JP2007261986A - Method for producing furandicarboxylic acid (fdca) - Google Patents

Method for producing furandicarboxylic acid (fdca) Download PDF

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JP2007261986A
JP2007261986A JP2006088310A JP2006088310A JP2007261986A JP 2007261986 A JP2007261986 A JP 2007261986A JP 2006088310 A JP2006088310 A JP 2006088310A JP 2006088310 A JP2006088310 A JP 2006088310A JP 2007261986 A JP2007261986 A JP 2007261986A
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alkali
producing
dff
furandicarboxylic acid
diformylfuran
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JP5006561B2 (en
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Takenobu Kono
岳信 河野
Hirohide Matsuhisa
裕英 松久
Toshinari Miura
俊成 三浦
Hirokazu Kakinuma
宏和 柿沼
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Canon Inc
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Canon Inc
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing FDCA by which the amount of a used catalyst can be reduced, the energy consumption can be reduced by a mild condition, the FDCA can be produced from diformylfuran (DFF), and the technique is enriched. <P>SOLUTION: The FDCA is produced by feeding the DFF, water, a metal oxide catalyst, an alkali, and air or oxygen to oxidize the DFF. One or more of hydroxides of alkali metals and hydroxides of alkaline earth metals are used as the alkali, and silver oxide and copper oxide are used as the metal oxide catalyst. The reaction is preferably carried out at ≥1°C and ≤50°C. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、穏やかな条件で、効率よく、高収率でフランジカルボン酸を得ることができるフランジカルボン酸の製造方法に関する。   The present invention relates to a method for producing furandicarboxylic acid, which can obtain furandicarboxylic acid efficiently at a high yield under mild conditions.

フランジカルボン酸（ＦＤＣＡ）、特に、フラン−２，５−ジカルボン酸は医薬、農薬、殺虫剤、抗菌剤、香料、その他各種の分野の中間体として利用価値が高い。ＦＤＣＡの合成方法としては、ジホルミルフラン（ＤＦＦ）を酸化する方法が知られている。   Flanged carboxylic acid (FDCA), in particular, furan-2,5-dicarboxylic acid, has high utility value as an intermediate in pharmaceuticals, agricultural chemicals, insecticides, antibacterial agents, fragrances, and other various fields. As a method for synthesizing FDCA, a method for oxidizing diformylfuran (DFF) is known.

ＤＦＦを酸化してＦＤＣＡを合成する方法としては、具体的には、ＤＦＦ０.４ｇと酸化銀０.９ｇとを共存させ、９０〜９５℃で１５分程度、攪拌する方法が報告されている（非特許文献１）。また、酸化銅-酸化銀触媒を用いて、水酸化ナトリウム水溶液中でフルフラールを５５℃において酸素酸化し、フランカルボン酸を８６〜９０％の収率で得る方法が報告されている（非特許文献２）。   As a method for synthesizing FDCA by oxidizing DFF, specifically, a method in which 0.4 g of DFF and 0.9 g of silver oxide coexist and stirred at 90 to 95 ° C. for about 15 minutes has been reported ( Non-patent document 1). In addition, a method has been reported in which furfural is oxidized with oxygen at 55 ° C. in a sodium hydroxide aqueous solution using a copper oxide-silver oxide catalyst to obtain furancarboxylic acid in a yield of 86 to 90% (non-patent document). 2).

しかしながら、非特許文献１に記載される製法においては、酸化銀触媒の使用量が多量であり、温度が９０℃以上必要であること、ＦＤＣＡの収率は８０％程度であることなどから、工業的製造に適用するにはエネルギー消費量が多く、触媒費用等コスト面でも問題がある。また、非特許文献２に記載される製法は、1官能基を酸化する方法であり、また温度が５５℃必要で、エネルギー消費量のより一層の低減を図る必要がある。
Ｅｌ−Ｈａｊｊ，Ｔ．Ｂｕｌｌ．Ｓｏｃ．Ｃｈｉｍ．Ｆｒ．１９８７，８５５−８６０ 第四版実験化学講座２３、有機合成Ｖ、酸化反応、Ｐ４１５ However, in the production method described in Non-Patent Document 1, the amount of silver oxide catalyst used is large, the temperature is required to be 90 ° C. or higher, and the yield of FDCA is about 80%. When applied to industrial production, the amount of energy consumed is large, and there are problems in terms of costs such as catalyst costs. In addition, the production method described in Non-Patent Document 2 is a method of oxidizing one functional group, requires a temperature of 55 ° C., and needs to further reduce energy consumption.
El-Hajj, T .; Bull. Soc. Chim. Fr. 1987, 855-860 Fourth Edition Experimental Chemistry Course 23, Organic Synthesis V, Oxidation Reaction, P415

