CN113563289B - Method for preparing 2, 5-furandicarboxylic acid from furfural - Google Patents
Method for preparing 2, 5-furandicarboxylic acid from furfural Download PDFInfo
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Abstract
The application discloses a synthesis method of 2, 5-furandicarboxylic acid, which comprises the following steps: the first step is selective hydrogenation of furfurol to furfuryl alcohol, the second step is methylolation of furfurol to 2, 5-furandimethanol, and the third step is oxidation of 2, 5-furandimethanol to 2, 5-furandicarboxylic acid. The advantages are as follows: the biomass platform derivative compound furfural is used as a raw material, is wide in source, low in cost and easy to obtain, and is simple in process through the hydroxymethylation of furfuryl alcohol, so that the biomass platform derivative compound furfural accords with the concept of green sustainable development.
Description
Technical Field
The application relates to the technical field of synthesis of 2, 5-furandicarboxylic acid, in particular to a preparation method for synthesizing 2, 5-furandicarboxylic acid from biomass-based furfural.
Background
2, 5-furandicarboxylic acid is a biomass-derived chemical, which has a similar structure and chemical properties to terephthalic acid, a petroleum-derived chemical, and can replace paraxylene to play a role in the fields of polyesters, polyamides, and the like, and is classified as one of 12 bio-based platform chemicals by the U.S. department of energy in 2004. Therefore, a new process study on how to efficiently and environmentally prepare 2, 5-furandicarboxylic acid is of great significance.
Currently, the synthesis technology of 2, 5-furandicarboxylic acid mainly includes a 5-Hydroxymethylfurfural (HMF) route and a furoic acid route. The HMF route is that fructose and the like are used as raw materials to prepare HMF through hydrolysis, and the 2, 5-furandicarboxylic acid is obtained through oxidation of 5-hydroxymethylfurfural. The HMF route is currently the most promising route for the large-scale preparation of 2, 5-furandicarboxylic acid, but there are still a number of problems. HMF is mainly a hydrolysis product of cellulose, and this process is temporarily not industrialized, so that 5-hydroxymethylfurfural has a small reserve and is difficult to prepare, and aldehyde groups and hydroxymethyl groups exist in the structure at the same time, so that the HMF cannot exist stably, and the cost is quite high; in addition, in the preparation of 2, 5-furandicarboxylic acid by HMF oxidation, oxidation tends to remain in an intermediate step, resulting in incomplete reaction, and the intermediate product is difficult to separate from 2, 5-furandicarboxylic acid. Chinese patent CN110172049a discloses a method for preparing dimethyl 2, 5-furandicarboxylate from 5-hydroxymethylfurfural by oxidative esterification. Under the condition that air is taken as an oxidant, methanol is taken as a solvent and a reactant, and a catalyst taking metal Au as an active center is adopted to catalyze, oxidize and esterify 5-hydroxymethylfurfural to synthesize the 2, 5-dimethyl furandicarboxylate. This process is simple and has a high HMF conversion>The selectivity of the dimethyl 2, 5-furandicarboxylate is up to 99% at the same time of 95%. Patent CN110799504a discloses a method for preparing dimethyl 2, 5-furandicarboxylate from hydroxymethylfurfural by reacting in the presence of Au nanoparticle supported catalystThe reaction mixture containing HMF, air and alcohol solvent is oxidized and esterified to produce the target product. The yield of the product obtained by the method is 85-90%. Because noble metal catalysts such as Au, pd, pt and the like are needed for oxidizing the 5-hydroxymethylfurfural, the path cost is higher. Ribeiro et al (Catalysis Communications,2003,4 (2): 83-86.) have designed a novel catalyst Co (acac) 3-gel for use in a system for the one-pot synthesis of FDCA from fructose, wherein SiO 2 Gel for promoting dehydration of fructose to synthesize HMF, co (acac) 3 The resulting HMF was promoted to oxidize and synthesize FDCA, and a yield of FDCA in liquid phase of 71% was obtained. The bifunctional catalyst avoids the rehydration reaction of HMF in an acidic aqueous solution to a certain extent, but the liquid phase yield of the final product FDCA is not high, and the catalyst is unstable.
