CN110437190B - Method for preparing 2, 5-furandicarboxylic acid from 5-hydroxymethylfurfural - Google Patents
Method for preparing 2, 5-furandicarboxylic acid from 5-hydroxymethylfurfural Download PDFInfo
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Abstract
The present application relates to a process for preparing 2, 5-furandicarboxylic acid (FDCA) from 5-hydroxymethylfurfural (5-HMF), comprising: at the temperature of 30-100 ℃, in a mixed solvent of a tertiary alcohol compound and water, a raw material, namely 5-Hydroxymethylfurfural (HMF), reacts in the presence of a TEMPO catalyst, an inorganic acid or solid acid cocatalyst, a nitrite auxiliary agent and an oxidant to be converted into 2, 5-furandicarboxylic acid (FDCA). By utilizing the method, the target product 2, 5-furan dicarboxylic acid (FDCA) can be obtained by converting the raw material 5-hydroxymethyl furfural (5-HMF) under mild conditions with high selectivity and high yield, and the method has a simple process route and huge industrial application prospects.
Description
Technical Field
The invention relates to a preparation method of chemicals, in particular to a method for preparing 2, 5-furan dicarboxylic acid (FDCA) from 5-hydroxymethyl furfural (5-HMF).
Background
The increasing decrease of petroleum resources and global warming requires people to find a green, environmentally friendly and sustainable energy source to reduce the dependence on fossil fuels. 2, 5-furan dicarboxylic acid (FDCA) is taken as a novel polymeric structural monomer and has stable performance per se. The polyethylene furan dicarboxylate (PEF) prepared by FDCA is regarded as an important polyester material for substituting polyethylene terephthalate (PET), and has the advantages of biodegradability, environmental protection and the like. FDCA also plays an important role in pharmacology, and researches show that diethyl furandicarboxylate has a strong anesthetic effect similar to cocaine. The dicalcium furandicarboxylate has an inhibitory effect on the growth of Bacillus megaterium.
In view of the important role and use of furandicarboxylic acid, it is of great interest to study the conversion of carbohydrates, especially HMF, to FDCA. Oxidizing HMF to FDCA uses heterogeneous catalysts that mainly include noble metal catalysts and base metal catalysts. The noble metal catalyst mainly comprises Au-based, pd-based, pt-based and Ru-based catalysts. It was found that Au/CeO2 and Au/TiO2 have higher catalytic activities than Au/C and Au/Fe2O3, and that quantitative FDCA yields can be obtained (Applied Catalysis B: environmental,2015, 163. The use of an alkaline carrier instead of the addition of an inorganic base reduces the use of inorganic acid and base because the reaction requires acid neutralization, which results in a large amount of inorganic salt waste, usually with excess base in the FDCA production process. Yan et al use Pt/PVP catalysts to effect conversion of HMF to FDCA without base addition, but with high catalyst metal loading, poor cyclability, and long reaction times (Journal of Catalysis,2014, 315. The reports of HMF to FDCA using base metal catalysts at present mainly include Fe-POP (Journal of Catalysis,2013, 299. Base metal catalysts have cost advantages, but the reaction conditions are high and the product selectivity is poor. Therefore, the method has important significance for preparing the carboxylic acid product by oxidizing the HMF under mild and alkali-free conditions.
Accordingly, there remains a need in the art for a new process for preparing 2, 5-furandicarboxylic acid (FDCA) from 5-hydroxymethylfurfural (5-HMF) under mild reaction conditions (e.g., normal temperature and pressure) in a simple, low-cost process and with high selectivity and high yield.
Disclosure of Invention
In view of the above, it is an object of the present invention to provide a novel method for preparing 2, 5-furandicarboxylic acid (FDCA) from 5-hydroxymethylfurfural (5-HMF) under mild reaction conditions (e.g., normal temperature and pressure) with a simple low-cost process and with high selectivity and high yield.
The invention provides a method for preparing 2, 5-furandicarboxylic acid from 5-hydroxymethylfurfural, which comprises the following steps: at the temperature of 30-100 ℃, in a mixed solvent of a tertiary alcohol compound and water, the raw material 5-hydroxymethylfurfural reacts in the presence of a TEMPO catalyst, an inorganic acid or solid acid cocatalyst, a nitrite auxiliary agent and an oxidant to be converted into 2, 5-furandicarboxylic acid,
wherein the TEMPO catalyst is one or more selected from catalysts 1-6 having the following structure:
in a preferred embodiment, the inorganic acid or solid acid co-catalyst is one or more selected from the group consisting of: sulfuric acid, hydrochloric acid, hydrobromic acid, nitric acid, phosphoric acid, amberlite-15, phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, and silicomolybdic acid.