本発明の課題は、触媒の使用量の減少を図り、穏やかな条件で、エネルギー消費量の低減を図り、ＤＦＦから定量的にＦＤＣＡを製造することができるＦＤＣＡの製造方法を提供し、技術の豊富化を図ることができるＦＤＣＡの製造方法を提供することにある。   An object of the present invention is to provide a method for producing FDCA that can reduce the amount of catalyst used, reduce energy consumption under mild conditions, and produce FDCA quantitatively from DFF. An object of the present invention is to provide a method of manufacturing FDCA that can be enriched.

本発明者らは、穏やかな条件により、ＤＦＦを酸化してＦＤＣＡを製造する方法について鋭意研究した。その結果、アルカリ存在下で、ＤＦＦに、水、金属酸化物触媒、空気または酸素を供給することにより、５０℃以下の温度で、触媒の使用量を少量にしてもＤＦＦの酸化反応が進行し、高収率でＦＤＣＡを得ることができることを見い出した。かかる知見に基づき、本発明を完成するに至った。   The present inventors have intensively studied a method for producing FDCA by oxidizing DFF under mild conditions. As a result, by supplying water, metal oxide catalyst, air or oxygen to the DFF in the presence of alkali, the oxidation reaction of the DFF proceeds at a temperature of 50 ° C. or less even if the amount of the catalyst used is small. It has been found that FDCA can be obtained in high yield. Based on this knowledge, the present invention has been completed.

すなわち、本発明は、ジホルミルフランと、水と、金属酸化物触媒と、アルカリと、空気または酸素とを供給して、ジホルミルフランを酸化することを特徴とするフランジカルボン酸の製造方法に関する。   That is, the present invention relates to a process for producing furandicarboxylic acid, characterized in that diformylfuran, water, metal oxide catalyst, alkali, air or oxygen are supplied to oxidize diformylfuran. .

また、本発明は、ジホルミルフラン水溶液に、金属酸化物触媒と、アルカリと、空気または酸素とを供給して、ジホミルフランを酸化することを特徴とするフランジカルボン酸の製造方法に関する。   The present invention also relates to a method for producing furandicarboxylic acid, which comprises oxidizing a diformylfuran by supplying a metal oxide catalyst, an alkali, and air or oxygen to a diformylfuran aqueous solution.

本発明のフランジカルボン酸の製造方法は、触媒の使用量の減少を図り、穏やかな条件で、エネルギー消費量の低減を図り、ＤＦＦから定量的にＦＤＣＡを製造することができるＦＤＣＡの製造方法を提供し、技術の豊富化を図ることができる。   The method for producing furandicarboxylic acid of the present invention is a method for producing FDCA capable of reducing the amount of catalyst used, reducing energy consumption under mild conditions, and producing FDCA quantitatively from DFF. It can be provided to enrich the technology.

本発明のフランジカルボン酸の製造方法は、ジホルミルフランと、水と、金属酸化物触媒と、アルカリと、空気または酸素とを供給して、ジホルミルフランを酸化することを特徴とする。   The method for producing furandicarboxylic acid according to the present invention is characterized in that diformylfuran is oxidized by supplying diformylfuran, water, a metal oxide catalyst, an alkali, and air or oxygen.