The furoic acid route is mainly to obtain furoic acid by furfuraldehyde catalytic oxidation, and then to prepare 2, 5-furandicarboxylic acid by disproportionation reaction or carbonylation reaction. The reaction conditions of the route are harsh, high temperature and high pressure are usually needed, and the yield is low, so that the method is not beneficial to industrialization. Chinese patent CN109678823a uses inorganic carbonate as catalyst to make furoic acid and CO 2 Introducing into a high-pressure reaction kettle to synthesize the 2, 5-furandicarboxylic acid. The product yield obtained by the method is more than 80 percent, but the reaction temperature is higher (190-260 ℃), the conditions are severe, and the energy consumption is high. Chinese patent CN108997278A provides a process for the preparation of 2, 5-furandicarboxylic acid and 2, 5-furanyl polyesters. The method takes non-grain biomass as raw material to prepare furfural, furoic acid is obtained by oxidation, and furoic acid and CO are then carried out 2 The 2, 5-furandicarboxylic acid is obtained by addition under the action of catalysts such as potassium carbonate, sodium oxalate and the like, the yield is about 75 percent, however, the reaction conditions are harsh when furoic acid is catalyzed to generate 2, 5-furandicarboxylic acid, the reaction temperature and CO in a reaction kettle are severe 2 The pressure is as high as 10MPa, which is not beneficial to realizing industrialization. Thiyagarajan et al (RSC adv.,2013,3,15678-15686) reported a method of CdI 2 As a catalyst, the potassium furoate is catalyzed to disproportionate at 260 ℃ to generate the 2, 5-furandicarboxylic acid, the yield can reach 89%, but the byproduct 2, 4-furandicarboxylic acid is generated, and the separation is difficult.
In summary, the existing production route of 2, 5-furandicarboxylic acid mainly has the problems of harsh reaction conditions, complex process, few raw materials, difficult separation and purification of products and the like. Based on the method, the novel synthesis route which is mild, efficient and environment-friendly is provided, the biomass-based furfural with wide sources is used as the raw material to prepare the 2, 5-furandicarboxylic acid, the route is simple, the product purity is high, and no other pollution byproducts are generated in the whole route.
Disclosure of Invention
The application provides a method for producing 2, 5-furandicarboxylic acid by using furfural as a raw material through three steps.
The application adopts the following technical scheme:
a synthesis method of 2, 5-furandicarboxylic acid, which comprises the following steps:
(1) Adding furfural, a hydrogenation catalyst and a solvent into a reactor respectively, keeping the hydrogen pressure at 0.1MPa-6 MPa, heating the reactor to 100-350 ℃, continuously reacting for 0.1-12h, and obtaining furfuryl alcohol through simple filtering operation after the reaction is finished.
(2) Adding furfuryl alcohol, formaldehyde and a catalyst in a certain proportion into a reactor filled with a proper amount of solvent respectively, controlling the reaction temperature to be 0-80 ℃, placing the mixture under magnetic stirring for continuous reaction for 0.1-24 hours, and obtaining 2, 5-furandimethanol through simple filtration and distillation operation after the reaction is finished.
(3) Mixing 2, 5-furandimethanol, an oxidant and a solvent, adding the mixture into an oxidation kettle with a polytetrafluoroethylene lining, heating the reactor to 80-240 ℃, continuously reacting for 0.1-24 hours, and separating and purifying after the reaction is finished to obtain 2, 5-furandicarboxylic acid.
The solvent in the step (1) is one or more of methanol, ethanol, isopropanol, tetrahydrofuran, dichloromethane, trichloromethane, 1, 2-dichloroethane, tetrachloroethane, acetic acid and C6-C12 chain alkane.
The active center of the hydrogenation catalyst in the step (1) is Au, pd, ru, pt, ni, cu,One or more of Co and metal are combined, and the metal loading amount accounts for 0.1-15% of the carrier mass ratio. The carrier is activated carbon, carbon nanofiber and Al 2 O 3 、SiO 2 Pure silicon molecular sieve, zrO 2 One or more of the following.
The mass ratio of furfuryl alcohol to formaldehyde in step (2) is 20:1-1:20.
The formaldehyde as the reaction substrate in the step (2) is one or more of formaldehyde aqueous solution, trioxymethylene and paraformaldehyde. The solvent is one or more of water, alkane, cycloalkane, ethyl acetate, acetone and tetrahydrofuran or a solvent-free system.
The catalyst for the methylolation reaction in the step (2) is solid acid such as HZSM-5, amberlyst-15, HBEA, HY, HMOR, HUSY and the like, and HCl and CH 3 COOH、H 2 SO 4 Isoliquid acid and lactic acid-HBEA, P-SiO 2 One or more of the equally supported solid catalysts.
