WO2018082234A1 - Method for preparing 2,5-furandicarboxylic acid by catalytic oxidation of 2,5-diformylfuran - Google Patents
Method for preparing 2,5-furandicarboxylic acid by catalytic oxidation of 2,5-diformylfuran Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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- This invention relates to a process for the oxidation of a dialdehyde to produce a dibasic acid.
- 2,5-furandicarboxylic acid is an organic dibasic acid having a furan ring structure, and has many similarities with the molecular structure of the bulk chemical terephthalic acid. For example, they are all organic dibasic acids having a cyclic structure, and the number of cyclic conjugated electrons is the same. 2,5-furandicarboxylic acid is an important intermediate for the synthesis of various fine chemicals and furan-based polymers, and has important potential applications in the synthesis of new fibers and polyesters.
- 2,5-furandicarboxylic acid is mainly prepared by catalytically selective oxidation of 5-hydroxymethylfurfural.
- 5-hydroxymethylfurfural there are -CH 2 OH (hydroxymethyl) and -CHO (aldehyde) difunctional groups.
- the preparation of 2,5-furandicarboxylic acid starting from 5-hydroxymethylfurfural requires simultaneous selective oxidation of the methylol group and selective oxidation of the aldehyde group. Since the selective oxidation reaction mechanism of two different functional groups of hydroxymethyl and aldehyde groups may be different, the use of conventional oxidation catalysts and oxidation techniques may result in very complex types of reaction products and intermediates, including 5-hydroxymethyl decanoic acid.
- 2,5-diformylfuran Compared with 5-hydroxymethylfurfural, 2,5-diformylfuran has only aldehyde functional groups in the molecular structure, and the oxidation product is relatively simple, including 5-formyl decanoic acid and 2,5-furandicarboxylic acid.
- Xu Jie's group has made great progress in the preparation of 2,5-diformylfuran by high-selective oxidation of 5-hydroxymethylfurfural.
- the present invention relates to a process for the catalytic oxidation of 2,5-diformylfuran to 2,5-furandicarboxylic acid.
- 2,5-diformylfuran is oxidized to 2,5-furandicarboxylic acid under the action of a sulfonic acid-based catalyst.
- the sulfonic acid-based catalyst is one or more of methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, Amberlyst-15, and carbonic acid.
- the density of the sulfonic acid group (-SO 3 H) in the sulfonic acid is 0.05-1.00 mmol g -1 ;
- mesoporous carbon (MC) or activated carbon (AC) in concentrated sulfuric acid, under nitrogen atmosphere, boiling at 70-250 ° C for 0.5-15h, preferably at 100-180 ° C temperature Boil for 5-10h, cool, care, wash well with hot water, and dry the resulting sample.
- the drying temperature is 60-100 ° C
- the drying time is 10-24 h.
- the amount of the catalyst is from 0.5 to 20 mol% based on the amount of the sulfonic acid group, and preferably the amount of the catalyst is from 5 to 15 mol% of the 2,5-formylfuran.
- the peroxide oxidizing agent is one or more selected from the group consisting of 5 to 70% by weight of hydrogen peroxide, t-butyl hydroperoxide, and 5 to 35% by weight of peroxyacetic acid, and the concentration of hydrogen peroxide is preferably 25 to 50% by weight, and the concentration of peroxyacetic acid is preferably 15 -25%.
- the molar ratio of peroxide oxidizing agent to 2,5-diformylfuran is from 2.1 to 10:1, preferably peroxide oxidation
- the molar ratio of the agent to 2,5-formylfuran is 4.8-8.2:1.
- the reaction temperature is 30-120 ° C, preferably the reaction temperature is 50-90 ° C;
- the reaction time is from 0.5 to 48 h, preferably from 4 to 24 h.
- the reaction is carried out in a solvent, and the solvent is one of acetonitrile, dioxane, methanol, ethanol, tert-butanol, acetone, and acetic acid.
- the solvent is one of acetonitrile, dioxane, methanol, ethanol, tert-butanol, acetone, and acetic acid.
- a solution is provided: a sulfonic acid-based catalyst, 2,5-formylfuran and a solvent are added to the reaction device, and the temperature is raised to a set temperature under stirring, and the peroxide oxidant is slowly dropped and dropped.
- the reaction is continued for a while, the 2,5-diformylfuran is oxidized to 2,5-furandicarboxylic acid.
- the invention provides a method for preparing high-quality 2,5-furandicarboxylic acid by high-selective oxidation of 2,5-diformylfuran under mild conditions, and the invention uses a peroxide as an oxygen source, and has high oxidation efficiency;
- the yield is high, clean and environmentally friendly;
- the catalyst system is simple and efficient, the product and the catalyst are easily separated, the by-products are few, the post-treatment is simple, and the application prospect is good.
- the catalysts used in Examples 7-16 are the catalysts in the table, specifically prepared according to the method described in Example 5, but this is merely illustrative, and the scope of the invention that can be practiced and protected is not limited thereto.
- MCS-x-y Mesoporous carbon sulfonic acid
- ACS-x-y activated carbon sulfonic acid
- the catalysts used in Examples 17-20 are the catalysts in the table, specifically prepared in accordance with the method described in Example 6, but this is merely illustrative, and the scope of the invention that can be practiced and protected is not limited thereto.
- the qualitative analysis of the product was carried out by liquid chromatography-mass spectrometry and compared with the retention time of the standard sample; the quantitative analysis was carried out by internal standard liquid chromatography.
- the invention develops a method for preparing 2,5-furandicarboxylic acid by selective oxidation of 2,5-diformylfuran.
- the catalyst system is simple and efficient, and the by-products are few.
- the catalyst and the product are easy to be separated and have a good application prospect.
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Abstract
A method for preparing 2,5-Furandicarboxylic acid by catalytic oxidation of 2,5-Diformylfuran. The method uses hyperoxide as an oxygen source; the 2,5-Diformylfuran is oxidized to be the 2,5-Furandicarboxylic acid under the effect of a sulfuric acid based catalyst. The method has high oxidation efficiency and high yield of product, is economical and environmentally friendly by using hyperoxide the oxygen source, and has considerable promise for application for the easily separated product and catalyst and simple after-treatment.
Description
本发明涉及到一种二元醛氧化制备二元酸的方法。This invention relates to a process for the oxidation of a dialdehyde to produce a dibasic acid.
2,5-呋喃二甲酸是以具有呋喃环结构的有机二元酸，与大宗化学品对苯二甲酸的分子结构相比，具有诸多的相似性。例如，都是含有环状结构的有机二元酸，且环状共轭电子的数目相同。2,5-呋喃二甲酸是合成多种精细化学品和呋喃基聚合物的重要中间体，在合成新型纤维和聚酯中具有重要的潜在应用价值。2,5-furandicarboxylic acid is an organic dibasic acid having a furan ring structure, and has many similarities with the molecular structure of the bulk chemical terephthalic acid. For example, they are all organic dibasic acids having a cyclic structure, and the number of cyclic conjugated electrons is the same. 2,5-furandicarboxylic acid is an important intermediate for the synthesis of various fine chemicals and furan-based polymers, and has important potential applications in the synthesis of new fibers and polyesters.