In a preferred embodiment, the nitrite based adjuvant is one or more selected from the group consisting of: naNO2 and KNO2.
In a preferred embodiment, the oxidizing agent is one or more selected from the group consisting of: air, oxygen, hydrogen peroxide, peroxide salt and hypohalite; preferably the reaction is carried out in an air or oxygen atmosphere of 0.1 to 2.0 MPa.
In a preferred embodiment, the reaction is carried out at a temperature of 50 to 100 ℃; the reaction is carried out at a temperature of 50 to 70 ℃.
In a preferred embodiment, the reaction time is 1 to 96 hours; preferably the reaction time is 1 to 48h.
In a preferred embodiment, the tertiary alcohol compound is one or more selected from the group consisting of: tert-butanol, 2-methyl-pentan-2-ol, 3-methyl-pentan-3-ol and 2-methyl-butan-2-ol.
In a preferred embodiment, the volume ratio of the tertiary alcohol compound to water in the mixed solvent is 100:1 to 1:1.
In a preferred embodiment, the mass ratio of the TEMPO catalyst to the raw material 5-hydroxymethylfurfural used is 0.01:1 to 1:1.
In a preferred embodiment, the mass ratio of the inorganic acid or solid acid cocatalyst to the raw material 5-hydroxymethylfurfural is 0.01:1 to 5:1.
In a preferred embodiment, the mass ratio of the nitrite auxiliary agent to the raw material 5-hydroxymethylfurfural is 0.01: 1-2: 1.
The invention uses cheap and easily-obtained specific catalyst, cocatalyst and nitrite auxiliary agent, takes 5-hydroxymethylfurfural (5-HMF) as raw material, and obtains 2, 5-furan Dicarbaldehyde (DFF) by catalytic oxidation in a mixed solvent of tertiary alcohol compound and water. The process of the present invention can provide 2, 5-furandicarboxylic acid (FDCA) under extremely mild (e.g., normal temperature and pressure) conditions. The method increases the solubility of the FDCA product in tertiary alcohol solvent, avoids the inactivation of the catalyst, simultaneously uses inorganic acid and solid acid auxiliary agent which can effectively promote the catalytic circulation of TEMPO, obtains products with high selectivity and yield under mild conditions, has simple process and has huge industrial application value.
Detailed Description
The invention provides a method for preparing 2, 5-furandicarboxylic acid from 5-hydroxymethylfurfural, which comprises the following steps: at the temperature of 30-100 ℃, in a mixed solvent of a tertiary alcohol compound and water, a raw material 5-hydroxymethylfurfural reacts in the presence of a TEMPO catalyst, an inorganic acid or solid acid cocatalyst, a nitrite auxiliary agent and an oxidant to be converted into 2, 5-furandicarboxylic acid.
In the process of the invention, the TEMPO catalyst used is one or more selected from the group consisting of catalysts 1 to 6 having the following structure:
such TEMPO catalysts are known in the art and are commercially available, for example catalyst 1 described above may be obtained from ann gill corporation (98% purity). Furthermore, such TEMPO catalysts may sometimes also be present, obtained or used in the following active form (i.e. free radical form), respectively:
TEMPO catalysts are highly effective catalysts for the catalytic oxidation of alcohols to aldehydes, allowing for the oxidation of alcohols under mild conditions, and an exemplary catalytic reaction mechanism is shown below:
in the process of the present invention, preferably, the TEMPO catalyst is used in an amount of 0.01 to 1 times the amount by mass of the raw material 5-hydroxymethylfurfural (i.e., the mass ratio of the two is 0.01:1 to 1: 1). If the amount of the catalyst is too low, the reaction process will be too long and the industrial significance will be impaired; if the amount of the catalyst is too high, the process cost is increased and the industrial significance is also impaired.