The oxidant in the reaction in the step (3) is K 2 Cr 2 O 7 KMnO, acidic solution of (a) 4 Acidic solution, H 2 O 2 Solution filled with 0.1-6MPa O 2 Co, br, mn, mo system filled with O 2 One or more of the systems of supported metal catalysts.
The active center of the supported metal catalyst used for oxidation in the step (3) is one or more of Au, pd, ru, pt, fe, zn, mn, and the carrier is C, tiO 2 、ZrO 2 、Fe 3 O 4 、CeO 2 、La 2 O 3 One or more of MgO, hydrotalcite, spinel, etc.
The solvent for the reaction in the step (3) is one or more of acetonitrile, 1, 2-dichloroethane, tetrahydrofuran, ethyl acetate, chloroform, acetic acid, propionic acid or n-butyric acid.
The application provides a method for preparing 2, 5-furandicarboxylic acid from biomass platform chemical furfural, which adopts biomass platform chemical furfural as a raw material, has the advantages of wide sources, low cost and easy obtainment, simple production process, high product purity and no other pollution by-products in the whole path, and accords with the concept of green sustainable development.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be clearly and completely described below in connection with specific embodiments of the present application. It will be apparent that the described embodiments are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
Example 1
(1) Selective hydrogenation of furfural to furfuryl alcohol
The hydrogenation catalyst is prepared by an impregnation method. An amount of PdCl 2 Dissolving in appropriate amount of water, weighing 1g SiO 2 Added to PdCl 2 In the solution, the loading of metal Pd was 2%. The mixture was stirred to dryness, dried overnight at 80 ℃ and ground to a powder. Calcining the powder in a nitrogen atmosphere at 350 ℃, reducing the powder with hydrogen at the same temperature, cooling the powder, and then introducing a mixed gas of nitrogen and air for aging to obtain the hydrogenation catalyst.
In the embodiment, furfural is used as a raw material. 0.2g of hydrogenation catalyst was added to the reaction vessel, 1g of furfural was added, and 40mL of anhydrous methanol was added as a solvent. After the reaction kettle is sealed, N is used first 2 Air in the reaction kettle is replaced and H is used again 2 N in the replacement reaction kettle 2 Charging 2MPa of H 2 . The reaction vessel was heated to 150℃and allowed to react for 4 hours.
After the reaction is finished, the reactor body is cooled to room temperature, and the catalyst and the liquid phase product are separated by filtration. The liquid phase product was quantitatively analyzed by gas chromatography-mass spectrometer. The chromatographic analysis result shows that the conversion rate of furfural reaches 100%, and the yield of furfuryl alcohol reaches 94%.
(2) Carrying out methylolation reaction on furfuryl alcohol and formaldehyde
1mL of furfuryl alcohol, 2mL of aqueous formaldehyde solution, and 5mL of H were removed with a pipette 2 O is added into a round bottom flask one by one, and 0.6g of HUSY molecular sieve is weighed and added intoIn the flask, the temperature was raised to 40℃in an oil bath, and the reaction was carried out for 6 hours. After the reaction is finished, the reaction solution is subjected to simple filtering operation and then the redundant solvent is removed by rotary evaporation to obtain the 2, 5-furandimethanol.
The chromatographic analysis result shows that the conversion rate of furfuryl alcohol is 100%, and the yield of 2, 5-furandimethanol reaches 98%.
(3) Oxidation of 2, 5-furandimethanol to 2, 5-furandicarboxylic acid
0.5g of 2, 5-furandimethanol, 0.015g of NaBr and 0.010g of MnCl are added into a small oxidation kettle in sequence 2 、0.025g CoCl 2 ·6H 2 O, 5mL acetic acid, the reaction vessel is sealed first, and N is used for 2 The gas washing is carried out three times, and then O with the pressure of 1.5MPa is filled 2 . The reaction vessel was heated to 140℃and allowed to react for 1 hour. After the reaction is finished, cooling the kettle body to room temperature, and obtaining the 2, 5-furandicarboxylic acid after simple filtering and purifying operation. The white solid was analyzed by high performance liquid chromatography, and the result showed that the yield of 2, 5-furandicarboxylic acid was 96%.
Example 2
(1) Selective hydrogenation of furfural to furfuryl alcohol
The hydrogenation catalyst is prepared by an impregnation method. A certain amount of nickel nitrate was dissolved in a proper amount of water, and 1g of ZrO was added to the solution 2 So that the loading of metallic Ni was 10%. The mixture was stirred to dryness, dried overnight at 80 ℃ and ground to a powder. Calcining the powder in a nitrogen atmosphere at 450 ℃, reducing the powder with hydrogen at the same temperature, cooling the powder, and then introducing a mixed gas of nitrogen and air for aging to obtain the hydrogenation catalyst.