目前，2,5-呋喃二甲酸主要是催化选择氧化5-羟甲基糠醛制备的。5-羟甲基糠醛分子结构中，存在有-CH2OH(羟甲基)和-CHO(醛基)双官能团。由5-羟甲基糠醛出发制备2,5-呋喃二甲酸，需要同时完成羟甲基的选择氧化和醛基的选择氧化。由于羟甲基和醛基两类不同官能团的选择氧化反应机制可能不同，使用传统的氧化催化剂和氧化技术时，会导致反应产物和中间产物的种类非常复杂，包括5-羟甲基糠酸、2,5-二甲酰基呋喃、5-甲酰基糠酸和2,5-呋喃二甲酸等，这些中间产物可能会对下游应用产生不良影响；如5-羟甲基糠酸分子结构中同时有羟甲基和羧基官能团，易发生自聚。即使2,5-呋喃二甲酸产物中含有极少量醛基化合物，也可能会对其后续聚合应用有非常重要的影响。因此，如何获得高品质的2,5-呋喃二甲酸产物，是选择氧化过程面临的挑战之一。At present, 2,5-furandicarboxylic acid is mainly prepared by catalytically selective oxidation of 5-hydroxymethylfurfural. In the molecular structure of 5-hydroxymethylfurfural, there are -CH 2 OH (hydroxymethyl) and -CHO (aldehyde) difunctional groups. The preparation of 2,5-furandicarboxylic acid starting from 5-hydroxymethylfurfural requires simultaneous selective oxidation of the methylol group and selective oxidation of the aldehyde group. Since the selective oxidation reaction mechanism of two different functional groups of hydroxymethyl and aldehyde groups may be different, the use of conventional oxidation catalysts and oxidation techniques may result in very complex types of reaction products and intermediates, including 5-hydroxymethyl decanoic acid. 2,5-Diformylfuran, 5-formyl decanoic acid and 2,5-furandicarboxylic acid, etc. These intermediates may have adverse effects on downstream applications; for example, in the molecular structure of 5-hydroxymethyl decanoic acid Hydroxymethyl and carboxyl functional groups are prone to self-polymerization. Even a very small amount of aldehyde-based compound in the 2,5-furandicarboxylic acid product may have a very important influence on its subsequent polymerization application. Therefore, how to obtain high quality 2,5-furandicarboxylic acid products is one of the challenges in selecting an oxidation process.
2,5-二甲酰基呋喃与5-羟甲基糠醛相比，分子结构中只有醛基官能团，氧化产物相对简单，包括5-甲酰基糠酸和2,5-呋喃二甲酸。在5-羟甲基糠醛高选择性氧化制备2,5-二甲酰基呋喃方面，徐杰课题组已经取得了极大的进展。如公开发表的文献和已经授权的专利：(1)J.P.Ma,Z.T.Du,J.Xu,Q.H.Chu,Y.Pang,ChemSusChem 2011,4,51-54；(2)X.Q.Jia,J.P.Ma,M.Wang,Z.T.Du,F.Lu,F.Wang,J.Xu,Appl.Catal.A-Gen.2014,482,231-236；(3)ZL200810230244.3；(4)ZL200910012844.7)。Compared with 5-hydroxymethylfurfural, 2,5-diformylfuran has only aldehyde functional groups in the molecular structure, and the oxidation product is relatively simple, including 5-formyl decanoic acid and 2,5-furandicarboxylic acid. Xu Jie's group has made great progress in the preparation of 2,5-diformylfuran by high-selective oxidation of 5-hydroxymethylfurfural. Such as published literature and patents already granted: (1) JPMa, ZTDu, J. Xu, QHChu, Y. Pang, ChemSusChem 2011, 4, 51-54; (2) XQJia, JPMA, M .Wang, ZTDu, F. Lu, F. Wang, J. Xu, Appl. Catal. A-Gen. 2014, 482, 231-236; (3) ZL200810230244.3; (4) ZL200910012844.7).
发明内容Summary of the invention
本发明涉及一种催化氧化2,5-二甲酰基呋喃制备2,5-呋喃二甲酸的方法。The present invention relates to a process for the catalytic oxidation of 2,5-diformylfuran to 2,5-furandicarboxylic acid.
本发明采用的技术方案为:The technical solution adopted by the invention is:
一种催化氧化2,5-二甲酰基呋喃制备2,5-呋喃二甲酸的方法：A method for preparing 2,5-furandicarboxylic acid by catalytic oxidation of 2,5-diformylfuran:
以过氧化物为氧化剂，在磺酸基催化剂作用下，2,5-二甲酰基呋喃被氧化为2,5-呋喃二甲酸。Using a peroxide as an oxidizing agent, 2,5-diformylfuran is oxidized to 2,5-furandicarboxylic acid under the action of a sulfonic acid-based catalyst.
所述磺酸基催化剂为甲磺酸、三氟甲磺酸、对甲苯磺酸、Amberlyst-15、碳基磺酸中的一种或二种以上。The sulfonic acid-based catalyst is one or more of methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, Amberlyst-15, and carbonic acid.
碳基磺酸中磺酸基(-SO3H)的密度为0.05-1.00mmol g-1；The density of the sulfonic acid group (-SO 3 H) in the sulfonic acid is 0.05-1.00 mmol g -1 ;
所述碳基磺酸的制备：介孔碳(MC)或者活性碳(AC)于浓硫酸中，氮气气氛下，在70-250℃温度下煮0.5-15h，优选在100-180℃温度下煮5-10h，冷却，抽虑，热水充分洗涤，再将所得样品干燥。Preparation of the carbon-based sulfonic acid: mesoporous carbon (MC) or activated carbon (AC) in concentrated sulfuric acid, under nitrogen atmosphere, boiling at 70-250 ° C for 0.5-15h, preferably at 100-180 ° C temperature Boil for 5-10h, cool, care, wash well with hot water, and dry the resulting sample.
具体提供一种方案：干燥温度为60-100℃，干燥时间为10-24h。Specifically, a solution is provided: the drying temperature is 60-100 ° C, and the drying time is 10-24 h.
以磺酸基团的量计，催化剂用量为2,5-二甲酰基呋喃的0.5-20mol％，优选催化剂用量为2,5-二甲酰基呋喃的5-15mol％。The amount of the catalyst is from 0.5 to 20 mol% based on the amount of the sulfonic acid group, and preferably the amount of the catalyst is from 5 to 15 mol% of the 2,5-formylfuran.
过氧化物氧化剂为5-70wt％双氧水、叔丁基过氧化氢、5-35wt％过氧乙酸中的一种或二种以上，双氧水的浓度优选25-50wt％，过氧乙酸的浓度优选15-25％。The peroxide oxidizing agent is one or more selected from the group consisting of 5 to 70% by weight of hydrogen peroxide, t-butyl hydroperoxide, and 5 to 35% by weight of peroxyacetic acid, and the concentration of hydrogen peroxide is preferably 25 to 50% by weight, and the concentration of peroxyacetic acid is preferably 15 -25%.
