CN106967019B - Method for preparing 2, 5-diformylfuran - Google Patents
Method for preparing 2, 5-diformylfuran Download PDFInfo
- Publication number
- CN106967019B CN106967019B CN201710317239.5A CN201710317239A CN106967019B CN 106967019 B CN106967019 B CN 106967019B CN 201710317239 A CN201710317239 A CN 201710317239A CN 106967019 B CN106967019 B CN 106967019B
- Authority
- CN
- China
- Prior art keywords
- diformylfuran
- hydroxymethylfurfural
- phosphorus oxide
- catalyst
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C07D307/38—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A method for preparing 2, 5-diformylfuran comprises the steps of catalyzing high-selectivity oxidation of 5-hydroxymethylfurfural by taking a biomass-based platform compound 5-hydroxymethylfurfural as a raw material and vanadium-phosphorus oxide or copper, manganese and bismuth-doped vanadium-phosphorus oxide as a catalyst in an organic solvent system to obtain a product 2, 5-diformylfuran. The invention has the advantages that: the used catalyst has high activity, simple preparation and low cost compared with other noble metal catalysts and the like; the method has higher selectivity for preparing 2, 5-diformylfuran by oxidizing 5-hydroxymethylfurfural; the reaction system is carried out under normal pressure, the condition is mild, the catalytic oxidation efficiency is high, the byproducts are few, the post-treatment is convenient, and the method has important guiding significance for realizing the industrial large-scale production of the 2, 5-diformylfuran.
Description
Technical Field
The invention belongs to the field of biomass energy chemical industry, and relates to a method for preparing 2, 5-diformylfuran by catalyzing 5-hydroxymethylfurfural with vanadium phosphorus oxide.
Background
The production of novel materials and fine chemical raw materials with high added values by utilizing abundant and renewable biomass resources is one of important ways for solving the problems of future energy and environment of human beings, and has very important strategic significance for realizing the replacement of fossil resources. Almost all basic organic chemical raw materials can be produced by taking biomass as a source, and a plurality of products show good economy.
The 5-hydroxymethylfurfural is a main product of biomass carbohydrate deoxidation, and is an important platform compound for realizing the comprehensive utilization of biomass resources. 5-hydroxymethylfurfural is also known as 5-hydroxymethyl-2-furfural or 5-hydroxymethyl-2-furfural, abbreviated in English to HMF. The chemical structure of 5-hydroxymethylfurfural contains aldehyde groups, hydroxyl groups and furan rings, which are very chemically active functional groups, since various fine chemicals can be derived from 5-hydroxymethylfurfural.
Among numerous chemicals derived from 5-hydroxymethylfurfural, 2, 5-diformylfuran is the most important organic intermediate with wide application prospects. 2, 5-diformylfuran has multiple purposes, such as the capability of generating polymeric Schiff base containing furan groups by condensing the 2, 5-diformylfuran with a certain amount of diamine or synthesizing high-end drugs, macrocyclic ligands, pesticide antifungal agents, fluorescent materials and the like; because the molecule has a symmetrical and unsaturated structure, the compound can be used as a monomer for synthesizing various polymer materials such as 2, 5-diformylfuran-urea resin and other novel polymer materials. The above-mentioned furan-based polymeric materials have gained increasing attention in recent years due to their particular properties. The development of various furan-based materials with potential application values is rapidly developed, and a series of chemical products capable of replacing petroleum-based materials are formed.