In the method of the present invention, in order to catalytically oxidize 5-hydroxymethylfurfural into the target 2, 5-furandicarboxylic acid with high selectivity and high yield, an inorganic acid or a solid acid-based co-catalyst is used. The addition of an inorganic acid or solid acid cocatalyst can not only assist the dehydrating agent to form a nitrogen oxide intermediate, but also facilitate the hydration of the aldehyde group of the intermediate, thereby further promoting the conversion of the aldehyde group to carboxylic acid, which enables the preparation of carboxylic acid to be achieved under mild and acidic conditions.
In the process of the invention, the inorganic acid or solid acid cocatalyst used is one or more selected from: sulfuric acid, hydrochloric acid, hydrobromic acid, nitric acid, phosphoric acid, amberlite-15, phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, and silicomolybdic acid.
In the method of the present invention, the amount of the inorganic acid or solid acid-based co-catalyst is preferably 0.01 to 5 times the amount of the 5-hydroxymethylfurfural in the raw material (i.e., the mass ratio of the inorganic acid or solid acid-based co-catalyst is 0.01:1 to 5: 1). If the amount of inorganic acid or solid acid co-catalyst is too low, the reaction will continue too long and the target acid product will not be obtained; if the amount of the inorganic acid or solid acid-based cocatalyst is too high, the process cost is increased, and the industrial significance is also impaired.
In the process of the present invention, the nitrite type adjuvant used may preferably be NaNO 2 And KNO 2 . The nitrite assistant is used for promoting the circulation circle of TEMPO and realizing the circulation of TEMPO, thereby promoting the generation of oxidation reaction.
In the method of the present invention, the nitrite-based auxiliary is preferably used in an amount of 0.01 to 2 times the mass of the raw material 5-hydroxymethylfurfural (i.e., the mass ratio of the nitrite-based auxiliary to the raw material is 0.01:1 to 2: 1). If the dosage of the nitrite auxiliary agent is too low, the oxidation reaction speed is slowed down; if the dosage of the nitrite type auxiliary agent is too high, the waste salt is discharged more, and the atom economy is poorer.
In the method, the tertiary alcohol solvent not only keeps the high-efficiency solubility of the alcohol solvent to reaction substrates and products, but also can reduce the toxic action to a catalyst TEMPO because the tertiary alcohol solvent is difficult to be further oxidized, and the addition of water is favorable for the generation of aldehyde group hydration reaction and promotes the acquisition of carboxylic acid products. In the present invention, there is no particular limitation on the tertiary alcohol compound, and preferably, the tertiary alcohol compound used may be one or more selected from the group consisting of: tert-butanol, 2-methyl-pentan-2-ol, 3-methyl-pentan-3-ol and 2-methyl-butan-2-ol. More preferably, the volume ratio of the tertiary alcohol compound to water in the mixed solvent is 100:1 to 1:1.
In the method of the present invention, there is no particular limitation on the oxidant used, and preferably, the oxidant used may be one or more selected from the group consisting of: air, oxygen, hydrogen peroxide, peroxide salts and hypohalites. Although in the process of the invention it is mentioned that it is carried out in the presence of an oxidizing agent, in fact, since the process of the invention can be carried out entirely in an air atmosphere, for example in an open reactor, the oxidizing agent mentioned in the invention can also be regarded as being absent to some extent. In other words, the process of the present invention may be carried out in the absence of an oxidizing agent.
In the method of the present invention, preferably, when air or oxygen is used as the oxidizing agent, the reaction may be directly performed under an air or oxygen atmosphere, or may be performed by bubbling oxygen or oxygen into the reaction system, or may be performed under an air or oxygen atmosphere of 0.1 to 2.0MPa (for example, by using a closed reactor).
The process of the invention can be carried out at a temperature of from 30 to 100 ℃, preferably the reaction is carried out at a temperature of from 50 to 100 ℃; more preferably the reaction is carried out at a temperature of 50 to 70 ℃.
In the method of the present invention, the reaction time is not particularly limited, and preferably, the reaction time is 1 to 96 hours; the reaction time is preferably 1 to 48 hours.
The following examples are provided to further illustrate the practice of the present invention. The following description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto.
In the following examples, the raw materials and reagents used, if not specifically indicated, were all available from the national reagents company and used as such without further treatment; the reactor used, schlecer tube, was available from Xinville and high performance liquid chromatography, was available from Shimadzu.