过氧化物氧化剂与2,5-二甲酰基呋喃的摩尔比为2.1-10：1，优选过氧化物氧化
剂与2,5-二甲酰基呋喃的摩尔比为4.8-8.2：1。The molar ratio of peroxide oxidizing agent to 2,5-diformylfuran is from 2.1 to 10:1, preferably peroxide oxidation
The molar ratio of the agent to 2,5-formylfuran is 4.8-8.2:1.
反应温度为30-120℃，优选反应温度为50-90℃；The reaction temperature is 30-120 ° C, preferably the reaction temperature is 50-90 ° C;
反应时间为0.5-48h，优选反应时间为4-24h。The reaction time is from 0.5 to 48 h, preferably from 4 to 24 h.
反应于溶剂中进行，溶剂为乙腈、二氧六环、甲醇、乙醇、叔丁醇、丙酮、乙酸中的一种。The reaction is carried out in a solvent, and the solvent is one of acetonitrile, dioxane, methanol, ethanol, tert-butanol, acetone, and acetic acid.
具体操作时，提供一种方案：反应装置中加入磺酸基催化剂、2,5-二甲酰基呋喃以及溶剂，搅拌状态下升温至设定温度，再将过氧化物氧化剂缓慢滴入，滴加完毕，继续反应一段时间后，2,5-二甲酰基呋喃被氧化为2,5-呋喃二甲酸。In the specific operation, a solution is provided: a sulfonic acid-based catalyst, 2,5-formylfuran and a solvent are added to the reaction device, and the temperature is raised to a set temperature under stirring, and the peroxide oxidant is slowly dropped and dropped. When the reaction is continued for a while, the 2,5-diformylfuran is oxidized to 2,5-furandicarboxylic acid.
本发明产物2,5-呋喃二甲酸的纯化，若使用多相催化剂，反应混合液冷却至室温，离心除去催化剂，旋蒸除去溶剂，然后加入氢氧化钠溶液调节至pH＝8，加入乙酸乙酯萃取。水层用盐酸溶液酸化至pH＝1，2,5-呋喃二甲酸析出。然后用水重结晶提纯，40℃真空干燥，称重计算分离收率。Purification of the product 2,5-furandicarboxylic acid of the invention, if a heterogeneous catalyst is used, the reaction mixture is cooled to room temperature, the catalyst is removed by centrifugation, the solvent is removed by rotary evaporation, and then sodium hydroxide solution is added to adjust to pH=8, and ethyl acetate is added. Ester extraction. The aqueous layer was acidified to pH = 1,2,5-furandicarboxylic acid with a hydrochloric acid solution. Then, it was recrystallized and purified by water, dried under vacuum at 40 ° C, and the isolated yield was weighed.
2,5-呋喃二甲酸的纯化，若使用均相催化剂，反应混合液冷却至室温，旋蒸除去溶剂，然后加入氢氧化钠溶液调节至pH＝8，加入乙酸乙酯萃取。水层用盐酸溶液酸化至pH＝1，2,5-呋喃二甲酸析出。然后用水重结晶提纯，40℃真空干燥，称重计算分离收率。Purification of 2,5-furandicarboxylic acid, if a homogeneous catalyst is used, the reaction mixture is cooled to room temperature, and the solvent is removed by rotary evaporation. Then, sodium hydroxide solution is added to adjust to pH = 8 and ethyl acetate is added to extract. The aqueous layer was acidified to pH = 1,2,5-furandicarboxylic acid with a hydrochloric acid solution. Then, it was recrystallized and purified by water, dried under vacuum at 40 ° C, and the isolated yield was weighed.
本发明的有益效果为：The beneficial effects of the invention are:
本发明提供一种在温和条件下将2,5-二甲酰基呋喃高选择性氧化制备高品质2,5-呋喃二甲酸的方法，本发明以过氧化物为氧源，氧化效率高；产品收率高，清洁环保；催化剂体系简单、高效，产物和催化剂容易分离，副产物少，后处理简单，具有良好的应用前景。The invention provides a method for preparing high-quality 2,5-furandicarboxylic acid by high-selective oxidation of 2,5-diformylfuran under mild conditions, and the invention uses a peroxide as an oxygen source, and has high oxidation efficiency; The yield is high, clean and environmentally friendly; the catalyst system is simple and efficient, the product and the catalyst are easily separated, the by-products are few, the post-treatment is simple, and the application prospect is good.
以下通过实施例来对本发明予以进一步的说明，需要注意的是，下面的实施例仅用作举例说明，本发明能够实施以及所要保护的范围并不局限于此。The invention is further illustrated by the following examples, and it is to be noted that the following examples are merely illustrative, and the scope of the invention is not limited thereto.
实施例1Example 1
将1mmol 2,5-二甲酰基呋喃，0.005mmol甲磺酸催化剂，10mL乙腈加入到25mL三口圆底烧瓶中，搅拌下升至60℃，开始滴加30wt％双氧水至3mmol H2O2，在此温度下继续反应5h，冷却，所得样品定性分析采用液相色谱-质谱联用技术，定量分析由液相色谱实现。2,5-二甲酰基呋喃的转化率为80％，2,5-呋喃二甲酸的选择性为92％。2,5-呋喃二甲酸的分离收率为70％，高效液相色谱纯度为99.1％。1 mmol of 2,5-formylfuran, 0.005 mmol of methanesulfonic acid catalyst, 10 mL of acetonitrile was added to a 25 mL three-neck round bottom flask, and the mixture was stirred to 60 ° C, and 30 wt% hydrogen peroxide was added dropwise to 3 mmol H 2 O 2 . The reaction was continued for 5 h at this temperature, and the obtained sample was qualitatively analyzed by liquid chromatography-mass spectrometry, and quantitative analysis was carried out by liquid chromatography. The conversion of 2,5-diformylfuran was 80%, and the selectivity of 2,5-furandicarboxylic acid was 92%. The isolated yield of 2,5-furandicarboxylic acid was 70%, and the purity of the high performance liquid chromatography was 99.1%.
实施例2Example 2
将1mmol 2,5-二甲酰基呋喃，0.05mmol三氟甲磺酸催化剂，10mL乙酸加入到25mL三口圆底烧瓶中，搅拌下升至100℃，开始滴加60wt％双氧水至6mmol H2O2，在此温度下继续反应1h，冷却，所得样品定性分析采用液相色谱-质谱联用技术，定量分析由液相色谱实现。2,5-二甲酰基呋喃的转化率为100％，2,5-呋喃二甲酸的选择性为98％。2,5-呋喃二甲酸的分离收率为97％，高效液相色谱纯度为99.9％。1 mmol of 2,5-formylfuran, 0.05 mmol of trifluoromethanesulfonic acid catalyst, 10 mL of acetic acid was added to a 25 mL three-neck round bottom flask, and the mixture was raised to 100 ° C with stirring, and 60 wt% hydrogen peroxide was added dropwise to 6 mmol H 2 O 2 . The reaction was continued at this temperature for 1 h, and the obtained sample was qualitatively analyzed by liquid chromatography-mass spectrometry, and quantitative analysis was carried out by liquid chromatography. The conversion of 2,5-diformylfuran was 100%, and the selectivity of 2,5-furandicarboxylic acid was 98%. The isolated yield of 2,5-furandicarboxylic acid was 97%, and the purity of the high performance liquid chromatography was 99.9%.
