過しても、ＨＭＦ含有量比はほとんど変化なく、ＨＭＦがフミン質などに変化する傾向は見られなかった。 A portion of this HMF-containing THF solution was collected and left at room temperature and pressure for 15 days. The ratio of the HMF content after time to the HMF content immediately after collection (HMF content after time/HMF content immediately after collection (hereinafter sometimes referred to as "HMF content ratio")) is: The value was 0.98 after 1 day, 1.10 after 4 days, 0.95 after 5 days, 1.02 after 6 days, and 1.01 after 15 days. Even after 15 days had passed since the collection of the THF solution containing HMF, the HMF content ratio hardly changed, and no tendency for HMF to change into humic substances was observed.
一方、ＨＭＦを含むＴＨＦ溶液を一部採取して、２０分間でＴＨＦを留去した直後にＴＨＦと同じ量のトルエンを加えてＨＭＦ含有量を測定したところ、ＨＭＦ含有量比は０．６５であった。さらに、ＨＭＦを含むＴＨＦ溶液を一部採取し、そこにＴＨＦの沸点より高沸点のトルエンをＴＨＦの１．５倍量加え、ＴＨＦと水分を留去し、ＨＭＦ含有量を測定したところ、ＨＭＦ含有量比は０．９であった。これらの結果から、ＨＭＦは有機液体中で安定しており、ＴＨＦの沸点より高沸点の有機液体を用いることで、ＨＭＦのロスを抑えた溶媒置換が可能であることがわかった。 On the other hand, when a portion of the THF solution containing HMF was sampled and the THF was distilled off for 20 minutes, the same amount of toluene as THF was added to measure the HMF content, and the HMF content ratio was 0.65. there were. Furthermore, a portion of the THF solution containing HMF was collected, and 1.5 times the amount of toluene, which has a boiling point higher than that of THF, was added thereto, THF and water were distilled off, and the HMF content was measured. The content ratio was 0.9. From these results, it was found that HMF is stable in organic liquids, and by using an organic liquid with a boiling point higher than that of THF, it is possible to perform solvent replacement with suppressed loss of HMF.
（実施例１５：ＨＭＦからＤＦＦの合成２）
下記の表７に示すように、実施例１４の方法で得られたＨＭＦを含有する反応液を芳香族系のトルエンとアニソールでそれぞれ置換したＨＭＦを含有する含有液に、触媒である５質量％ルテニウム担持アルミナ触媒（和光純薬社製）２００ｍｇを加え、さらに酸素を導入して酸化工程を行った。トルエンとアニソールのそれぞれの沸点は、ＴＨＦおよび水の沸点より高い。その結果を表７に示す。
(Example 15: Synthesis of DFF from HMF 2)
As shown in Table 7 below, 5% by mass of a catalyst was added to the HMF-containing solution obtained by replacing the HMF-containing reaction solution obtained by the method of Example 14 with aromatic toluene and anisole, respectively. 200 mg of a ruthenium-supported alumina catalyst (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and oxygen was further introduced to perform an oxidation step. The respective boiling points of toluene and anisole are higher than the boiling points of THF and water. The results are shown in Table 7.
実施例８では、パルプから得られたＨＭＦをルテニウム担持アルミナ触媒で酸素酸化したとき、触媒被毒によりＤＦＦが得られなかった（表６のＮｏ．１）。このため、酸化マンガンを用いて酸化工程を行う必要があった。しかし、リグニンなどの芳香族化合物を含まない糖液を原料として得られたＨＭＦは、ルテニウム担持アルミナ触媒で酸素酸化を行えることが判明した。表７に示すように、ＤＦＦが収率９０％以上で得られた。また、実施例６では空気が酸化剤であったが、本実施例では、酸化剤として空気以外の酸素を用いることで、短時間でＤＦＦが得られた。 In Example 8, when HMF obtained from pulp was oxidized with oxygen using a ruthenium-supported alumina catalyst, DFF was not obtained due to catalyst poisoning (No. 1 in Table 6). Therefore, it was necessary to perform an oxidation step using manganese oxide. However, it has been found that HMF obtained from a sugar solution that does not contain aromatic compounds such as lignin can be oxidized with oxygen using a ruthenium-supported alumina catalyst. As shown in Table 7, DFF was obtained with a yield of 90% or more. Further, in Example 6, air was used as the oxidizing agent, but in this example, DFF was obtained in a short time by using oxygen other than air as the oxidizing agent.