Example 1
In a 10mL Schlenk tube, 126mg of 5-hydroxymethylfurfural (5-HMF), 11 mg of catalyst 1 and 24mg of NaNO were charged 2 Then 60mg of H was added 3 PO 4 0.2mL of water and 2mL of tert-butanol, and heating the water bath to 55 ℃ for reaction for 48h under magnetic stirring (stirring rate of 800 r/min) in an oxygen atmosphere at normal pressure. After the reaction is completed, sampling is carried out to High Performance Liquid Chromatography (HPLC) detection under the stirring state, wherein the detection conditions are as follows: hitachi L2000 HPLC System, alltech C18 column, mobile phase CH 3 OH∶H 2 O = 20: 80; flow rate: 1.0mL/min, column temperature: 30 ℃, detector: DAD, detection wavelength: 264nm. The product, 2, 5-furandicarboxylic acid (FDCA), was determined to be 92.17% yield, 95% selectivity and 99% purity by HPLC.
Example 2
The specific reaction process and detection method were the same as in example 1 except that t-butanol was changed to 3-methyl-pentan-3-ol, and as a result, 2, 5-furandicarboxylic acid (FDCA) was obtained as a main product, and the yield was 85.76%, the selectivity was 96%, and the purity was 99.3%.
Example 3
The specific reaction process and detection method were the same as in example 1 except that t-butanol was changed to t-amyl alcohol, and as a result, 2, 5-furandicarboxylic acid (FDCA) was obtained as a main product with a yield of 80.33%, selectivity of 98%, and purity of 98.6%.
Example 4
The specific reaction process and detection method were the same as in example 1 except that catalyst 1 was changed to catalyst 2, and as a result, 2, 5-furandicarboxylic acid (FDCA) was obtained as a main product in a yield of 85.08%, a selectivity of 95%, and a purity of 99.1%.
Example 5
The specific reaction procedure and detection method were the same as in example 1 except that catalyst 1 was changed to catalyst 3, and as a result, 2, 5-furandicarboxylic acid (FDCA) was obtained as a main product in a yield of 89%, a selectivity of 94%, and a purity of 98%.
Example 6
The specific reaction procedure and detection method were the same as in example 1 except that catalyst 1 was changed to catalyst 5, and as a result, 2, 5-furandicarboxylic acid (FDCA) was obtained as a main product in a yield of 76.76%, a selectivity of 96%, and a purity of 98.7%.
Example 7
The specific reaction procedure and detection method were the same as in example 1 except that phosphoric acid was changed to hydrochloric acid, and as a result, 2, 5-furandicarboxylic acid (FDCA) was obtained as a main product with a yield of 77.59%, selectivity of 96%, and purity of 99.7%.
Example 8
The specific reaction procedure and detection method were the same as in example 1 except that phosphoric acid was changed to sulfuric acid, and as a result, 2, 5-furandicarboxylic acid (FDCA) was obtained as a main product with a yield of 79.70%, selectivity of 97%, and purity of 98.6%.
Example 9
The specific reaction process and detection method were the same as in example 1 except that phosphoric acid was changed to nitric acid, and as a result, 2, 5-furandicarboxylic acid (FDCA) was obtained as a main product, and the yield was 80.47%, the selectivity was 93%, and the purity was 97.7%.
Example 10
The specific reaction process and detection method were the same as in example 1 except that phosphoric acid was changed to phosphotungstic acid, and as a result, 2, 5-furandicarboxylic acid (FDCA) was obtained as a main product with a yield of 80%, a selectivity of 94%, and a purity of 97.7%.
Example 11
The specific reaction procedure and detection method were the same as in example 1 except that phosphoric acid was changed to phosphomolybdic acid. As a result, 2, 5-furandicarboxylic acid (FDCA) was obtained as a main product, and the yield was 85.09%, the selectivity was 95%, and the purity thereof was 98.3%.
Example 12
The specific reaction process and detection method are the same as example 1, except that NaNO is added 2 Changed to KNO 2 . As a result, 2, 5-furandicarboxylic acid (FDCA) was obtained as a main product, and the yield was 86.76%, the selectivity was 93%, and the purity thereof was 99.3%.
Example 13
The specific reaction procedure and detection method were the same as in example 1 except that phosphoric acid was changed to silicomolybdic acid. As a result, 2, 5-furandicarboxylic acid (FDCA) was obtained as a main product, and the yield was 90.01%, the selectivity was 92%, and the purity thereof was 97.3%.