实施例3Example 3
将1mmol 2,5-二甲酰基呋喃，0.1mmol Amberlyst-15催化剂，10mL乙酸加入到25mL三口圆底烧瓶中，搅拌下升至120℃，开始滴加10mmol叔丁基过氧化氢，在此温度下继续反应0.5h，冷却，所得样品定性分析采用液相色谱-质谱联用技术，定量分析由液相色谱实现。2,5-二甲酰基呋喃的转化率为100％，2,5-呋喃二甲酸的选择性为97％。2,5-呋喃二甲酸的分离收率为96％，高效液相色谱纯度为99.8％。1 mmol of 2,5-formylfuran, 0.1 mmol of Amberlyst-15 catalyst, 10 mL of acetic acid was added to a 25 mL three-neck round bottom flask, and the mixture was raised to 120 ° C with stirring, and 10 mmol of t-butyl hydroperoxide was added dropwise at this temperature. The reaction was continued for 0.5 h, and the obtained sample was qualitatively analyzed by liquid chromatography-mass spectrometry, and quantitative analysis was carried out by liquid chromatography. The conversion of 2,5-diformylfuran was 100%, and the selectivity of 2,5-furandicarboxylic acid was 97%. The isolated yield of 2,5-furandicarboxylic acid was 96%, and the purity of the high performance liquid chromatography was 99.8%.
实施例4Example 4
将1mmol 2,5-二甲酰基呋喃，0.18mmol对甲苯磺酸催化剂，10mL丙酮加入
到25mL三口圆底烧瓶中，搅拌下升至30℃，开始滴加30wt％双氧水至8mmolH2O2，在此温度下继续反应48h，冷却，所得样品定性分析采用液相色谱-质谱联用技术，定量分析由液相色谱实现。2,5-二甲酰基呋喃的转化率为100％，2,5-呋喃二甲酸的选择性为99％。2,5-呋喃二甲酸的分离收率为98％，高效液相色谱纯度为99.9％。1 mmol of 2,5-diformylfuran, 0.18 mmol of p-toluenesulfonic acid catalyst, 10 mL of acetone was added to a 25 mL three-neck round bottom flask, and the mixture was stirred to 30 ° C, and 30 wt% hydrogen peroxide was added dropwise to 8 mmol H 2 O 2 . The reaction was continued for 48 h at this temperature, and the obtained sample was qualitatively analyzed by liquid chromatography-mass spectrometry, and quantitative analysis was carried out by liquid chromatography. The conversion of 2,5-diformylfuran was 100%, and the selectivity of 2,5-furandicarboxylic acid was 99%. The isolated yield of 2,5-furandicarboxylic acid was 98%, and the purity of the high performance liquid chromatography was 99.9%.
实施例5Example 5
碳基磺酸催化剂的制备：称取5g介孔碳(MC)或者活性碳(AC)于100mL 98％浓硫酸，氮气气氛下，在设定温度x(x为磺化温度)下煮15h。冷却，抽虑，用大量热水充分洗涤，至到滤液不能使0.02mol L-1氯化钡溶液变混浊。所得样品80℃干燥12h，命名为MCS-x或者ACS-x，x为磺化温度。样品的磺酸基(-SO3H)密度mmol g-1通过X-射线荧光仪测定。所得碳基磺酸物理性质如表1所示。Preparation of carbon-based sulfonic acid catalyst: 5 g of mesoporous carbon (MC) or activated carbon (AC) was weighed in 100 mL of 98% concentrated sulfuric acid under a nitrogen atmosphere at a set temperature x (x is the sulfonation temperature) for 15 h. Cooling, pumping, and washing with a large amount of hot water until the filtrate could not make 0.02 mol L -1 cerium chloride solution turbid. The resulting sample was dried at 80 ° C for 12 h and designated as MCS-x or ACS-x, where x is the sulfonation temperature. Samples of a sulfonic acid group (-SO 3 H) Density mmol g -1 as determined by X- ray fluorescence. The physical properties of the obtained carbon-based sulfonic acid are shown in Table 1.
表1介孔碳基磺酸(MCS-x)或者活性碳基磺酸(ACS-x)磺酸基密度Table 1 Density of mesoporous carbon sulfonic acid (MCS-x) or activated carbon sulfonic acid (ACS-x) sulfonic acid
| 催化剂catalyst | 磺酸基密度(mmol g-1)Sulfonic acid group density (mmol g -1 ) |
| MCMC | -- |
| MCS-80MCS-80 | 0.410.41 |
| MCS-120MCS-120 | 0.680.68 |
| MCS-150MCS-150 | 0.710.71 |
| MCS-180MCS-180 | 0.820.82 |
| MCS-200MCS-200 | 0.960.96 |
| ACAC | -- |
| ACS-80ACS-80 | 0.430.43 |
| ACS-120ACS-120 | 0.650.65 |
| ACS-150ACS-150 | 0.700.70 |
| ACS-180ACS-180 | 0.800.80 |
| ACS-200ACS-200 | 0.950.95 |
实施例7-16中所采用的催化剂即是表格中的催化剂，具体是按照实施例5所述方法进行制备的，但这只是举例说明，本发明所能够实施以及保护的范围并不限于此。The catalysts used in Examples 7-16 are the catalysts in the table, specifically prepared according to the method described in Example 5, but this is merely illustrative, and the scope of the invention that can be practiced and protected is not limited thereto.
实施例6Example 6
碳基磺酸催化剂的制备：称取5g介孔碳(MC)或者活性碳(AC)于100mL 98％浓硫酸，氮气气氛下，在设定温度x(x为磺化温度)下煮设定时间y(y为磺化时间)。冷却，抽虑，用大量热水充分洗涤，至到滤液不能使0.02mol L-1氯化钡溶液变混浊。所得样品80℃干燥12h，命名为MCS-x-y或者ACS-x-y，x为磺化温度。样品的磺酸基(-SO3H)密度mmol g-1通过X-射线荧光仪测定。所得碳基磺酸物理性质如表2所示。Preparation of carbon-based sulfonic acid catalyst: Weigh 5g mesoporous carbon (MC) or activated carbon (AC) in 100mL 98% concentrated sulfuric acid, set at a set temperature x (x is the sulfonation temperature) under nitrogen atmosphere Time y (y is the sulfonation time). Cooling, pumping, and washing with a large amount of hot water until the filtrate could not make 0.02 mol L -1 cerium chloride solution turbid. The resulting sample was dried at 80 ° C for 12 h and designated as MCS-xy or ACS-xy, where x is the sulfonation temperature. Samples of a sulfonic acid group (-SO 3 H) Density mmol g -1 as determined by X- ray fluorescence. The physical properties of the obtained carbon-based sulfonic acid are shown in Table 2.