本発明のフランジカルボン酸の製造方法に用いるＤＦＦとしては、２，５−ジホルミルフランが、反応性に優れ、中間体としての利用範囲が広く、好ましい。ＤＦＦは、セルロース、澱粉などの六糖類などの多糖類、ショ糖、マルトース、セロビオース、ラクトースなどの少糖類、フルクトース、グルコースなどの単糖類等の糖類の脱水反応によって得られる５−ヒドロキシメチルフルフラールを酸化して得ることができる。ＤＦＦは固体の状態で使用することもでき、また、水などの媒体に分散・溶解して使用することもできる。   As the DFF used in the method for producing furandicarboxylic acid of the present invention, 2,5-diformylfuran is preferable because of its excellent reactivity and wide range of use as an intermediate. DFF is 5-hydroxymethylfurfural obtained by dehydration reaction of polysaccharides such as hexasaccharides such as cellulose and starch, oligosaccharides such as sucrose, maltose, cellobiose and lactose, and monosaccharides such as fructose and glucose. It can be obtained by oxidation. DFF can be used in a solid state, or can be used after being dispersed and dissolved in a medium such as water.

ＤＦＦの原料中の含有量としては、０．１質量％以上２０．０質量％以下であることが好ましい。ここで原料とは、ジホルミルフランと、水と、金属酸化物触媒と、アルカリとを含むものをいう。ＤＦＦの原料中の含有量が０．１質量％以上であれば、得られるＦＤＣＡ濃度が高く、回収が容易であり、２０．０質量％以下であれば、ＦＤＣＡへの酸化反応が効率よく進行する。   As content in the raw material of DFF, it is preferable that they are 0.1 mass% or more and 20.0 mass% or less. Here, the raw material means a material containing diformyl furan, water, a metal oxide catalyst, and an alkali. If the content of DFF in the raw material is 0.1% by mass or more, the resulting FDCA concentration is high and easy to recover, and if it is 20.0% by mass or less, the oxidation reaction to FDCA proceeds efficiently. To do.

また、ＤＦＦは予め水に分散・溶解して用いることができる。この場合、水分散・溶解液のＤＦＦの濃度はＤＦＦが均一に溶解するほどの量を用いることが好ましい。この水の使用量は原料中の水に含まれる。   Moreover, DFF can be dispersed and dissolved in water in advance. In this case, it is preferable to use the amount of DFF in the aqueous dispersion / dissolution so that the DFF is uniformly dissolved. The amount of water used is included in the water in the raw material.

本発明のフランジカルボン酸の製造方法に用いる金属酸化物触媒としては、例えば、酸化銀、酸化銅などの金属酸化物を挙げることができ、これらを組み合わせて使用することが好ましい。金属酸化物触媒として、米国特許３３２６９４４（１９６７）実施例２に準じた方法で調製したものを好ましいものとして挙げることができる。具体的には、硫酸銅と硝酸銀の混合溶液に水酸化ナトリウム水溶液を加え、析出する酸化銅・酸化銀の混合物を用いることができる。   As a metal oxide catalyst used for the manufacturing method of furandicarboxylic acid of this invention, metal oxides, such as silver oxide and copper oxide, can be mentioned, for example, It is preferable to use combining these. As a metal oxide catalyst, what was prepared by the method according to US Patent 3326944 (1967) Example 2 can be mentioned as a preferable thing. Specifically, a sodium hydroxide aqueous solution is added to a mixed solution of copper sulfate and silver nitrate, and a mixture of precipitated copper oxide and silver oxide can be used.

上記金属酸化物触媒の使用量としては、ＤＦＦに対して１．０質量％以上１００質量％以下の範囲が好ましい。金属酸化物触媒の使用量がＤＦＦに対して１．０質量％以上であれば、ＦＤＣＡを効率よく製造することができ、１００質量％以下であれば経済的な観点から好ましい。   As the usage-amount of the said metal oxide catalyst, the range of 1.0 mass% or more and 100 mass% or less is preferable with respect to DFF. If the amount of the metal oxide catalyst used is 1.0% by mass or more with respect to DFF, FDCA can be produced efficiently, and if it is 100% by mass or less, it is preferable from an economical viewpoint.

本発明のフランジカルボン酸の製造方法に用いるアルカリとしては、例えば、アルカリ金属の水酸化物、またはアルカリ土類金属の水酸化物を挙げることができる。アルカリ金属の水酸化物としては、具体的には、水酸化ナトリウム、水酸化カリウム等、また、アルカリ土類金属の水酸化物としては、水酸化カルシウム、水酸化バリウム等を挙げることができ、これらは１種または２種以上を組み合わせて使用することができる。   Examples of the alkali used in the method for producing furandicarboxylic acid of the present invention include an alkali metal hydroxide and an alkaline earth metal hydroxide. Specific examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide, and examples of the alkaline earth metal hydroxide include calcium hydroxide and barium hydroxide. These can be used alone or in combination of two or more.