In the embodiment, furfural is used as a raw material. 1g of hydrogenation catalyst was added to the reaction vessel, 10g of furfural was added, and 40mL of n-hexane was added as a solvent. After the reaction kettle is sealed, N is used first 2 Air in the reaction kettle is replaced and H is used again 2 N in the replacement reaction kettle 2 Recharging with 4MPa of H 2 . The reaction vessel was heated to 180℃and allowed to react for 2 hours.
After the reaction is finished, the reactor body is cooled to room temperature, and the catalyst and the liquid phase product are separated by filtration. The liquid phase product was quantitatively analyzed by gas chromatography-mass spectrometer. The chromatographic analysis result shows that the conversion rate of furfural reaches 100%, and the yield of furfuryl alcohol reaches 96%.
(2) Carrying out methylolation reaction on furfuryl alcohol and formaldehyde
10mL of furfuryl alcohol and 10g of trioxymethylene were removed by a pipette and added to the round bottom flask one by one, and then 4g of HBEA molecular sieve was weighed and added to the flask for reaction at 0℃for 6h. After the reaction is finished, the reaction solution is filtered simply to obtain the 2, 5-furandimethanol.
The chromatographic analysis result shows that the conversion rate of furfuryl alcohol is 100%, and the yield of 2, 5-furandimethanol reaches 98%.
(3) Oxidation of 2, 5-furandimethanol to 2, 5-furandicarboxylic acid
0.5g of 2, 5-furandimethanol and 0.25g of Au-CeO are added into a small reaction kettle 2 And 5mL of water, the reaction vessel was sealed with N 2 The gas washing is carried out three times, and then O with the pressure of 2.5MPa is filled 2 . The reaction vessel was heated to 90℃and allowed to react for 4 hours. After the reaction is finished, cooling the kettle body to room temperature, and obtaining the 2, 5-furandicarboxylic acid after simple filtering and purifying operation. The white solid was analyzed by high performance liquid chromatography, and the result showed that the yield of 2, 5-furandicarboxylic acid was 99%.
Example 3
(1) Selective hydrogenation of furfural to furfuryl alcohol
The hydrogenation catalyst is prepared by an impregnation method. A certain amount of ruthenium chloride was dissolved in a proper amount of water, 1g of activated carbon was added to the solution, and the loading of metal Ru was kept at 1.5%. The mixture was stirred to dryness, dried overnight at 80 ℃ and ground to a powder. Calcining the powder in a nitrogen atmosphere at 350 ℃, reducing the powder with hydrogen at the same temperature, cooling the powder, and then introducing a mixed gas of nitrogen and air for aging to obtain the hydrogenation catalyst.
In the embodiment, furfural is used as a raw material. 0.2g of hydrogenation catalyst was added to the reaction vessel, 2g of furfural was added, and 40mL of tetrahydrofuran was added as a solvent. After the reaction kettle is sealed, N is used first 2 Air in the reaction kettle is replaced and H is used again 2 N in the replacement reaction kettle 2 Recharging with 5MPa of H 2 . Will be reversedThe kettle is heated to 140 ℃ and reacts for 4 hours.
After the reaction is finished, the reactor body is cooled to room temperature, and the catalyst and the liquid phase product are separated by filtration. The liquid phase product was quantitatively analyzed by gas chromatography-mass spectrometer. The chromatographic analysis result shows that the conversion rate of furfural reaches 100 percent and the yield of furfuryl alcohol reaches 100 percent.
(2) Carrying out methylolation reaction on furfuryl alcohol and formaldehyde
10mL of furfuryl alcohol and 20mL of formaldehyde aqueous solution are removed by a pipette, added into a round bottom flask one by one, and then 6g P-SiO is weighed 2 Added to the flask and reacted at 25℃for 24 hours. After the reaction is finished, the reaction solution is filtered simply to obtain the 2, 5-furandimethanol.
The chromatographic analysis result shows that the conversion rate of furan is 100%, and the yield of 2, 5-furandimethanol reaches 100%.