表2介孔碳基磺酸(MCS-x-y)或者活性碳基磺酸(ACS-x-y)磺酸基密度Table 2 Mesoporous carbon sulfonic acid (MCS-x-y) or activated carbon sulfonic acid (ACS-x-y) sulfonic acid group density
| 催化剂catalyst | 磺酸基密度(mmol g-1)Sulfonic acid group density (mmol g -1 ) |
| MCMC | -- |
| MCS-80-15MCS-80-15 | 0.450.45 |
| MCS-120-4MCS-120-4 | 0.550.55 |
| MCS-150-6MCS-150-6 | 0.730.73 |
| MCS-180-8MCS-180-8 | 0.780.78 |
| MCS-200-0.5MCS-200-0.5 | 0.920.92 |
| ACAC | -- |
| ACS-80-15ACS-80-15 | 0.440.44 |
| ACS-120-4ACS-120-4 | 0.560.56 |
| ACS-150-6ACS-150-6 | 0.680.68 |
| ACS-180-8ACS-180-8 | 0.850.85 |
| ACS-200-0.5ACS-200-0.5 | 0.960.96 |
实施例17-20中所采用的催化剂即是表格中的催化剂，具体是按照实施例6所述方法进行制备的，但这只是举例说明，本发明所能够实施以及保护的范围并不限于此。The catalysts used in Examples 17-20 are the catalysts in the table, specifically prepared in accordance with the method described in Example 6, but this is merely illustrative, and the scope of the invention that can be practiced and protected is not limited thereto.
实施例7Example 7
将1mmol 2,5-二甲酰基呋喃，0.08mmol MCS-80催化剂，10mL二氧六环加入到25mL三口圆底烧瓶中，搅拌下升至90℃，开始滴加10wt％过氧乙酸至2.5mmolCH3COOOH，在此温度下继续反应24h，冷却，所得样品定性分析采用液相色谱-质谱联用技术，定量分析由液相色谱实现。2,5-二甲酰基呋喃的转化率为99％，2,5-呋喃二甲酸的选择性为99％。2,5-呋喃二甲酸的分离收率为97％，高效液相色谱纯度为99.9％。1 mmol of 2,5-diformylfuran, 0.08 mmol of MCS-80 catalyst, 10 mL of dioxane was added to a 25 mL three-neck round bottom flask, and the mixture was raised to 90 ° C with stirring, and 10 wt% peroxyacetic acid was added dropwise to 2.5 mmol CH. 3 COOOH, the reaction was continued at this temperature for 24 h, and the obtained sample was qualitatively analyzed by liquid chromatography-mass spectrometry, and quantitative analysis was carried out by liquid chromatography. The conversion of 2,5-diformylfuran was 99%, and the selectivity of 2,5-furandicarboxylic acid was 99%. The isolated yield of 2,5-furandicarboxylic acid was 97%, and the purity of the high performance liquid chromatography was 99.9%.
实施例8Example 8
将1mmol 2,5-二甲酰基呋喃，0.08mmol MCS-120催化剂，10mL甲醇加入到25mL三口圆底烧瓶中，搅拌下升至65℃，开始滴加30wt％过氧乙酸至5mmolCH3COOOH，在此温度下继续反应12h，冷却，所得样品定性分析采用液相色谱-质谱联用技术，定量分析由液相色谱实现。2,5-二甲酰基呋喃的转化率为98％，2,5-呋喃二甲酸的选择性为99％。2,5-呋喃二甲酸的分离收率为95％，高效液相色谱纯度为99.0％。1 mmol of 2,5-formylfuran, 0.08 mmol of MCS-120 catalyst, 10 mL of methanol was added to a 25 mL three-neck round bottom flask, and the mixture was raised to 65 ° C with stirring, and 30 wt% peroxyacetic acid was added dropwise to 5 mmol CH 3 COOOH. The reaction was continued for 12 h at this temperature, and the obtained sample was qualitatively analyzed by liquid chromatography-mass spectrometry, and quantitative analysis was carried out by liquid chromatography. The conversion of 2,5-diformylfuran was 98%, and the selectivity of 2,5-furandicarboxylic acid was 99%. The isolated yield of 2,5-furandicarboxylic acid was 95%, and the purity of the high performance liquid chromatography was 99.0%.
实施例9Example 9
将1mmol 2,5-二甲酰基呋喃，0.12mmol MCS-150催化剂，10mL乙醇加入到25mL三口圆底烧瓶中，搅拌下升至78℃，开始滴加50wt％双氧水至7mmol H2O2，在此温度下继续反应10h，冷却，所得样品定性分析采用液相色谱-质谱联用技术，定量分析由液相色谱实现。2,5-二甲酰基呋喃的转化率为92％，2,5-呋喃二甲酸的选择性为97％。2,5-呋喃二甲酸的分离收率为88％，高效液相色谱纯度为99.5％。1 mmol of 2,5-formylfuran, 0.12 mmol of MCS-150 catalyst, 10 mL of ethanol was added to a 25 mL three-neck round bottom flask, and the mixture was raised to 78 ° C with stirring, and 50 wt% hydrogen peroxide was added dropwise to 7 mmol H 2 O 2 . The reaction was continued at this temperature for 10 h, and the obtained sample was qualitatively analyzed by liquid chromatography-mass spectrometry, and quantitative analysis was carried out by liquid chromatography. The conversion of 2,5-diformylfuran was 92%, and the selectivity of 2,5-furandicarboxylic acid was 97%. The isolated yield of 2,5-furandicarboxylic acid was 88%, and the purity of the high performance liquid chromatography was 99.5%.
实施例10Example 10
将1mmol 2,5-二甲酰基呋喃，0.14mmol MCS-180催化剂，10mL乙酸加入到25mL三口圆底烧瓶中，搅拌下升至50℃，开始滴加30wt％双氧水至9mmol H2O2，在此温度下继续反应16h，冷却，所得样品定性分析采用液相色谱-质谱联用技术，定量分析由液相色谱实现。2,5-二甲酰基呋喃的转化率为99％，2,5-呋喃二甲酸的选择性为99％。2,5-呋喃二甲酸的分离收率为97％，高效液相色谱纯度为99.9％。1 mmol of 2,5-formylfuran, 0.14 mmol of MCS-180 catalyst, 10 mL of acetic acid was added to a 25 mL three-neck round bottom flask, and the mixture was raised to 50 ° C with stirring, and 30 wt% hydrogen peroxide was added dropwise to 9 mmol H 2 O 2 . The reaction was continued for 16 h at this temperature, and the obtained sample was qualitatively analyzed by liquid chromatography-mass spectrometry, and quantitative analysis was carried out by liquid chromatography. The conversion of 2,5-diformylfuran was 99%, and the selectivity of 2,5-furandicarboxylic acid was 99%. The isolated yield of 2,5-furandicarboxylic acid was 97%, and the purity of the high performance liquid chromatography was 99.9%.