At present, the 5-hydroxymethylfurfural is generally prepared into 2, 5-diformylfuran by catalytic oxidation through a catalyst. According to literature reports, catalysts used for preparing 2, 5-diformylfuran from 5-hydroxymethylfurfural mainly comprise noble metals of Au, Pt and Pd and supported catalysts thereof, and carriers such as activated carbon, hydrotalcite, metal oxides, carbon nanotubes and the like are generally used. Other metals or metal oxides such as Cu, Mn, Co, etc. have also been reported. It is to be noted that these catalysts generally use oxygen as oxidant, and in order to obtain a good selectivity, the reaction needs to be carried out at high pressure. In the previous research, the selectivity of 2, 5-diformylfuran obtained by using a supported noble metal Ru/C as a catalyst and toluene as a solvent at 110 ℃ under the oxygen pressure of 2.0 MPa reaches 95%. Compared with Ru/C, the supported noble metal Pt/C, Pd/C, Rh/C, Au/C has less than 75% selectivity of 2, 5-diformylfuran under the same conditions (Journal of Catalysis, 2013, 301: 83-91). VOPO for use by someone4·2H2The selectivity of the obtained 2, 5-diformylfuran can reach 100 percent by O catalytic oxidation, but the conversion rate of the raw material is very low and is only less than 10 percent, and the oxygen pressure required by the reaction is 0.1 MPa (Applied Catalysis A: General, 2005, 289: 197-204); also, C has been studied14VOPO4And C14VOHPO4As a catalyst, under the optimal conditions, the conversion rate of 5-hydroxymethylfurfural is 99%, and the selectivity of 2, 5-diformylfuran is 83%, but the pressure of oxygen required for the reaction is 0.1 MPa (RSC Advances, 2013, 3: 9942-9948).
As a monomer and a precursor material with potential application value, 2, 5-diformylfuran has wide application, but the industrial scale application of the 2, 5-diformylfuran is difficult to realize at present, mainly because the 2, 5-diformylfuran product which is industrially available at present has too high price and too low yield, the preparation route is immature, and the preparation method is still in the research stage. Most of the existing preparation methods have the defects of harsh reaction conditions, high catalyst cost, poor reaction selectivity, difficult product separation and the like.
Disclosure of Invention
The invention aims to provide a method for preparing 2, 5-diformylfuran, which aims at solving the problems in the prior art, adopts vanadium phosphorus oxide to catalyze 5-hydroxymethylfurfural to selectively oxidize to prepare the 2, 5-diformylfuran, and has the advantages of mild reaction conditions, simple process, good catalytic effect, high product selectivity and low production cost.
The technical scheme adopted for solving the technical problem is that the method for preparing the 2, 5-diformylfuran takes 5-hydroxymethylfurfural as a reaction substrate, takes vanadium-phosphorus oxide or vanadium-phosphorus oxide doped with copper, manganese and bismuth as a catalyst, and selectively oxidizes the 5-hydroxymethylfurfural to obtain the 2, 5-diformylfuran.
The specific method comprises the following steps: adding 5-hydroxymethylfurfural and an organic solvent into a reactor to form a mixed solution; and adding a catalyst and an oxidant into the mixed solution, and reacting for more than 3 hours (preferably 6-11 hours) under the stirring condition that the temperature is 110-150 ℃ and the rotating speed is 10-30 r/s to obtain the product 2, 5-diformylfuran.
The reaction time, in principle, is longer, the higher the conversion and selectivity, but when the time exceeds 11 hours, the improvement effect is limited, and therefore, the efficiency is lowered by the longer time.
The catalyst is vanadium phosphorus oxide, and more preferably vanadium phosphorus oxide doped with copper, manganese and bismuth.
The main raw material of the vanadium phosphorus oxide is V2O5And H3PO4. The copper, manganese and bismuth doped vanadium-phosphorus oxide is vanadium-phosphorus oxide, and at least one of copper salt, manganese salt and bismuth salt is added; more preferably, Cu (NO) is added3)2·3H2O、Mn(NO3)2·4H2O、Bi(NO3)3·5H2At least one of O.
Referring to the prior art, the preparation method of the vanadium-phosphorus oxide or the vanadium-phosphorus oxide doped with copper, manganese and bismuth can specifically adopt the following method:
the vanadium phosphorus oxide can be prepared by the following method: 1.18gV2O5And 10.46g of 85% by mass H3PO4Dissolving in 27.5 mL of water, refluxing at 100 ℃ for 16 hours, filtering, vacuum drying at 30 ℃ for 4 hours, washing the obtained solid with acetone for 3 times, and drying in static air at room temperature for 2 days to obtain the product. (see prior art, RSC Advances, 2013, 3: 9942-.