高沸点有機液体がトルエンの場合で反応温度について検討したところ、反応温度がトルエンの沸点を大幅に超えると収率が下がった。生成したＤＦＦが揮発するためだと考えられる。不純物を含む純度７５％の粗ＤＦＦ０．８９ｇを２００℃に加熱して昇華精製を行った。無色透明の針状の結晶０．４５ｇが得られた（収率６７％）。この結晶をＮＭＲ測定した結果、純度がほぼ１００％であった。すなわち、ＤＦＦは昇華性があり、昇華精製によって極めて高純度のＤＦＦが得られることがわかった。 When the reaction temperature was investigated when the high-boiling organic liquid was toluene, the yield decreased when the reaction temperature significantly exceeded the boiling point of toluene. This is thought to be due to the generated DFF volatilizing. 0.89 g of crude DFF containing impurities and having a purity of 75% was heated to 200° C. to perform sublimation purification. 0.45 g of colorless and transparent needle-shaped crystals were obtained (yield: 67%). As a result of NMR measurement of this crystal, the purity was approximately 100%. That is, it was found that DFF has sublimation property and that DFF of extremely high purity can be obtained by sublimation purification.
Claims (6)
前記反応液の有機液体層から水を除去して５－ヒドロキシメチル－２－フルフラールを含有する粗生成物を得る水除去工程と、
前記粗生成物中の５－ヒドロキシメチル－２－フルフラールを酸化して２，５－ジホルミルフランを得る酸化工程と、
を有する２，５－ジホルミルフランの合成方法。 5-Hydroxymethyl- 2-A hydrothermal step to obtain a reaction solution containing furfural;
a water removal step of removing water from the organic liquid layer of the reaction solution to obtain a crude product containing 5-hydroxymethyl-2-furfural;
an oxidation step of oxidizing 5-hydroxymethyl-2-furfural in the crude product to obtain 2,5-diformylfuran;
A method for synthesizing 2,5-diformylfuran having
前記水除去工程が、前記有機液体層中の水を氷として除去する過程を備える２，５－ジホルミルフランの合成方法。 In claim 1,
A method for synthesizing 2,5-diformylfuran, wherein the water removing step includes removing water in the organic liquid layer as ice.
前記有機液体層中の水を氷として除去する過程では、前記反応液を有機液体の凝固点以上０℃以下の温度に冷却する２，５－ジホルミルフランの合成方法。 In claim 2,
A method for synthesizing 2,5-diformylfuran, wherein in the step of removing water in the organic liquid layer as ice , the reaction liquid is cooled to a temperature above the freezing point of the organic liquid and below 0°C.
前記有機液体および水の沸点より沸点が高い高沸点有機液体を前記反応液に加えた後、前記有機液体および水の少なくとも一部を留去して、５－ヒドロキシメチル－２－フルフラールを含有する含有液を得る置換工程と、
前記含有液中の５－ヒドロキシメチル－２－フルフラールを酸化して２，５－ジホルミルフランを得る酸化工程と、
を有する２，５－ジホルミルフランの合成方法。 In the presence of one or more types of alkali metal salts and alkaline earth metal salts, 5-hydroxymethyl-2-furfural is produced by hydrothermally treating raw materials containing sugars using a mixed liquid of an organic liquid and water as a medium. a hydrothermal step to obtain a reaction solution containing;
After adding the organic liquid and a high-boiling organic liquid having a boiling point higher than the boiling point of water to the reaction liquid, at least a portion of the organic liquid and water are distilled off to obtain a mixture containing 5-hydroxymethyl-2-furfural. a replacement step for obtaining a containing liquid;
an oxidation step of oxidizing 5-hydroxymethyl-2-furfural in the containing liquid to obtain 2,5-diformylfuran;
A method for synthesizing 2,5-diformylfuran having
前記有機液体がテトラヒドロフランであり、
前記高沸点有機液体がトルエンまたはアニソールである２，５－ジホルミルフランの合成方法。 In claim 4,
the organic liquid is tetrahydrofuran,
A method for synthesizing 2,5-diformylfuran, wherein the high-boiling organic liquid is toluene or anisole.
前記原料が芳香族化合物を含まない２，５－ジホルミルフランの合成方法。 In claim 4 or 5,
A method for synthesizing 2,5-diformylfuran in which the raw material does not contain aromatic compounds.
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