(3) Oxidation of 2, 5-furandimethanol to 2, 5-furandicarboxylic acid
0.5g of 2, 5-furandimethanol, au/HT (hydrotalcite) and 5mL of propionic acid were added to a small reaction vessel, and the reaction vessel was sealed with N 2 The gas washing is carried out three times, and then O with the pressure of 2.5MPa is filled 2 . The reaction vessel was heated to 160℃and allowed to react for 2 hours. After the reaction is finished, cooling the kettle body to room temperature, and obtaining the 2, 5-furandicarboxylic acid after simple filtering and purifying operation. The white solid was analyzed by high performance liquid chromatography, and the result showed that the yield of 2, 5-furandicarboxylic acid was 94%.
Claims (3)
1. The synthesis method of the 2, 5-furandicarboxylic acid is characterized by comprising the following steps of:
step 1, selectively hydrogenating furfural to generate furfuryl alcohol:
the hydrogenation catalyst is prepared by an impregnation method: pdCl is added to 2 Dissolving in water, weighing 1g SiO 2 Added to PdCl 2 In the solution, the load of metal Pd is 2%, the mixed solution is stirred to be dry, dried at 80 ℃ overnight, ground into powder, the powder is calcined in nitrogen atmosphere at 350 ℃, then reduced by hydrogen at the same temperature, cooled and then aged by introducing the mixture of nitrogen and air, thus obtaining the catalystTo the hydrogenation catalyst, the catalyst is a catalyst,
adding 0.2g of hydrogenation catalyst into a reaction kettle, adding 1g of furfural, adding 40mL of absolute methanol as a solvent, sealing the reaction kettle, and using N firstly 2 Air in the reaction kettle is replaced and H is used again 2 N in the replacement reaction kettle 2 Charging 2MPa of H 2 Heating the reaction kettle to 150 ℃, reacting for 4 hours, cooling the kettle body to room temperature after the reaction is finished, and filtering to separate a catalyst and a liquid-phase product;
step 2, methylolation of furfuryl alcohol to form 2, 5-furandimethanol:
1mL of furfuryl alcohol, 2mL of aqueous formaldehyde solution, and 5mL of H were removed with a pipette 2 Adding O into a round-bottom flask one by one, weighing 0.6g of HUSY molecular sieve, adding into the flask, heating to 40 ℃ under an oil bath, reacting for 6 hours, filtering the reaction liquid after the reaction is finished, and removing redundant solvent by rotary evaporation to obtain 2, 5-furandimethanol;
step 3, oxidizing 2, 5-furandimethanol into 2, 5-furandicarboxylic acid:
0.5g of 2, 5-furandimethanol, 0.015g of NaBr and 0.010g of MnCl are added into a small oxidation kettle in sequence 2 、0.025g CoCl 2 ·6H 2 O, 5mL acetic acid, the reaction vessel is sealed first, and N is used for 2 The gas washing is carried out three times, and then O with the pressure of 1.5MPa is filled 2 Heating the reaction kettle to 140 ℃, reacting for 1 hour, cooling the kettle body to room temperature after the reaction is finished, and obtaining the 2, 5-furandicarboxylic acid after filtering and purifying operations.
2. The synthesis method of the 2, 5-furandicarboxylic acid is characterized by comprising the following steps of:
step 1, selectively hydrogenating furfural to generate furfuryl alcohol:
the hydrogenation catalyst is prepared by an impregnation method: nickel nitrate was dissolved in water, and 1g ZrO was added to the solution 2 The metal Ni loading is 10%, the mixed solution is stirred to be dry, dried at 80 ℃ overnight, ground into powder, the powder is calcined in nitrogen atmosphere at 450 ℃, then reduced by hydrogen at the same temperature, cooled and then the mixture of nitrogen and air is introduced for agingAnd the hydrogenation catalyst is obtained after the reaction,
adding 1g of hydrogenation catalyst into a reaction kettle, adding 10g of furfural, adding 40mL of normal hexane as a solvent, sealing the reaction kettle, and using N firstly 2 Air in the reaction kettle is replaced and H is used again 2 N in the replacement reaction kettle 2 Recharging with 4MPa of H 2 Heating the reaction kettle to 180 ℃ for 2 hours,
after the reaction is finished, after the kettle body is cooled to room temperature, filtering and separating the catalyst and the liquid phase product;
step 2, methylolation of furfuryl alcohol to form 2, 5-furandimethanol:
transferring 10mL of furfuryl alcohol and 10g of trioxymethylene by a liquid transferring gun, adding the furfuryl alcohol and 10g of trioxymethylene into a round-bottom flask one by one, weighing 4g of HBEA molecular sieve, adding the molecular sieve into the flask, reacting for 6 hours at 0 ℃, and filtering the reaction liquid after the reaction is finished to obtain 2, 5-furandimethanol;
step 3, oxidizing 2, 5-furandimethanol into 2, 5-furandicarboxylic acid:
0.5g of 2, 5-furandimethanol and 0.25g of Au-CeO are added into a small reaction kettle 2 And 5mL of water, the reaction vessel was sealed with N 2 The gas washing is carried out three times, and then O with the pressure of 2.5MPa is filled 2 Heating the reaction kettle to 90 ℃, reacting for 4 hours, cooling the kettle body to room temperature after the reaction is finished, and obtaining the 2, 5-furandicarboxylic acid after filtering and purifying operations.