上記アルカリの使用量としては、ＤＦＦに対して３．０モル当量以上２０．０モル当量以下であることが好ましい。アルカリの使用量がＤＦＦに対して３．０モル当量以上であれば、ＦＤＣＡを効率よく製造することができ、２０．０モル当量以下であれば、経済的な観点から好ましい。   The amount of the alkali used is preferably 3.0 to 20.0 molar equivalents relative to DFF. If the usage-amount of an alkali is 3.0 molar equivalent or more with respect to DFF, FDCA can be manufactured efficiently and if it is 20.0 molar equivalent or less, it is preferable from an economical viewpoint.

本発明のフランジカルボン酸の製造方法として、上記ＤＦＦ、水、金属酸化物触媒、アルカリと共に供給する空気または酸素は、バブリングにより供給することができる。空気に含まれる酸素、または酸素ガスにより、アルカリ性水溶媒中で金属酸化物触媒存在下、ＤＦＦの酸化反応を容易に進行させることができる。   As the method for producing furandicarboxylic acid of the present invention, the air or oxygen supplied together with the DFF, water, metal oxide catalyst, and alkali can be supplied by bubbling. Oxygen contained in the air or oxygen gas allows the DFF oxidation reaction to proceed easily in the presence of a metal oxide catalyst in an alkaline water solvent.

これらの各原料の供給順番としては、いずれであってもよいが、例えば、金属酸化物触媒とアルカリとを含有した水媒体に空気または酸素のバブリングを行い、これにＤＦＦの水溶液を攪拌しつつ滴下することができる。また、金属酸化物触媒を含有する水媒体に空気または酸素のバブリングを行い、これにＤＦＦとアルカリとを含有する水媒体を滴下することができる。また、ＤＦＦ、金属酸化物触媒、アルカリを水に同時に添加して混合し、空気または酸素のバブリングを行うこともできる。   Any of these raw materials may be supplied in any order. For example, air or oxygen is bubbled into an aqueous medium containing a metal oxide catalyst and an alkali, and an aqueous solution of DFF is stirred. Can be dripped. In addition, air or oxygen can be bubbled into an aqueous medium containing a metal oxide catalyst, and an aqueous medium containing DFF and alkali can be added dropwise thereto. Further, DFF, a metal oxide catalyst, and alkali can be simultaneously added to water and mixed to perform bubbling of air or oxygen.

かかるＤＦＦの酸化反応は、１℃から５０℃で行うことが好ましい。酸化反応温度が１℃以上であれば、ＦＤＣＡを効率よく製造することができ、５０℃以下であれば、ＤＦＦが熱により分解されるのを抑制することができる。副生成物のヒドロキシメチルフランカルボン酸（ＨＭＦＡ）の生成を抑制し、効率よくＦＤＣＡを製造できることに加え、エネルギー消費量を最小限とすることができるため、室温で行うことが、より好ましい。   The oxidation reaction of DFF is preferably performed at 1 ° C to 50 ° C. If the oxidation reaction temperature is 1 ° C. or higher, FDCA can be produced efficiently, and if it is 50 ° C. or lower, DFF can be prevented from being decomposed by heat. It is more preferable to carry out at room temperature because the production of by-product hydroxymethylfurancarboxylic acid (HMFA) can be suppressed and FDCA can be efficiently produced, and energy consumption can be minimized.

このようなフランジカルボン酸の製造方法により製造されるフランジカルボン酸としては、フラン−２，５−ジカルボン酸であることが、中間体として有用性に富むことから好ましい。   The furan carboxylic acid produced by such a method for producing furan carboxylic acid is preferably furan-2,5-dicarboxylic acid because it is highly useful as an intermediate.

以下に、本発明のフランジカルボン酸の製造方法を具体的に詳細に説明するが、本発明の技術的範囲はこれらに限定されるものではない。   Although the manufacturing method of the furandicarboxylic acid of this invention is demonstrated concretely below in detail, the technical scope of this invention is not limited to these.