实施例11Example 11
将1mmol 2,5-二甲酰基呋喃，0.2mmol介孔碳(MC)催化剂，10mL乙酸加入到25mL三口圆底烧瓶中，搅拌下升至50℃，开始滴加70wt％双氧水至9mmolH2O2，在此温度下继续反应16h，冷却，所得样品定性分析采用液相色谱-质谱联用技术，定量分析由液相色谱实现。2,5-二甲酰基呋喃的转化率为20％，2,5-呋喃二甲酸的选择性为99％。2,5-呋喃二甲酸的分离收率为15％，高效液相色谱纯度为99.0％。1 mmol of 2,5-diformylfuran, 0.2 mmol of mesoporous carbon (MC) catalyst, 10 mL of acetic acid was added to a 25 mL three-neck round bottom flask, and the mixture was stirred to 50 ° C, and 70 wt% hydrogen peroxide was added dropwise to 9 mmol H 2 O 2 . The reaction was continued at this temperature for 16 h, and the obtained sample was qualitatively analyzed by liquid chromatography-mass spectrometry, and quantitative analysis was carried out by liquid chromatography. The conversion of 2,5-diformylfuran was 20%, and the selectivity of 2,5-furandicarboxylic acid was 99%. The isolated yield of 2,5-furandicarboxylic acid was 15%, and the purity of the high performance liquid chromatography was 99.0%.
实施例12Example 12
将1mmol 2,5-二甲酰基呋喃，0.009mmol MCS-200催化剂，10mL叔丁醇加入
到25mL三口圆底烧瓶中，搅拌下升至82℃，开始滴加5wt％双氧水至3mmol H2O2，在此温度下继续反应20h，冷却，所得样品定性分析采用液相色谱-质谱联用技术，定量分析由液相色谱实现。2,5-二甲酰基呋喃的转化率为100％，2,5-呋喃二甲酸的选择性为99％。2,5-呋喃二甲酸的分离收率为98％，高效液相色谱纯度为99.9％。1 mmol of 2,5-diformylfuran, 0.009 mmol of MCS-200 catalyst, 10 mL of t-butanol was added to a 25 mL three-neck round bottom flask, and the mixture was raised to 82 ° C with stirring, and dropwise addition of 5 wt% hydrogen peroxide to 3 mmol H 2 O 2 was started. The reaction was continued at this temperature for 20 h, and the obtained sample was qualitatively analyzed by liquid chromatography-mass spectrometry, and quantitative analysis was carried out by liquid chromatography. The conversion of 2,5-diformylfuran was 100%, and the selectivity of 2,5-furandicarboxylic acid was 99%. The isolated yield of 2,5-furandicarboxylic acid was 98%, and the purity of the high performance liquid chromatography was 99.9%.
实施例13Example 13
将1mmol 2,5-二甲酰基呋喃，0.009mmol ACS-200催化剂，10mL乙酸加入到25mL三口圆底烧瓶中，搅拌下升至100℃，开始滴加35wt％双氧水至3mmol H2O2，在此温度下继续反应20h，冷却，所得样品定性分析采用液相色谱-质谱联用技术，定量分析由液相色谱实现。2,5-二甲酰基呋喃的转化率为100％，2,5-呋喃二甲酸的选择性为95％。2,5-呋喃二甲酸的分离收率为94％，高效液相色谱纯度为99.9％。1 mmol of 2,5-diformylfuran, 0.009 mmol of ACS-200 catalyst, 10 mL of acetic acid was added to a 25 mL three-neck round bottom flask, and the mixture was raised to 100 ° C with stirring, and dropwise addition of 35 wt% hydrogen peroxide to 3 mmol H 2 O 2 was started. The reaction was continued at this temperature for 20 h, and the obtained sample was qualitatively analyzed by liquid chromatography-mass spectrometry, and quantitative analysis was carried out by liquid chromatography. The conversion of 2,5-diformylfuran was 100%, and the selectivity of 2,5-furandicarboxylic acid was 95%. The isolated yield of 2,5-furandicarboxylic acid was 94%, and the purity of the high performance liquid chromatography was 99.9%.
实施例14Example 14
将1mmol 2,5-二甲酰基呋喃，0.009mmol ACS-80催化剂，10mL乙醇加入到25mL三口圆底烧瓶中，搅拌下升至50℃，开始滴加40wt％双氧水至7mmol H2O2，在此温度下继续反应36h，冷却，所得样品定性分析采用液相色谱-质谱联用技术，定量分析由液相色谱实现。2,5-二甲酰基呋喃的转化率为100％，2,5-呋喃二甲酸的选择性为97％。2,5-呋喃二甲酸的分离收率为96％，高效液相色谱纯度为99.9％。1 mmol of 2,5-diformylfuran, 0.009 mmol of ACS-80 catalyst, 10 mL of ethanol was added to a 25 mL three-neck round bottom flask, and the mixture was heated to 50 ° C with stirring, and 40 wt% hydrogen peroxide was added dropwise to 7 mmol H 2 O 2 . The reaction was continued for 36 h at this temperature, and the obtained sample was qualitatively analyzed by liquid chromatography-mass spectrometry, and quantitative analysis was carried out by liquid chromatography. The conversion of 2,5-diformylfuran was 100%, and the selectivity of 2,5-furandicarboxylic acid was 97%. The isolated yield of 2,5-furandicarboxylic acid was 96%, and the purity of the high performance liquid chromatography was 99.9%.
实施例15Example 15
将1mmol 2,5-二甲酰基呋喃，0.009mmol ACS-120催化剂，10mL甲醇加入到25mL三口圆底烧瓶中，搅拌下升至50℃，开始滴加30wt％双氧水至10mmol H2O2，在此温度下继续反应30h，冷却，所得样品定性分析采用液相色谱-质谱联用技术，定量分析由液相色谱实现。2,5-二甲酰基呋喃的转化率为99％，2,5-呋喃二甲酸的选择性为97％。2,5-呋喃二甲酸的分离收率为95％，高效液相色谱纯度为99.8％。1 mmol of 2,5-diformylfuran, 0.009 mmol of ACS-120 catalyst, 10 mL of methanol was added to a 25 mL three-neck round bottom flask, and the mixture was raised to 50 ° C with stirring, and 30 wt% hydrogen peroxide was added dropwise to 10 mmol H 2 O 2 . The reaction was continued for 30 h at this temperature, and the obtained sample was qualitatively analyzed by liquid chromatography-mass spectrometry, and quantitative analysis was carried out by liquid chromatography. The conversion of 2,5-diformylfuran was 99%, and the selectivity of 2,5-furandicarboxylic acid was 97%. The isolated yield of 2,5-furandicarboxylic acid was 95%, and the purity of the high performance liquid chromatography was 99.8%.
