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CN-121974875-A - Method for preparing 2, 5-diformylfuran by catalyzing fructose with ionic liquid and vanadium complex

CN121974875ACN 121974875 ACN121974875 ACN 121974875ACN-121974875-A

Abstract

The invention provides a method for preparing 2, 5-diformylfuran by catalyzing fructose with ionic liquid and vanadium complex, which comprises the steps of taking fructose as a raw material, taking ionic liquid as a reaction solvent and a catalyst for dehydration reaction to obtain 5-hydroxymethylfurfural, adding a V/HCP-AQ catalyst, and carrying out oxidation reaction on the 5-hydroxymethylfurfural in an oxygen atmosphere to obtain the 2, 5-diformylfuran. According to the invention, ionic liquid is adopted to replace DMSO as a solvent for dehydration and oxidation of fructose, ethyl acetate is added into a reaction system after the reaction is finished for extraction, so that the product 2, 5-diformylfuran can be obtained, and the problem that the product in the 2, 5-diformylfuran is difficult to separate by a fructose one-pot method under a traditional catalytic system is solved.

Inventors

  • LI MEICHAO
  • ZHANG PEIPENG
  • WANG BI
  • Xia Jiehao
  • SHEN ZHENLU

Assignees

  • 浙江工业大学

Dates

Publication Date
20260505
Application Date
20260122

Claims (10)

  1. 1. The method for preparing 2, 5-diformylfuran by catalyzing fructose with ionic liquid and vanadium complex is characterized in that fructose is used as a raw material, the ionic liquid is used as a reaction solvent and a catalyst for dehydration reaction to obtain 5-hydroxymethylfurfural, then a V/HCP-AQ catalyst is added, and the 5-hydroxymethylfurfural is subjected to oxidation reaction in an oxygen atmosphere to obtain 2, 5-diformylfuran.
  2. 2. The method of claim 1, wherein the V/HCP-AQ catalyst is prepared by a process comprising the steps of: (1) Dispersing 2-hydroxy-N- (quinoline-8-yl) benzamide, p-dichlorobenzene and anhydrous ferric trichloride in an organic solvent for reaction in a nitrogen atmosphere, carrying out solid-liquid separation, washing the solid, and drying to obtain a macromolecular ligand HCP-AQ; (2) Dissolving vanadyl sulfate and sodium propionate in methanol, adding macromolecular ligand HCP-AQ for reaction, separating solid from liquid, washing solid, and drying to obtain the V/HCP-AQ catalyst.
  3. 3. The method of claim 2, wherein in the step (1), the molar ratio of 2-hydroxy-N- (quinolin-8-yl) benzamide to p-dichlorobenzene to anhydrous ferric trichloride is 1 (1-3): 2-5.
  4. 4. The method according to claim 2, wherein in the step (1), the organic solvent is selected from one or more of toluene, methanol, ethyl acetate, ethanol and dichloroethane, the reaction temperature is 50-120 ℃, and the reaction time is 10-30 hours.
  5. 5. The method according to claim 2, wherein in the step (2), the mass ratio of the macromolecular ligand HCP-AQ to vanadyl sulfate to sodium propionate is 1 (1-3), the reaction temperature is 40-100 ℃, and the reaction time is 10-30 h.
  6. 6. The method according to claim 1, wherein the ionic liquid is one selected from the group consisting of 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium bisulfate, 1-butyl-3-methylimidazolium triflate, 1-butyl-3-methylimidazolium bromide and 1-butyl-3-methylimidazolium chloride.
  7. 7. The method of claim 1, wherein the mass ratio of fructose to ionic liquid is 1 (2-7).
  8. 8. The method according to claim 1, wherein the dehydration reaction temperature is 100-140 ℃ and the dehydration reaction time is 10 min-1 h.
  9. 9. The method of claim 1, wherein the mass ratio of the catalyst V/HCP-AQ to fructose is 1 (2-9).
  10. 10. The method of claim 1, wherein the oxidation reaction temperature is 100-140 ℃ and the reaction time is 10-20 hours.