［金属酸化物触媒の合成］
攪拌棒、温度計、ジムロート冷却管、玉栓を装着した５Ｌの四つロフラスコに、ＣｕＳＯ4・５Ｈ2Ｏ４００ｇとイオン交換水２Ｌとを仕込み、攪拌しながらマントルヒーターにより７０℃に昇温した。１Ｌの三角フラスコにＡｇＮＯ3８０ｇとイオン交換水５００ｍＬとを添加し、スターラーで攪拌し溶解させ、溶解したＡｇＮＯ3水溶液をできるだけ素早く上記四つ口フラスコに添加した。四つロフラスコの温度が一旦７０℃より下がるので、７０℃に戻し安定したのを確認した。白色結晶が析出した。別に１Ｌ三角フラスコに、水酸化ナトリウム２００ｇとイオン交換水５００ｍＬとを添加し、発熱を注意しながら攪拌し溶解した。溶解した水酸化ナトリウム水溶液を温度が下がらないように保温した。１００ｍＬ滴下ロートを用い、保温している水酸化ナトリウム水溶液を６０分間かけて、四つ口フラスコにゆっくり滴下した。四つ口フラスコ内の水溶液は徐々に茶黒色に着色した。水酸化ナトリウム水溶液滴下後７０℃で３０分間攪拌を継続して行った。室温まで冷却し、ブフナーロートと吸引瓶を用いてアスピレーターで吸引濾過した。イオン交換水で数回掛け洗浄を行い、酸化銀酸化銅触媒を得た。酸化銀酸化銅触媒はウエット状態のままサンプル瓶に保管し、使用した。 [Synthesis of metal oxide catalysts]
400 g CuSO 4 .5H 2 O and 2 L ion-exchanged water were charged into a 5 L four-neck flask equipped with a stir bar, thermometer, Dimroth condenser, and ball plug, and heated to 70 ° C. with a mantle heater while stirring. To a 1 L Erlenmeyer flask, 80 g of AgNO 3 and 500 mL of ion exchange water were added, stirred and dissolved with a stirrer, and the dissolved AgNO 3 aqueous solution was added to the four-necked flask as quickly as possible. Since the temperature of the four-flask was once lowered from 70 ° C, it was confirmed that the temperature was returned to 70 ° C and stabilized. White crystals precipitated. Separately, 200 g of sodium hydroxide and 500 mL of ion-exchanged water were added to a 1 L Erlenmeyer flask, and dissolved by stirring with careful attention to heat generation. The dissolved aqueous sodium hydroxide solution was kept warm so that the temperature did not drop. Using a 100 mL dropping funnel, a heated sodium hydroxide aqueous solution was slowly added dropwise to the four-necked flask over 60 minutes. The aqueous solution in the four-necked flask was gradually colored brown black. After dropwise addition of the aqueous sodium hydroxide solution, stirring was continued at 70 ° C. for 30 minutes. The mixture was cooled to room temperature, and suction filtered with an aspirator using a Buchner funnel and a suction bottle. It was washed several times with ion-exchanged water to obtain a silver oxide copper oxide catalyst. The silver oxide copper oxide catalyst was stored in a sample bottle in a wet state and used.

［実施例１］
水５．７ｇに酸化銀酸化銅触媒を０．１２４ｇ添加し、攪拌しつつ２Ｌ／分の量の空気をバブリングした。また２，５−ＤＦＦ０．１２４ｇを、水５．７ｇに溶解し、２，５−ＤＦＦに対して５．２モル当量の水酸化ナトリウムを添加した。この２，５−ＤＦＦのアルカリ溶液を酸化銀酸化銅触媒分散溶液に３０分間滴下した。このとき溶液中の温度は２５℃であった。滴下終了後、１０分間攪拌を継続した。 [Example 1]
0.124 g of silver oxide copper oxide catalyst was added to 5.7 g of water, and 2 L / min of air was bubbled with stirring. Further, 0.124 g of 2,5-DFF was dissolved in 5.7 g of water, and 5.2 molar equivalent of sodium hydroxide was added to 2,5-DFF. This alkaline solution of 2,5-DFF was added dropwise to the silver oxide copper oxide catalyst dispersion for 30 minutes. At this time, the temperature in the solution was 25 ° C. After completion of the dropping, stirring was continued for 10 minutes.