The bismuth-doped vanadium phosphorus oxide can be prepared by the following method:
weighing 3.0 g V2O5And 0.16g Bi (NO)3)3·5H2O, adding 0.257g of dimethyl sulfoxide (DMSO), 24mL of isobutanol and 6mL of benzyl alcohol in sequence, refluxing at 110 ℃ for 16H, and adding 2.0 g of 85 mass% H dropwise3PO4The reaction was continued for 10 h. After suction filtration, washing with isobutanol for 3 times, and drying in static air at room temperature for 2 days to obtain the product. (see "one-step preparation of nanometer layered vanadium phosphorus oxide catalyst, Von Jingong, Lichunfu, petrochemical, 2010, vol 39, No. 11, page 1211, left column 1.2)
The preparation method of the vanadium-phosphorus oxide doped with copper and manganese is the same as that of the vanadium-phosphorus oxide doped with bismuth. With the difference that Cu (NO) is used separately3)2·3H2O、Mn(NO3)2·4H2O instead of Bi (NO)3)3·5H2O。
The mass ratio of the catalyst to the 5-hydroxymethylfurfural is 0.45-0.87: 1.
the oxidant is at least one of tert-butyl hydroperoxide and hydrogen peroxide. The oxidizing agent may be in the form of a solution. The solution is preferably a solution having a mass concentration of 10% or more, more preferably a tert-butyl hydroperoxide having a mass concentration of 65% or a hydroperoxide having a mass concentration of 30%. The molar ratio of the effective components in the added oxidant to the 5-hydroxymethylfurfural is 1.00-1.32: 1.
Research shows that the effect of selecting tert-butyl hydroperoxide as the catalyst is better.
The organic solvent is at least one of benzene, toluene, dimethyl sulfoxide, acetonitrile and tetrahydrofuran.
Studies have shown that the best results are obtained with dimethyl sulfoxide.
The invention has the advantages that the preparation of the used catalyst is simple and easy to operate, and the invention is environment-friendly. Vanadium phosphorus oxide or copper, manganese and bismuth doped vanadium phosphorus oxide is used as a catalyst, high temperature and high pressure are not needed, the reaction is carried out under normal pressure, the conditions are very mild, the product selectivity is high, and the catalyst is easy to recover. Can efficiently and selectively catalyze 5-hydroxymethylfurfural to selectively oxidize and prepare 2, 5-diformylfuran, and has obvious technical and economic effects and good application prospect.
The invention has the advantages that: the used catalyst has high activity, simple preparation and low cost compared with other noble metal catalysts and the like; the method has higher selectivity for preparing 2, 5-diformylfuran by oxidizing 5-hydroxymethylfurfural; the reaction system is carried out under normal pressure, the condition is mild, the catalytic oxidation efficiency is high, the byproducts are few, the post-treatment is convenient, and the method has important guiding significance for realizing the industrial large-scale production of the 2, 5-diformylfuran.
Detailed Description
The present invention is further described below by way of examples, but the embodiments of the present invention are not limited thereto. The following description is only exemplary of the invention, and any person skilled in the art may make modifications to the disclosed embodiments by using equivalent variations. Any simple modification or equivalent changes made to the following embodiments according to the technical essence of the present invention, without departing from the technical spirit of the present invention, fall within the scope of the present invention. Unless otherwise specified, the experimental procedures in the following examples are all conventional.
The preparation method of the catalyst in each example:
referring to the prior art, the preparation method of the vanadium-phosphorus oxide or the vanadium-phosphorus oxide doped with copper, manganese and bismuth can specifically adopt the following method:
the vanadium phosphorus oxide can be prepared by the following method: 1.18gV2O5And 10.46g of 85% by mass H3PO4Dissolving in 27.5 mL of water, refluxing at 100 ℃ for 16 hours, filtering, vacuum drying at 30 ℃ for 4 hours, washing the obtained solid with acetone for 3 times, and drying in static air at room temperature for 2 days to obtain the product. (see prior art, RSC Advances, 2013, 3: 9942-.