Description

Method for preparing 2, 5-diformylfuran by catalyzing fructose with ionic liquid and vanadium complex Technical Field The invention relates to the technical fields of catalyst application and organic synthesis, in particular to a method for preparing 2, 5-diformylfuran by catalyzing fructose by utilizing ionic liquid and vanadium complex. Background With the excessive consumption of fossil resources and the increasing rise in energy and environmental problems, the use of renewable biomass resources to produce high value-added chemicals has become an important direction in the sustainable chemical industry. The 2, 5-diformylfuran as an important biomass-based platform compound has wide application prospect in the fields of adhesives, foam materials, drug synthesis, novel polymer material monomers and the like. Currently, the synthesis of 2, 5-diformylfuran is largely dependent on the oxidation of its precursor 5-hydroxymethylfurfural. However, 5-hydroxymethyl furfural is active in chemical property, and is easy to decompose or polymerize under the conditions of acid, alkali, light and oxygen, so that the stability is poor, the separation and purification are difficult, and the production cost is high. Therefore, development of a technology for efficiently preparing 2, 5-diformylfuran from a carbohydrate in a direct one-pot process has become a research hotspot in this field. The prior studies show that the one-pot synthesis of 2, 5-diformylfuran from carbohydrates (if sugar, glucose, etc.) mainly adopts two types of catalytic strategies (1) a combined catalytic system, namely, a dehydration catalyst (such as solid acid) and an oxidation catalyst (such as V-base, mn-base and Ru-base catalysts) are used step by step or simultaneously, and dehydration and oxidation of the carbohydrates are realized in a single reactor. (2) The double-function catalyst constructs an acid site (responsible for dehydration) and an oxidation active site (responsible for oxidation) on the same catalyst at the same time, thereby simplifying the reaction flow. Although many researches exist, the prior art still has the outstanding problems that the reaction conditions are harsh, most reaction systems need to use environment-unfriendly solvent DMSO, products are difficult to separate from the reaction systems, the catalyst is difficult to design and recover, the homogeneous catalyst is difficult to recover and easy to cause metal pollution, the heterogeneous catalyst is easy to deactivate due to carbon deposition, the synergistic action mechanism of acidity and oxidation sites in the bifunctional catalyst is not clear, and the activity and stability are difficult to be compatible. Disclosure of Invention In view of the above-mentioned drawbacks of the prior art, the present invention aims to provide a method for preparing 2, 5-diformylfuran by using ionic liquid and vanadium complex to catalyze fructose, which is used for solving the problems that the existing synthesis method of 2, 5-diformylfuran has harsh reaction conditions, needs to use an environment-friendly solvent, is difficult to separate products, is difficult to recover and inactivate a catalyst, is easy to cause metal pollution, and is difficult to compromise the activity and stability of the catalyst. In order to achieve the above and other related objects, the present invention provides a method for preparing 2, 5-diformylfuran by catalyzing fructose with ionic liquid and vanadium complex, which is characterized in that fructose is used as raw material, ionic liquid is used as reaction solvent and catalyst to carry out dehydration reaction to obtain 5-hydroxymethylfurfural, then V/HCP-AQ catalyst is added, and oxidation reaction is carried out on 5-hydroxymethylfurfural under oxygen atmosphere to obtain 2, 5-diformylfuran. The catalytic system of the invention can realize the high-efficiency synthesis of 2, 5-diformylfuran from fructose by a one-pot two-step method. Preferably, the V/HCP-AQ catalyst is prepared by a process comprising the steps of: (1) Dispersing 2-hydroxy-N- (quinoline-8-yl) benzamide, p-dichlorobenzene and anhydrous ferric trichloride in an organic solvent for reaction in a nitrogen atmosphere, carrying out solid-liquid separation, washing the solid, and drying to obtain a macromolecular ligand HCP-AQ; (2) Dissolving vanadyl sulfate and sodium propionate in methanol, adding macromolecular ligand HCP-AQ for reaction, separating solid from liquid, washing solid, and drying to obtain the V/HCP-AQ catalyst. The preparation route of the V/HCP-AQ catalyst is shown below: 。 more preferably, the V/HCP-AQ catalyst is prepared by a process comprising the steps of: (1) Adding 2-hydroxy-N- (quinoline-8-yl) benzamide, p-dichlorobenzene, anhydrous ferric trichloride and an organic solvent into a reaction bottle, and reacting at a certain temperature in a nitrogen atmosphere; (2) Dissolving vanadyl sulfate and sodium propionate in methanol, adding macromolecular liga