实施例16Example 16
将1mmol 2,5-二甲酰基呋喃，0.10mmol活性碳(AC)催化剂，10mL乙酸加入到25mL三口圆底烧瓶中，搅拌下升至120℃，开始滴加30wt％双氧水至10mmol H2O2，在此温度下继续反应30h，冷却，所得样品定性分析采用液相色谱-质谱联用技术，定量分析由液相色谱实现。2,5-二甲酰基呋喃的转化率为29％，2,5-呋喃二甲酸的选择性为95％。2,5-呋喃二甲酸的分离收率为25％，高效液相色谱纯度为99.7％。1 mmol of 2,5-formylfuran, 0.10 mmol of activated carbon (AC) catalyst, 10 mL of acetic acid was added to a 25 mL three-neck round bottom flask, and the mixture was stirred to 120 ° C, and 30 wt% hydrogen peroxide was added dropwise to 10 mmol H 2 O 2 . The reaction was continued at this temperature for 30 h, and the obtained sample was qualitatively analyzed by liquid chromatography-mass spectrometry, and quantitative analysis was carried out by liquid chromatography. The conversion of 2,5-diformylfuran was 29%, and the selectivity of 2,5-furandicarboxylic acid was 95%. The isolated yield of 2,5-furandicarboxylic acid was 25%, and the purity of the high performance liquid chromatography was 99.7%.
实施例17Example 17
将1mmol 2,5-二甲酰基呋喃，0.10mmol ACS-180-8催化剂，10mL乙酸加入到25mL三口圆底烧瓶中，搅拌下升至80℃，开始滴加40wt％双氧水至6mmol H2O2，在此温度下继续反应20h，冷却，所得样品定性分析采用液相色谱-质谱联用技术，定量分析由液相色谱实现。2,5-二甲酰基呋喃的转化率为99％，2,5-呋喃二甲酸的选择性为98％。2,5-呋喃二甲酸的分离收率为96％，高效液相色谱纯度为99.9％。1 mmol of 2,5-formylfuran, 0.10 mmol of ACS-180-8 catalyst, 10 mL of acetic acid was added to a 25 mL three-neck round bottom flask, and the mixture was raised to 80 ° C with stirring, and 40 wt% hydrogen peroxide was added dropwise to 6 mmol H 2 O 2 . The reaction was continued at this temperature for 20 h, and the obtained sample was qualitatively analyzed by liquid chromatography-mass spectrometry, and quantitative analysis was carried out by liquid chromatography. The conversion of 2,5-diformylfuran was 99%, and the selectivity of 2,5-furandicarboxylic acid was 98%. The isolated yield of 2,5-furandicarboxylic acid was 96%, and the purity of the high performance liquid chromatography was 99.9%.
实施例18Example 18
将1mmol 2,5-二甲酰基呋喃，0.10mmol MCS-180-8催化剂，10mL乙酸加入到25mL三口圆底烧瓶中，搅拌下升至70℃，开始滴加20wt％过氧乙酸至5.5mmol CH3COOOH，在此温度下继续反应16h，冷却，所得样品定性分析采用液相色谱-质谱联用技术，定量分析由液相色谱实现。2,5-二甲酰基呋喃的转化率为98％，2,5-呋喃二甲酸的选择性为99％。2,5-呋喃二甲酸的分离收率为96％，高效液相色谱纯度为99.8％。1 mmol of 2,5-formylfuran, 0.10 mmol of MCS-180-8 catalyst, 10 mL of acetic acid was added to a 25 mL three-neck round bottom flask, and the mixture was raised to 70 ° C with stirring, and 20 wt% peroxyacetic acid was added dropwise to 5.5 mmol CH. 3 COOOH, the reaction was continued at this temperature for 16 h, and the obtained sample was qualitatively analyzed by liquid chromatography-mass spectrometry, and quantitative analysis was carried out by liquid chromatography. The conversion of 2,5-diformylfuran was 98%, and the selectivity of 2,5-furandicarboxylic acid was 99%. The isolated yield of 2,5-furandicarboxylic acid was 96%, and the purity of the high performance liquid chromatography was 99.8%.
实施例19Example 19
将1mmol 2,5-二甲酰基呋喃，0.12mmol MCS-120-4催化剂，10mL乙酸加入到25mL三口圆底烧瓶中，搅拌下升至75℃，开始滴加22wt％过氧乙酸至6.2mmol
CH3COOOH，在此温度下继续反应10h，冷却，所得样品定性分析采用液相色谱-质谱联用技术，定量分析由液相色谱实现。2,5-二甲酰基呋喃的转化率为95％，2,5-呋喃二甲酸的选择性为99％。2,5-呋喃二甲酸的分离收率为93％，高效液相色谱纯度为99.9％。1 mmol of 2,5-formylfuran, 0.12 mmol of MCS-120-4 catalyst, 10 mL of acetic acid was added to a 25 mL three-neck round bottom flask, and the mixture was raised to 75 ° C with stirring, and 22 wt% peroxyacetic acid was added dropwise to 6.2 mmol CH. 3 COOOH, the reaction was continued at this temperature for 10 h, and the obtained sample was qualitatively analyzed by liquid chromatography-mass spectrometry, and quantitative analysis was carried out by liquid chromatography. The conversion of 2,5-diformylfuran was 95%, and the selectivity of 2,5-furandicarboxylic acid was 99%. The isolated yield of 2,5-furandicarboxylic acid was 93%, and the purity of the high performance liquid chromatography was 99.9%.
实施例20Example 20
将1mmol 2,5-二甲酰基呋喃，0.08mmol ACS-120-4催化剂，10mL乙酸加入到25mL三口圆底烧瓶中，搅拌下升至85℃，开始滴加40wt％过氧乙酸至8.0mmol CH3COOOH，在此温度下继续反应20h，冷却，所得样品定性分析采用液相色谱-质谱联用技术，定量分析由液相色谱实现。2,5-二甲酰基呋喃的转化率为99％，2,5-呋喃二甲酸的选择性为99％。2,5-呋喃二甲酸的分离收率为95％，高效液相色谱纯度为99.8％。1 mmol of 2,5-formylfuran, 0.08 mmol of ACS-120-4 catalyst, 10 mL of acetic acid was added to a 25 mL three-neck round bottom flask, and the mixture was raised to 85 ° C with stirring, and 40 wt% peroxyacetic acid was added dropwise to 8.0 mmol CH. 3 COOOH, the reaction was continued at this temperature for 20 h, and the obtained sample was qualitatively analyzed by liquid chromatography-mass spectrometry, and quantitative analysis was carried out by liquid chromatography. The conversion of 2,5-diformylfuran was 99%, and the selectivity of 2,5-furandicarboxylic acid was 99%. The isolated yield of 2,5-furandicarboxylic acid was 95%, and the purity of the high performance liquid chromatography was 99.8%.
产品的定性采用液相色谱-质谱分析，并和标准样品的保留时间进行比对；定量用内标法液相色谱分析。The qualitative analysis of the product was carried out by liquid chromatography-mass spectrometry and compared with the retention time of the standard sample; the quantitative analysis was carried out by internal standard liquid chromatography.