Example 14
The specific reaction process and detection method were the same as in example 1 except that the oxidizing agent was changed from atmospheric oxygen to air, and as a result, 2, 5-furandicarboxylic acid (FDCA) was obtained as a main product in a yield of 83.11%, a selectivity of 93%, and a purity of 97.7%.
Example 15
The specific reaction process and detection method were the same as in example 1 except that the oxidizing agent was changed from atmospheric oxygen to hydrogen peroxide, and as a result, 2, 5-furandicarboxylic acid (FDCA) was obtained as the main product, and the yield was 81.87%, the selectivity was 91%, and the purity was 96.5%.
Example 16
The specific reaction process and detection method were the same as in example 1 except that the oxidizing agent was changed from atmospheric oxygen to 1MPa air, and as a result, 2, 5-furandicarboxylic acid (FDCA) was obtained as a main product in a yield of 88.29%, selectivity of 86%, and purity of 96.7%.
Example 17
The specific reaction process and detection method were the same as in example 1 except that the reaction time from 5-hydroxymethylfurfural (5-HMF) to 2, 5-furandicarboxylic acid (FDCA) was changed from 48 hours to 12 hours, and as a result, 2, 5-furandicarboxylic acid (FDCA) was obtained as a main product with a yield of 80.90%, a selectivity of 83%, and a purity of 96.8%.
Example 18
The specific reaction process and detection method were the same as in example 1 except that the reaction time from 5-hydroxymethylfurfural (5-HMF) to 2, 5-furandicarboxylic acid (FDCA) was changed from 48h to 72h, and as a result, 2, 5-furandicarboxylic acid (FDCA) was obtained as a main product with a yield of 93.11%, a selectivity of 92%, and a purity of 99.1%.
Example 19
The specific reaction process and detection method were the same as in example 1 except that the reaction temperature of 5-hydroxymethylfurfural (5-HMF) to 2, 5-furandicarboxylic acid (FDCA) was changed from 55 ℃ to 80 ℃, and as a result, 2, 5-furandicarboxylic acid (FDCA) was obtained as a main product with a yield of 80.03%, a selectivity of 86%, and a purity of 97.9%.
Example 20
The specific reaction process was the same as in example 1 except that the reaction temperature of 5-hydroxymethylfurfural (5-HMF) to 2, 5-furandicarboxylic acid (FDCA) was changed from 55 ℃ to 70 ℃, and as a result, 2, 5-furandicarboxylic acid (FDCA) was obtained as a main product with a yield of 84.44%, a selectivity of 91%, and a purity of 98.4%.
Example 21
The specific reaction process was the same as in example 1 except that the reaction temperature of 5-hydroxymethylfurfural (5-HMF) to 2, 5-furandicarboxylic acid (FDCA) was changed from 55 ℃ to 100 ℃, and as a result, 2, 5-furandicarboxylic acid (FDCA) was obtained as a main product with a yield of 94.54%, a selectivity of 87%, and a purity of 98.7%.
Example 22
The specific reaction procedure and detection method were the same as in example 1 except that the oxygen reaction pressure of 5-hydroxymethylfurfural (5-HMF) to 2, 5-furandicarboxylic acid (FDCA) was changed from normal pressure to 0.5Mpa, and as a result, 2, 5-furandicarboxylic acid (FDCA) was obtained as a main product with a yield of 92.33%, a selectivity of 93%, and a purity of 98.6%.
Example 23
The specific reaction process and detection method were the same as in example 1 except that the oxygen reaction pressure of 5-hydroxymethylfurfural (5-HMF) to 2, 5-furandicarboxylic acid (FDCA) was changed from normal pressure to 2Mpa, and as a result, 2, 5-furandicarboxylic acid (FDCA) was obtained as a main product with a yield of 95.09%, a selectivity of 94%, and a purity of 99.4%.
Example 24
The specific reaction procedure and detection method were the same as in example 1 except that the volume of water in the mixed solvent of a tertiary alcohol and water was changed from 0.2mL to 2mL, and as a result, 2, 5-furandicarboxylic acid (FDCA) was obtained as a main product in a yield of 82.87%, a selectivity of 91%, and a purity of 96.8%.
Example 25
The specific reaction procedure and detection method were the same as in example 1 except that the volume of water in the mixed solvent of tertiary alcohol and water was changed from 0.2mL to 20. Mu.L, and as a result, 2, 5-furandicarboxylic acid (FDCA) was obtained as a main product in a yield of 80.99%, in a selectivity of 84%, and in a purity of 96.3%.