The bismuth-doped vanadium phosphorus oxide can be prepared by the following method:
weighing 3.0 g V2O5And 0.16g Bi (NO)3)3·5H2O, adding 0.257g of dimethyl sulfoxide (DMSO), 24mL of isobutanol and 6mL of benzyl alcohol in sequence, refluxing at 110 ℃ for 16H, and adding 2.0 g of 85 mass% H dropwise3PO4The reaction was continued for 10 h. After suction filtration, washing with isobutanol for 3 times, and drying in static air at room temperature for 2 days to obtain the product. (see "one-step preparation of nanometer layered vanadium phosphorus oxide catalyst, Von Jingong, Lichunfu, petrochemical, 2010, vol 39, No. 11, page 1211, left column 1.2)
The preparation method of the vanadium-phosphorus oxide doped with copper and manganese is the same as that of the vanadium-phosphorus oxide doped with bismuth. With the difference that Cu (NO) is used separately3)2·3H2O、Mn(NO3)2·4H2O instead of Bi (NO)3)3·5H2O。
Example 1: 1.30 g of 5-hydroxymethylfurfural (0.0103 mol) is dissolved in 10 mL of dimethyl sulfoxide, 1.0 g of vanadium phosphorus oxide and 1.48 g of tert-butyl hydroperoxide (0.0107 mol) with the mass concentration of 65% are added, and the mixture is reacted for 3 hours at the temperature of 110 ℃ and the stirring speed of 20 r/s to prepare the 2, 5-diformylfuran.
The conversion rate of 5-hydroxymethylfurfural was 54.5% and the selectivity of 2, 5-diformylfuran was 98.0% as a result of analysis by high performance liquid chromatography.
The test conditions of the Agilent 1100 high performance liquid chromatograph are as follows: the chromatographic column is a C18 analytical column (250X 4.6mm), the UV detector is used for detecting the content of 5-hydroxymethylfurfural and 2, 5-diformylfuran in the sample by an external standard method, the detection wavelength is 283 nm, the mobile phase is acetonitrile and 0.1 wt.% acetic acid (the volume ratio is 10: 90), the flow rate is 0.5 mL/min, the column temperature is 30 ℃.
Example 2: dissolving 1.42 g of 5-hydroxymethylfurfural (0.0113 mol) in 10 mL of dimethyl sulfoxide, adding 0.95 g of vanadium-phosphorus oxide and 1.62 g of tert-butyl hydroperoxide (0.0117 mol) with the mass concentration of 65%, and reacting for 11h at the temperature of 120 ℃ and the stirring speed of 30 r/s to prepare the 2, 5-diformylfuran. The conversion rate of 5-hydroxymethylfurfural was 96.4% and the selectivity of 2, 5-diformylfuran was 85.2% as a result of analysis by high performance liquid chromatography.
Example 3: 1.33 g of 5-hydroxymethylfurfural (0.0106 mol) is dissolved in 10 mL of dimethyl sulfoxide, 0.96 g of vanadium phosphorus oxide and 1.52 g of tert-butyl hydroperoxide (0.0110 mol) with the mass concentration of 65% are added, and the mixture is reacted for 11 hours at the temperature of 110 ℃ and the stirring speed of 20 r/s to prepare the 2, 5-diformylfuran. The conversion rate of 5-hydroxymethylfurfural was 96.8% and the selectivity of 2, 5-diformylfuran was 84.2% as a result of analysis by high performance liquid chromatography.
Example 4: 1.85 g of 5-hydroxymethylfurfural (0.0147 mol) was dissolved in 10 mL of dimethyl sulfoxide, and 1.55g of vanadium phosphorus oxide and 2.11 g of 65% by mass tert-butyl hydroperoxide (0.0152 mol) were added thereto to carry out a reaction at a temperature of 110 ℃ and a stirring rate of 20 rpm for 9 hours, thereby obtaining 2, 5-diformylfuran. The conversion rate of 5-hydroxymethylfurfural was 97.4% and the selectivity of 2, 5-diformylfuran was 84.9% as a result of analysis by high performance liquid chromatography.
Example 5: 2.10 g of 5-hydroxymethylfurfural (0.0167 mol) was dissolved in 10 mL of dimethyl sulfoxide, and 1.01 g of vanadium phosphorus oxide and 2.4g of 65% by mass tert-butyl hydroperoxide (0.0173 mol) were added to the solution to react at 130 ℃ and a stirring rate of 30 rpm for 5 hours to obtain 2, 5-diformylfuran. The conversion rate of 5-hydroxymethylfurfural was 88.2% and the selectivity of 2, 5-diformylfuran was 87.0% as a result of analysis by high performance liquid chromatography.