3. The synthesis method of the 2, 5-furandicarboxylic acid is characterized by comprising the following steps of:
step 1, selectively hydrogenating furfural to generate furfuryl alcohol:
the hydrogenation catalyst is prepared by an impregnation method: dissolving ruthenium chloride in water, adding 1g of active carbon into the solution, keeping the loading of metal Ru at 1.5%, stirring the mixed solution to be dry, drying at 80 ℃ overnight, grinding into powder, calcining the powder in nitrogen atmosphere at 350 ℃, reducing with hydrogen at the same temperature, cooling, then introducing mixed gas of nitrogen and air for aging to obtain a hydrogenation catalyst,
adding 0.2g of hydrogenation catalyst into a reaction kettle, addingAdding 2g of furfural, adding 40mL of tetrahydrofuran as a solvent, sealing the reaction kettle, and using N 2 Air in the reaction kettle is replaced and H is used again 2 N in the replacement reaction kettle 2 Recharging with 5MPa of H 2 Heating the reaction kettle to 140 ℃, reacting for 4 hours, cooling the kettle body to room temperature after the reaction is finished, filtering and separating the catalyst and the liquid phase product,
step 2, methylolation of furfuryl alcohol to form 2, 5-furandimethanol:
10mL of furfuryl alcohol and 20mL of formaldehyde aqueous solution are removed by a pipette, added into a round bottom flask one by one, and then 6g P-SiO is weighed 2 Adding the mixture into a flask, reacting for 24 hours at 25 ℃, and filtering the reaction solution after the reaction is finished to obtain 2, 5-furandimethanol;
step 3, oxidizing 2, 5-furandimethanol into 2, 5-furandicarboxylic acid:
0.5g of 2, 5-furandimethanol, au/hydrotalcite and 5mL of propionic acid were added to a small reactor, and the reactor was sealed with N 2 The gas washing is carried out three times, and then O with the pressure of 2.5MPa is filled 2 Heating the reaction kettle to 160 ℃, reacting for 2 hours, cooling the kettle body to room temperature after the reaction is finished, and obtaining the 2, 5-furandicarboxylic acid after filtering and purifying operations.
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| CN103058962B (en) * | 2013-01-24 | 2015-01-21 | 中国科学院青岛生物能源与过程研究所 | Method for preparing 2,5-furan methylene glycol dialkyl ether by furfuryl alcohol |
| CN104059037A (en) * | 2014-03-25 | 2014-09-24 | 浙江理工大学 | Preparation method of 2,5-furandicarboxylic acid |
| EP3265450B1 (en) * | 2015-03-05 | 2020-08-05 | BP Corporation North America Inc. | Synthesis of furans from sugars via keto intermediates |
| FR3053336B1 (en) * | 2016-07-01 | 2018-09-21 | Centre National De La Recherche Scientifique | PROCESS FOR THE PREPARATION OF DICARBOXYLIC 2,5-FURANE ACID (FDCA) FROM PENTOSIC DERIVATIVES |
| KR101791852B1 (en) * | 2017-03-20 | 2017-11-01 | 국도화학 주식회사 | Furan monomer with bifunctional hydroxymethyl group and Method for preparing the same |
| CN109851597A (en) * | 2018-12-25 | 2019-06-07 | 东莞理工学院 | A kind of preparation method of 2,5- furyl dimethyl carbinol dialkyl ether |
| CN111187238B (en) * | 2020-01-13 | 2022-03-22 | 华东师范大学 | Synthetic method of 2, 5-furandicarboxylic acid |
| CN112898252B (en) * | 2021-01-18 | 2022-09-13 | 中国科学院宁波材料技术与工程研究所 | Preparation method of 2, 5-furandicarboxylic acid |
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