反応液の分析を高速液体クロマトグラフィー（ＨＰＬＣ）を用いて行った。フラン−２，５−ジカルボン酸の収率は１００％であった。結果を表１に示す。   The reaction solution was analyzed using high performance liquid chromatography (HPLC). The yield of furan-2,5-dicarboxylic acid was 100%. The results are shown in Table 1.

［実施例２］
２，５−ＤＦＦ０．１２４ｇと２，５−ＤＦＦに対して５．２モル当量の水酸化ナトリウムと酸化銀酸化銅触媒０．１２４ｇを水１１．４ｇに添加し、攪拌しながら２Ｌ／分の量の空気をバブリングした。このとき溶液中の温度は２５℃であった。バブリングを６０分行った。 [Example 2]
0.124 g of 2,5-DFF and 0.124 g of sodium hydroxide and 0.124 g of silver oxide copper oxide catalyst with respect to 2,5-DFF were added to 11.4 g of water and stirred at 2 L / min. An amount of air was bubbled. At this time, the temperature in the solution was 25 ° C. Bubbling was performed for 60 minutes.

反応液の分析をＨＰＬＣを用いて行った。フラン−２，５−ジカルボン酸の収率は７５．９％、５−ヒドロキシメチルフラン−２−カルボン酸の収率は２４．１％であった。   The reaction solution was analyzed using HPLC. The yield of furan-2,5-dicarboxylic acid was 75.9%, and the yield of 5-hydroxymethylfuran-2-carboxylic acid was 24.1%.

その後、バブリングを継続し合計で８４０分行い、同様にしてＨＰＬＣによる分析を行った。フラン−２，５−ジカルボン酸の収率は７７．５％、５−ヒドロキシメチルフラン−２−カルボン酸の収率は２２．５％であった。結果を表２に示す。   Thereafter, bubbling was continued for a total of 840 minutes, and analysis by HPLC was performed in the same manner. The yield of furan-2,5-dicarboxylic acid was 77.5%, and the yield of 5-hydroxymethylfuran-2-carboxylic acid was 22.5%. The results are shown in Table 2.

［比較例１］
酸化銀酸化銅触媒を使用しない他は、実施例２と同様に行った。バブリングの開始後４０分経過した時点で、反応液の分析をＨＰＬＣを用いて行った。２−カルボキシ−５−ホルミルフラン（ＣＦＦ）と５−ヒドロキシメチルフルフラール（５−ＨＭＦ）の生成が確認されたが、フラン−２，５−ジカルボン酸は全く確認できなかった。 [Comparative Example 1]
The same procedure as in Example 2 was performed except that the silver oxide copper oxide catalyst was not used. When 40 minutes had passed after the start of bubbling, the reaction solution was analyzed using HPLC. Although formation of 2-carboxy-5-formylfuran (CFF) and 5-hydroxymethylfurfural (5-HMF) was confirmed, furan-2,5-dicarboxylic acid was not confirmed at all.

その後、バブリングを継続し合計で７８０分行ったが、ＦＤＣＡの生成は見られなかった。   Thereafter, bubbling was continued for a total of 780 minutes, but no FDCA formation was observed.

［比較例２］
２，５−ＤＦＦ０．１２４ｇと２，５−ＤＦＦに対して１.３モル当量の水酸化ナトリウムと酸化銀酸化銅触媒０．１２４ｇを水１１．４ｇに添加し、攪拌しながら２Ｌ／分の量の空気をバブリングした。このとき溶液中の温度は２５℃であった。バブリングの開始後４０分経過した時点で、反応液の分析をＨＰＬＣを用いて行った。フラン−２，５−ジカルボン酸の収率は１０.３％、２−カルボキシ−５−ホルミルフラン（ＣＦＦ）の収率は６４.７％、５−ヒドロキシメチルフルフラール（５−ＨＭＦ）の収率は７.６％であった。その後、バブリングを継続し合計で９０分行ったが、ＦＤＣＡの生成率は大きな向上は見られなかった。結果を表４に示す。 [Comparative Example 2]
0.124 g of 2,5-DFF and 1.3 molar equivalents of sodium hydroxide and 0.124 g of silver oxide copper oxide catalyst with respect to 2,5-DFF were added to 11.4 g of water, and 2 L / min with stirring. An amount of air was bubbled. At this time, the temperature in the solution was 25 ° C. When 40 minutes had passed after the start of bubbling, the reaction solution was analyzed using HPLC. The yield of furan-2,5-dicarboxylic acid was 10.3%, the yield of 2-carboxy-5-formylfuran (CFF) was 64.7%, and the yield of 5-hydroxymethylfurfural (5-HMF). Was 7.6%. Thereafter, bubbling was continued for a total of 90 minutes, but no significant improvement was observed in the production rate of FDCA. The results are shown in Table 4.