Example 6: 1.97 g of 5-hydroxymethylfurfural (0.0156 mol) is dissolved in 10 mL of dimethyl sulfoxide, 1.00 g of vanadium phosphorus oxide and 2.25 g of tert-butyl hydroperoxide (0.0162 mol) with the mass concentration of 65% are added, and the mixture is reacted for 3 hours at the temperature of 140 ℃ and the stirring speed of 20 r/s to prepare 2, 5-diformylfuran. The conversion rate of 5-hydroxymethylfurfural was 82.0% and the selectivity of 2, 5-diformylfuran was 78.4% as a result of analysis by high performance liquid chromatography.
Example 7: 2.05 g of 5-hydroxymethylfurfural (0.0163 mol) is dissolved in 10 mL of dimethyl sulfoxide, 1.07 g of copper-doped vanadium phosphorus oxide and 2.34 g of tert-butyl hydroperoxide (0.0169 mol) with the mass concentration of 65% are added, and the mixture is reacted for 9 hours at the temperature of 130 ℃ and the stirring speed of 20 r/s to prepare 2, 5-diformylfuran. The conversion rate of 5-hydroxymethylfurfural was 99.5% and the selectivity of 2, 5-diformylfuran was 86.9% as a result of analysis by high performance liquid chromatography.
Example 8: 2.60 g of 5-hydroxymethylfurfural (0.0206 mol) is dissolved in 10 mL of toluene, 1.4 g of vanadium phosphorus oxide and 2.97 g of tert-butyl hydroperoxide (0.0214 mol) with the mass concentration of 65% are added, and the mixture is reacted for 3 hours at the temperature of 110 ℃ and the stirring speed of 30 r/s to obtain 2, 5-diformylfuran. The conversion rate of 5-hydroxymethylfurfural was 46.0% and the selectivity of 2, 5-diformylfuran was 81.9% as a result of analysis by high performance liquid chromatography.
Example 9: dissolving 1.43 g of 5-hydroxymethylfurfural (0.0113 mol) in 10 mL of acetonitrile, adding 0.95 g of vanadium phosphorus oxide and 1.63 g of tert-butyl hydroperoxide (0.0118 mol) with the mass concentration of 65%, and reacting for 3 h at the temperature of 110 ℃ and the stirring speed of 20 r/s to prepare the 2, 5-diformylfuran. The conversion rate of 5-hydroxymethylfurfural was 64.6% and the selectivity of 2, 5-diformylfuran was 67.5% as a result of analysis by high performance liquid chromatography.
Example 10: 1.36 g of 5-hydroxymethylfurfural (0.0108 mol) is dissolved in 10 mL of acetonitrile, 1.18g of vanadium phosphorus oxide and 1.55g of tert-butyl hydroperoxide (0.0112 mol) with the mass concentration of 65% are added, and the mixture is reacted for 3 hours at the temperature of 120 ℃ and the stirring speed of 20 r/s to prepare 2,5 diformylfuran. The conversion rate of 5-hydroxymethylfurfural was 59.6% and the selectivity of 2, 5-diformylfuran was 76.3% as a result of analysis by high performance liquid chromatography.
Example 11: 1.72 g of 5-hydroxymethylfurfural (0.0136 mol) was dissolved in 10 mL of dimethyl sulfoxide, and 1.04 g of bismuth-doped vanadium phosphorus oxide and 1.96 g of 65% by mass tert-butyl hydroperoxide (0.0141 mol) were added to the solution to react at 130 ℃ and a stirring rate of 20 rpm for 9 hours to obtain 2, 5-diformylfuran. The conversion rate of 5-hydroxymethylfurfural was 96.9% and the selectivity of 2, 5-diformylfuran was 57.0% as a result of analysis by high performance liquid chromatography.
Example 12: 1.99 g of 5-hydroxymethylfurfural (0.0158 mol) is dissolved in 10 mL of dimethyl sulfoxide, 0.98g of vanadium phosphorus oxide and 2.27g of hydrogen peroxide (0.02 mol) with the mass concentration of 30% are added, and the mixture is reacted for 9 hours at the temperature of 130 ℃ and the stirring speed of 20 r/s to prepare 2, 5-diformylfuran. The conversion rate of 5-hydroxymethylfurfural was 67.2% and the selectivity of 2, 5-diformylfuran was 39.7% as a result of analysis by high performance liquid chromatography.