2,5-二甲酰基呋喃的转化率＝(转化2,5-二甲酰基呋喃的摩尔数/投入2,5-二甲酰基呋喃的摩尔数)×100％Conversion of 2,5-diformylfuran = (moles of 2,5-diformylfuran / number of moles of 2,5-diformylfuran) × 100%
2,5-呋喃二甲酸的选择性＝(2,5-呋喃二甲酸的摩尔数/转化2,5-二甲酰基呋喃的摩尔数)×100％Selectivity of 2,5-furandicarboxylic acid = (moles of 2,5-furandicarboxylic acid / number of moles of converted 2,5-formylfuran) × 100%
本发明开发了一种2,5-二甲酰基呋喃选择氧化制备2,5-呋喃二甲酸的方法，催化剂体系简单、高效，副产物少，催化剂与产物易分离具有很好的应用前景。
The invention develops a method for preparing 2,5-furandicarboxylic acid by selective oxidation of 2,5-diformylfuran. The catalyst system is simple and efficient, and the by-products are few. The catalyst and the product are easy to be separated and have a good application prospect.
Claims (10)
- 一种催化氧化2,5-二甲酰基呋喃制备2,5-呋喃二甲酸的方法，其特征在于：A method for catalytically oxidizing 2,5-diformylfuran to prepare 2,5-furandicarboxylic acid, characterized in that:以过氧化物为氧化剂，在磺酸基催化剂作用下，2,5-二甲酰基呋喃被氧化为2,5-呋喃二甲酸。Using a peroxide as an oxidizing agent, 2,5-diformylfuran is oxidized to 2,5-furandicarboxylic acid under the action of a sulfonic acid-based catalyst.
- 按照权利要求1所述的方法，其特征在于：The method of claim 1 wherein:所述磺酸基催化剂为甲磺酸、三氟甲磺酸、对甲苯磺酸、Amberlyst-15、碳基磺酸中的一种或二种以上。The sulfonic acid-based catalyst is one or more of methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, Amberlyst-15, and carbonic acid.
- 按照权利要求2所述的方法，其特征在于：The method of claim 2 wherein:碳基磺酸中磺酸基(-SO3H)的密度为0.05-1.00mmol g-1。The sulfonic acid group (-SO 3 H) in the carbamic sulfonic acid has a density of from 0.05 to 1.00 mmol g -1 .
- 按照权利要求2所述的方法，其特征在于：The method of claim 2 wherein:所述碳基磺酸的制备：所述碳基磺酸的制备：介孔碳(MC)或者活性碳(AC)于浓硫酸中，氮气气氛下，在70-250℃温度下煮0.5-15h，优选在100-180℃温度下煮5-10h，冷却，抽虑，热水充分洗涤，再将所得样品干燥。Preparation of the carbon-based sulfonic acid: preparation of the carbon-based sulfonic acid: mesoporous carbon (MC) or activated carbon (AC) in concentrated sulfuric acid, nitrogen atmosphere, boiling at 70-250 ° C for 0.5-15h It is preferably boiled at a temperature of 100-180 ° C for 5-10 h, cooled, pumped, washed thoroughly with hot water, and the resulting sample is dried.
- 按照权利要求1所述的方法，其特征在于：The method of claim 1 wherein:以磺酸基团的量计，催化剂用量为2,5-二甲酰基呋喃的0.5-20mol％，优选催化剂用量为2,5-二甲酰基呋喃的5-15mol％。The amount of the catalyst is from 0.5 to 20 mol% based on the amount of the sulfonic acid group, and preferably the amount of the catalyst is from 5 to 15 mol% of the 2,5-formylfuran.
- 按照权利要求1所述的方法，其特征在于：过氧化物氧化剂为5-70wt％双氧水、叔丁基过氧化氢、5-35wt％过氧乙酸中的一种或二种以上，双氧水的浓度优选25-50wt％，过氧乙酸的浓度优选15-25％。The method according to claim 1, wherein the peroxide oxidizing agent is one or more of 5-70% by weight of hydrogen peroxide, t-butyl hydroperoxide and 5-35% by weight of peroxyacetic acid, and the concentration of hydrogen peroxide is Preferably, it is 25-50% by weight, and the concentration of peracetic acid is preferably 15-25%.
- 按照权利要求1所述的方法，其特征在于：过氧化物氧化剂与2,5-二甲酰基呋喃的摩尔比为2.1-10：1，优选过氧化物氧化剂与2,5-二甲酰基呋喃的摩尔比为4.8-8.2：1。The method according to claim 1, wherein the molar ratio of the peroxide oxidizing agent to the 2,5-formylfuran is from 2.1 to 10:1, preferably the peroxide oxidizing agent and the 2,5-diformylfuran. The molar ratio is 4.8-8.2:1.
- 按照权利要求1所述的方法，其特征在于：The method of claim 1 wherein:反应温度为30-120℃，优选反应温度为50-90℃；反应时间为0.5-48h，优选反应时间为4-24h。The reaction temperature is 30-120 ° C, preferably the reaction temperature is 50-90 ° C; the reaction time is 0.5-48 h, preferably the reaction time is 4-24 h.
- 按照权利要求1所述的方法，其特征在于：反应于溶剂中进行，溶剂为乙腈、二氧六环、甲醇、乙醇、叔丁醇、丙酮、乙酸中的一种。The method according to claim 1, wherein the reaction is carried out in a solvent of one of acetonitrile, dioxane, methanol, ethanol, tert-butanol, acetone, and acetic acid.
- 按照权利要求1所述的方法，其特征在于：反应装置中加入磺酸基催化剂、2,5-二甲酰基呋喃以及溶剂，搅拌状态下升温至设定温度，再将过氧化物氧化剂缓慢滴入，滴加完毕，继续反应一段时间后，2,5-二甲酰基呋喃被氧化为2,5-呋喃二甲酸。 The method according to claim 1, wherein a sulfonic acid-based catalyst, 2,5-formylfuran and a solvent are added to the reaction apparatus, and the temperature is raised to a set temperature under stirring, and the peroxide oxidant is slowly dropped. After the completion of the dropwise addition, the reaction was continued for a while, and the 2,5-diformylfuran was oxidized to 2,5-furandicarboxylic acid.
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| CN104684903A (en) * | 2012-09-27 | 2015-06-03 | 罗盖特公司 | Method for synthesising 2, 5-furandicarboxylic acid from a composition containing furan-2, 5-dialdehyde |
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| CN104529957A (en) * | 2014-12-26 | 2015-04-22 | 中国科学技术大学先进技术研究院 | Preparation method of 2,5-furandicarboxylate |
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| HEMANT CHOUDHARY ET AL.: "Metal-free oxidative synthesis of succinic acid from biomass-derived furan compounds using a solid acid catalyst with hydr gen peroxide", APPLIED CATALYSIS A: GENERAL, vol. 458, 30 March 2013 (2013-03-30), pages 55 - 62, XP055451194, ISSN: 0926-860X, DOI: doi:10.1016/j.apcata.2013.03.033 * |
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