Figure 2007261986
Figure 2007261986

Figure 2007261986
Figure 2007261986

Figure 2007261986
Figure 2007261986

Figure 2007261986
Figure 2007261986

Claims (9)

ジホルミルフランと、水と、金属酸化物触媒と、アルカリと、空気または酸素とを供給して、ジホルミルフランを酸化することを特徴とするフランジカルボン酸の製造方法。   A method for producing furancarboxylic acid, which comprises oxidizing diformylfuran by supplying diformylfuran, water, a metal oxide catalyst, an alkali, air or oxygen. ジホルミルフラン水溶液に、金属酸化物触媒と、アルカリと、空気または酸素とを供給して、ジホミルフランを酸化することを特徴とするフランジカルボン酸の製造方法。   A method for producing furandicarboxylic acid, comprising supplying a metal oxide catalyst, an alkali, and air or oxygen to a diformylfuran aqueous solution to oxidize diformylfuran. アルカリとして、アルカリ金属の水酸化物およびアルカリ土類金属の水酸化物のいずれか１種または２種以上を用いることを特徴とする請求項１または２記載のフランジカルボン酸の製造方法。   The method for producing furandicarboxylic acid according to claim 1 or 2, wherein any one or more of alkali metal hydroxides and alkaline earth metal hydroxides are used as the alkali. アルカリとして、水酸化ナトリウム、水酸化カリウム、水酸化カルシウムおよび水酸化バリウムから選ばれるいずれか１種または２種以上を用いることを特徴とする請求項１または２記載のフランジカルボン酸の製造方法。   The method for producing furandicarboxylic acid according to claim 1 or 2, wherein any one or more selected from sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide is used as the alkali. アルカリを、ジホルミルフランの３．０モル当量以上２０．０モル当量以下の範囲で使用することを特徴とする請求項１から４のいずれか記載のフランジカルボン酸の製造方法。   The method for producing furandicarboxylic acid according to any one of claims 1 to 4, wherein the alkali is used in a range of 3.0 to 20.0 molar equivalents of diformylfuran. 金属酸化物触媒として、酸化銀と酸化銅とを用いることを特徴とする請求項１から５のいずれか記載のフランジカルボン酸の製造方法。   6. The method for producing flange carboxylic acid according to claim 1, wherein silver oxide and copper oxide are used as the metal oxide catalyst. 金属酸化物触媒を、ジホルミルフランに対して１．０質量％以上１００質量％以下の範囲で使用することを特徴とする請求項１から６のいずれか記載のフランジカルボン酸の製造方法。   The method for producing furandicarboxylic acid according to any one of claims 1 to 6, wherein the metal oxide catalyst is used in a range of 1.0 to 100 mass% with respect to diformylfuran. ジホルミルフランを、原料全体に対して０．１質量％以上２０．０質量％以下の範囲で使用することを特徴とする請求項１から７のいずれか記載のフランジカルボン酸の製造方法。   The method for producing furandicarboxylic acid according to any one of claims 1 to 7, wherein diformyl furan is used in a range of 0.1% by mass or more and 20.0% by mass or less based on the whole raw material. １℃以上５０℃以下の温度で行うことを特徴とする請求項１から８のいずれか記載のフランジカルボン酸の製造方法。


The method for producing furandicarboxylic acid according to any one of claims 1 to 8, wherein the method is performed at a temperature of 1 ° C or higher and 50 ° C or lower.


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