Example 13: dissolving 1.20g of 5-hydroxymethylfurfural (0.0095 mol) in 10 mL of dimethyl sulfoxide, adding 0.8 g of vanadium phosphorus oxide and 1.58 g of tert-butyl hydroperoxide (0.0114 mol) with the mass concentration of 65%, and reacting for 11h at the temperature of 120 ℃ and the stirring speed of 20 r/s to obtain the 2, 5-diformylfuran. The conversion rate of 5-hydroxymethylfurfural was 90.0% and the selectivity of 2, 5-diformylfuran was 81.6% as a result of analysis by high performance liquid chromatography.
Example 14: dissolving 1.20g of 5-hydroxymethylfurfural (0.0095 mol) in 10 mL of dimethyl sulfoxide, adding 0.72 g of vanadium-phosphorus oxide and 3.23g of hydrogen peroxide (0.0095 mol) with the mass concentration of 10%, and reacting for 5 hours at the temperature of 130 ℃ and the stirring speed of 20 r/s to obtain the 2, 5-diformylfuran. The conversion rate of 5-hydroxymethylfurfural was 55.6% and the selectivity of 2, 5-diformylfuran was 83.4% as a result of analysis by high performance liquid chromatography.
Example 15: dissolving 1.20g of 5-hydroxymethylfurfural (0.0095 mol) in 10 mL of dimethyl sulfoxide, adding 0.58 g of vanadium phosphorus oxide and 4.28g of tert-butyl hydroperoxide (0.0095 mol) with the mass concentration of 20%, and reacting for 5 hours at the temperature of 120 ℃ and the stirring speed of 20 r/s to obtain the 2, 5-diformylfuran. The conversion rate of 5-hydroxymethylfurfural was 74.1% and the selectivity of 2, 5-diformylfuran was 83.7% as a result of analysis by high performance liquid chromatography.
Example 16: dissolving 1.20g of 5-hydroxymethylfurfural (0.0095 mol) in 10 mL of dimethyl sulfoxide, adding 0.58 g of vanadium phosphorus oxide and 8.56g of tert-butyl hydroperoxide (0.0095 mol) with the mass concentration of 10%, and reacting for 5 hours at the temperature of 130 ℃ and the stirring speed of 20 r/s to obtain the 2, 5-diformylfuran. The conversion rate of 5-hydroxymethylfurfural was 65.3% and the selectivity of 2, 5-diformylfuran was 80.7% as a result of analysis by high performance liquid chromatography.
Claims (5)
1. A method for preparing 2, 5-diformylfuran is characterized in that 5-hydroxymethylfurfural is used as a reaction substrate, vanadium phosphorus oxide is used as a catalyst, and selective oxidation is carried out on the 5-hydroxymethylfurfural to obtain 2, 5-diformylfuran;
the method specifically comprises the following steps:
adding 5-hydroxymethylfurfural and an organic solvent into a reactor to form a mixed solution; adding a catalyst and an oxidant into the mixed solution, and reacting for more than 3 hours under the stirring conditions that the temperature is 110-150 ℃ and the rotating speed is 10-30 r/s to obtain a product 2, 5-diformylfuran;
the organic solvent is at least one of benzene, toluene, dimethyl sulfoxide, acetonitrile and tetrahydrofuran;
the catalyst is vanadium phosphorus oxide doped with copper, manganese and bismuth;
the oxidant is at least one of tert-butyl hydroperoxide and hydrogen peroxide.
2. The method for preparing 2, 5-diformylfuran according to claim 1, wherein the reaction time is 6-11 h.
3. The method for preparing 2, 5-diformylfuran according to claim 1, wherein the mass ratio of the catalyst to 5-hydroxymethylfurfural is 0.45-0.87: 1.
4. the method for preparing 2, 5-diformylfuran according to claim 1, wherein the oxidizing agent is a solution having a mass concentration of 10% or more.