The present invention has been described in detail above, but the present invention is not limited to the specific embodiments described herein. It will be understood by those skilled in the art that other modifications and variations may be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.
Claims (13)
1. A process for producing 2, 5-furandicarboxylic acid from 5-hydroxymethylfurfural, the process comprising: at the temperature of 30-100 ℃, in a mixed solvent of a tertiary alcohol compound and water, the raw material 5-hydroxymethyl furfural reacts in the presence of a TEMPO catalyst, an inorganic acid or solid acid cocatalyst, a nitrite auxiliary agent and an oxidant to be converted into 2, 5-furandicarboxylic acid,
wherein the TEMPO catalyst is one or more selected from catalysts 1-6 having the following structure:
and the inorganic acid or solid acid co-catalyst is selected from one or more of the following: hydrobromic acid, nitric acid, phosphoric acid, amberlite-15, phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, and silicomolybdic acid.
2. The method of claim 1, wherein the nitrite-based adjuvant is one or more selected from the group consisting of: naNO 2 And KNO 2 。
3. The method of claim 1, wherein the oxidizing agent is one or more selected from the group consisting of: air, oxygen, hydrogen peroxide, peroxide salts and hypohalites.
4. The method according to claim 1, wherein the reaction is carried out in an air or oxygen atmosphere of 0.1 to 2.0 MPa.
5. The process according to claim 1, wherein the reaction is carried out at a temperature of 50 to 100 ℃.
6. The process according to claim 1, wherein the reaction is carried out at a temperature of 50 to 70 ℃.
7. The method according to claim 1, wherein the reaction time is 1 to 96 hours.
8. The method of claim 1, wherein the reaction time is 1 to 48 hours.
9. The process according to claim 1, characterized in that the tertiary alcohol compound is one or more selected from the group consisting of: tert-butanol, 2-methyl-pentan-2-ol, 3-methyl-pentan-3-ol and 2-methyl-butan-2-ol.
10. The method according to claim 1, wherein the volume ratio of the tertiary alcohol compound to water in the mixed solvent is from 100 to 1.
11. The method according to claim 1, wherein the mass ratio of the TEMPO catalyst to the raw material 5-hydroxymethylfurfural is 0.01.
12. The method according to claim 1, wherein the mass ratio of the inorganic acid or solid acid cocatalyst to the raw material 5-hydroxymethylfurfural is from 0.01.
13. The method according to claim 1, wherein the mass ratio of the nitrite-based auxiliary agent to the raw material 5-hydroxymethylfurfural is 0.01.
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| CN111559994A (en) * | 2020-05-14 | 2020-08-21 | 安徽中羰碳一工业技术有限责任公司 | Method for preparing 2, 5-furan dicarbaldehyde from fructose |
| CN112830916B (en) * | 2020-07-02 | 2021-08-13 | 中国科学院宁波材料技术与工程研究所 | Preparation method of 2, 5-furandicarboxylic acid under mild condition |
| CN114634472A (en) * | 2022-04-07 | 2022-06-17 | 广西科技大学 | Method for synthesizing 2, 5-furandicarboxylic acid by oxidizing 5-hydroxymethylfurfural |
| CN114853700B (en) * | 2022-04-21 | 2023-03-21 | 合肥利夫生物科技有限公司 | Production method for preparing 2, 5-furandicarboxylic acid from 5-hydroxymethylfurfural |
| US11873286B2 (en) | 2022-05-27 | 2024-01-16 | Shanghai Wokai Biotechnology Co., Ltd. | Method for preparing 2,5-furandicarboxylic acid (FDCA) from furfural |
| CN114773300A (en) * | 2022-05-27 | 2022-07-22 | 上海沃凯生物技术有限公司 | Method for preparing 2, 5-furandicarboxylic acid from furfural |
| CN115141167B (en) * | 2022-07-25 | 2023-07-04 | 合肥利夫生物科技有限公司 | Method for preparing furandicarboxylic acid by metal-free catalytic fructose one-pot method |
| CN115739093B (en) * | 2022-10-10 | 2024-08-16 | 河南省生物基材料产业研究院有限公司 | Catalyst for preparing 2, 5-furandicarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural and preparation method thereof |
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