5. The method of claim 1, wherein the molar ratio of the active ingredient to 5-hydroxymethylfurfural in the oxidant is 1.00-1.32: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710317239.5A CN106967019B (en) | 2017-05-08 | 2017-05-08 | Method for preparing 2, 5-diformylfuran |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710317239.5A CN106967019B (en) | 2017-05-08 | 2017-05-08 | Method for preparing 2, 5-diformylfuran |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106967019A CN106967019A (en) | 2017-07-21 |
| CN106967019B true CN106967019B (en) | 2020-01-24 |
Family
ID=59331730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710317239.5A Active CN106967019B (en) | 2017-05-08 | 2017-05-08 | Method for preparing 2, 5-diformylfuran |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106967019B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109438399B (en) * | 2018-12-27 | 2022-10-11 | 南京林业大学 | Method for preparing 2,5-diformylfuran by selectively oxidizing 5-hydroxymethylfurfural |
| CN116510742A (en) * | 2023-04-06 | 2023-08-01 | 济南大学 | Preparation method and application of molybdenum-vanadium-oxygen cluster modified carbon-based ferric manganate composite catalyst |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619050B (en) * | 2008-07-04 | 2011-06-22 | 中国科学院大连化学物理研究所 | Method for preparing 2,5-diformyl furan by catalyzing 5-hydroxy methyl furfural |
| CN102731448B (en) * | 2012-06-27 | 2014-08-13 | 北京大学 | Preparation method for furan-2,5-dicarbaldehyde |
| CN104275210A (en) * | 2014-10-14 | 2015-01-14 | 天津理工大学 | Catalytic system for preparing 2, 5-furan dicarboxaldehyde by using 5-hydroxymethyl furfural and application thereof |
| CN104529957B (en) * | 2014-12-26 | 2016-04-13 | 中国科学技术大学先进技术研究院 | A kind of preparation method of FDCA |
-
2017
- 2017-05-08 CN CN201710317239.5A patent/CN106967019B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106967019A (en) | 2017-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Metal-free and solvent-free oxidative coupling of amines to imines with mesoporous carbon from macrocyclic compounds | |
| CN109603819B (en) | Graphene-loaded PdRu bimetallic catalyst and preparation method and application thereof | |
| Prati et al. | From renewable to fine chemicals through selective oxidation: the case of glycerol | |
| Bystroem et al. | Palladium-catalyzed allylic oxidation of cyclohexenes using molecular oxygen as oxidant | |
| CN102206147B (en) | Method for oxidizing cyclohexane | |
| CN110102350A (en) | Catalyst and its preparation method and application for oxidative synthesis 2,5- furandicarboxylic acid | |
| Long et al. | 4, 4′-Bipyridine-modified molybdovanadophosphoric acid: A reusable heterogeneous catalyst for direct hydroxylation of benzene with O2 | |
| CN109503524B (en) | Method for preparing lactone by catalytic oxidation of cycloalkanol/cycloalkanone | |
| Albonetti et al. | Homogeneous, heterogeneous and nanocatalysis | |
| CN106967019B (en) | Method for preparing 2, 5-diformylfuran | |
| CN108821952B (en) | Method for cracking lignin by heterogeneous cobalt catalytic oxidation | |
| CN109912549A (en) | A kind of 5 hydroxymethyl furfural selective oxidation prepares the new method of 5-HMFA | |
| CN103864549B (en) | Method for preparing diphenyl ketone compound | |
| CN111195514B (en) | Monoatomic dispersion rhodium-based catalyst, preparation method thereof and application thereof in methane low-temperature oxidation reaction | |
| CN101279911A (en) | Method for preparing glyceric acid directly by dioxygen catalytic oxidation of glycerol | |
| CN113387911A (en) | Method for preparing 2, 5-furan dicarboxaldehyde by photo-catalytic dehydrogenation of 5-hydroxymethyl furfural | |
| CN111187238B (en) | Synthetic method of 2, 5-furandicarboxylic acid | |
| CN106944050A (en) | A kind of catalyst for synthesizing 1,3 propane diols and its preparation method and application | |
| CN108970604B (en) | Molybdenum vanadium niobium-based composite oxide and synthesis method and application thereof | |
| CN113845500B (en) | Method for preparing 5-formyl-2-furancarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural | |
| CN106588819B (en) | A kind of preparation method of highly selective epoxypinane | |
| CN115518653A (en) | Catalyst for efficiently catalyzing ethanol oxidative carbonylation to prepare diethyl carbonate and preparation method thereof | |
| US6881870B2 (en) | Process for producing adamantanol and adamantanone | |
| CN101450324A (en) | Polymer-bound tripe amino-acid schiff base metal copper complexes catalyst and synthesis method thereof | |
| CN114939438A (en) | Method for selective hydrogenation of olefinic unsaturated carbonyl compound and catalyst thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |