CN111187238B - Synthetic method of 2, 5-furandicarboxylic acid - Google Patents
Synthetic method of 2, 5-furandicarboxylic acid Download PDFInfo
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Abstract
The application discloses a synthetic method of 2, 5-furandicarboxylic acid, which comprises the following steps: the first step is hydrogenation of furfural into methylfuran, and the second step is acetylation of methylfuran; the third step is the hydrogenation of 5-methyl-2-acetylfuran; the fourth step is the oxidation of 2-methyl-5-ethylfuran. Compared with a process for preparing 2, 5-furandicarboxylic acid by using 5-hydroxymethylfurfural as a raw material, the method has the advantages that the green and renewable bio-based platform compound furfural is used as the raw material, the source of the used raw material is wider, the raw material is easy to produce, the yield is higher, the cost of the raw material is lower, and the cost of the used oxidation catalyst is low, so that the method is favorable for large-scale production. Compared with a noble metal complex catalyst used in a process of taking CO carbonylation as carbon chain growth, the catalyst used in the carbon chain growth strategy is solid acid, so that the cost is greatly reduced.
Description
Technical Field
The application relates to the technical field of catalytic synthesis, in particular to a synthetic method of 2, 5-furandicarboxylic acid.
Background
With the steady development of Chinese economy and industry, the domestic demand for polymer materials is increasing, and the problem with the increasing demand is the degradation problem of the polymer materials. Polyolefin polymers are difficult to degrade in nature to form white garbage, so that environmental pollution is caused, and the living environment of human beings and the living environment of other organisms are influenced. There is a growing interest in degradable polyester-based polymer materials. Terephthalic acid is used as an important monomer of polyester, and the source of the terephthalic acid is mainly non-renewable petroleum resources, which are influenced by the increasing exhaustion of petrochemical resources. 2, 5-Furandicarboxylic acid is a derivative of bio-based sugars (5-carbon sugars and 6-carbon sugars) and has a rigid aromatic ring structure similar to that of terephthalic acid, and can be used as a monomer for producing polyester-based polymers in place of terephthalic acid. The polyester prepared from 2, 5-furandicarboxylic acid has higher strength, and the furan ring has lower aromaticity than the benzene ring, and the prepared polyester is more easily degraded. Therefore, the 2, 5-furandicarboxylic acid has good production and application prospects.
The major pathways currently used to produce 2, 5-furandicarboxylic acid from biobased sugars are the carbon 6 sugar pathway and the carbon 5 sugar pathway. The steps of the carbon 6 sugar pathway are mainly the hydrolysis of the carbon 6 sugar to prepare 5-hydroxymethylfurfural, followed by the oxidation of the 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid. This route has few steps and is simple and convenient, and thus has received attention from many researchers. Chinese patent CN107880002A discloses a method for preparing 2, 5-furandicarboxylic acid and furan polyester from straws. The method comprises the steps of hydrolyzing straws under an acidic condition to obtain a water solution containing sugar, continuously hydrolyzing the water solution containing sugar under the acidic condition to obtain 5-hydroxymethylfurfural, oxidizing the 5-hydroxymethylfurfural to obtain 2, 5-furandicarboxylic acid, and then carrying out esterification and polycondensation to obtain furan polyester. This process is simple but has a low yield of only 7% of the total yield. Mainly due to the low hydrolysis efficiency of the first two steps under acidic conditions. And the 5-hydroxymethylfurfural obtained by hydrolyzing the sugar water solution in the second step has the defects of difficult separation, instability and the like. Meanwhile, the oxidation of 5-hydroxymethylfurfural needs to use noble metal catalysts such as Au, Pd, Pt and the like. These reasons make the route from hydrolysis of the carbon 6 sugars to 5-hydroxymethylfurfural followed by oxidation of the 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid more costly.
The main steps of the carbon 5 sugar path are that the carbon 5 sugar is hydrolyzed to prepare furfural, and the furfural is subjected to carbon growth and oxidation steps to obtain 2,5 furandicarboxylic acid. Most of the carbon 5 sugar in the path is extracted from the agricultural and forestry wastes such as corncobs, straws and bagasse, so that the method does not compete for grains with people, is low in cost and has wide application prospect. Chinese patent CN 106977476B discloses a method for preparing furandicarboxylic acid from furoic acid. The method comprises the following specific steps: brominating furoic acid such that the hydrogen at position 5 of furoic acid is replaced by bromine; esterification, namely esterifying carboxyl; carbonylation, and reaction with carbon monoxide under the catalysis of a palladium complex catalyst; hydrolyzing to obtain the final reaction product furan dicarboxylic acid. The reaction condition of the process is mild, but the palladium complex catalyst used for carbonylation is high in price and is not suitable for large-scale production. Another similar method of carbon growth is carbonate catalyzed carbon dioxide insertion. Chinese patent CN 109678823A discloses a method for extracting furfural from furfural through CO2A process for the manufacture of 2, 5-furandicarboxylic acid by intercalation. Specifically, furfural is oxidized to be called furoic acid, and then carbonate, furoic acid and carbon dioxide which are supported by inorganic oxides are introduced into a high-pressure reaction kettle to react at the temperature of 190 ℃ and 260 ℃. The method is simple and does not require ligand combinationHowever, the cesium carbonate used is relatively expensive and is still difficult to scale up.
Disclosure of Invention
The application provides a method for producing 2, 5-furandicarboxylic acid by taking furfural as a raw material through four steps.
The following technical scheme is adopted in the application:
synthetic route developed by the scheme
A method for synthesizing 2, 5-furandicarboxylic acid, comprising the steps of:
(1) mixing furfural, a hydrogenation catalyst and a solvent, adding the mixture into a reactor, introducing inert gas to replace air in the reactor, then introducing hydrogen to replace the inert gas, keeping the pressure of the hydrogen at 0.1-4MPa, heating the temperature of the reactor to 180 ℃ and 280 ℃, continuously reacting for 0.1-24 hours, and separating to obtain methylfuran;
(2) mixing methylfuran with acetic anhydride, dissolving in a solvent, introducing into a normal-pressure fixed bed reactor filled with a solid acid catalyst, wherein the temperature of the reactor is 30-150 ℃, and separating to obtain 5-methyl-2-acetylfuran;
(3) adding 5-methyl-2-acetylfuran, a supported metal catalyst and a solvent into a reactor, introducing inert gas to replace air in the reactor, subsequently introducing hydrogen to replace the inert gas, keeping the pressure of the hydrogen at 1-4MPa, heating the reactor to 180 ℃ and 280 ℃, continuously reacting for 5 minutes-24 hours, and separating to obtain 2-methyl-5-ethylfuran;
(4) adding 2-methyl-5-ethyl furan into a reactor with a polytetrafluoroethylene lining, reacting for 0.1-16 hours under the catalytic action of an oxidant, and separating to obtain 2, 5-furandicarboxylic acid.
The hydrogenation catalyst in the step (1) is a supported catalyst containing one or more metals of Cu, Ni, Fe, Co and Ru, the total metal loading amount accounts for 0.05-50% of the mass ratio of the carrier, and the carrier is one or more of activated carbon, nano carbon fiber, silicon dioxide, titanium dioxide, alumina and pure silicon molecular sieves.
In the step (1), the mass ratio of the hydrogenation catalyst to the furfural is 5: 1 to 1: 20.
the solvent in the step (1) is one or more of methanol, ethanol, tetrahydrofuran, n-hexane and dodecane.
The solid acid catalyst in the step (2) is a solid molecular sieve, phosphotungstic acid, phosphomolybdic acid or a supported catalyst, and the supported catalyst takes phosphotungstic acid or phosphomolybdic acid as an active center. The solid molecular sieve is one or more of ZSM-5, HBEA, HY, HSUY and HMOR.
The solvent in the step (2) is chloralkane, and the chloralkane is ethyl chloride, dichloroethane, chloroform, chloropropane or dichloropropane.
The active center of the supported metal catalyst in the step (3) is one or more of Cu, Ni, Fe, Co and Ru, the total metal loading amount accounts for 0.05-50% of the mass ratio of the carrier, and the carrier is one or more of activated carbon, nano carbon fiber, silicon dioxide, titanium dioxide, aluminum oxide and pure silicon molecular sieve.
The solvent in the step (3) is one or more of methanol, ethanol, tetrahydrofuran, n-hexane and dodecane.
The oxidant in the step (4) is KMnO4Acid solution of (2) or H2O2And (3) solution.
The oxidant in the step (4) is oxygen of 0.1-4Mpa, the metallic salt of Co, the metallic salt of Mn, the metallic salt of Br or HBr solution is added into the reactor, wherein, the content of Co, Mn or Br accounts for 0.1-10% of the molar percentage of the raw material 2-methyl-5-ethyl furan, and the reactor is also added with solvent which is acetonitrile, 1, 2-dichloroethane, chloroform, acetic acid, propionic acid or n-butyric acid.
The above-mentioned at least one technical scheme that this application adopted can reach following beneficial effect:
the method takes a green renewable bio-based platform compound furfural as a raw material, generates methyl furan through hydrogenation, acetylates the methyl furan to increase a carbon chain, generates an ethyl group through hydrogenation of an acetyl group connected to a furan ring, and further oxidizes the ethyl group to generate the 2, 5-furandicarboxylic acid. Compared with the process for preparing 2, 5-furandicarboxylic acid by using 5-hydroxymethylfurfural as a raw material, the method has the advantages of wider raw material source, easy production of the raw material, higher yield, lower cost of the raw material, low cost of the used oxidation catalyst and contribution to large-scale production. Compared with a noble metal complex catalyst used in a process of taking CO carbonylation as carbon chain growth, the catalyst used in the carbon chain growth strategy is solid acid, so that the cost is greatly reduced.
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 described in detail and completely with reference to the specific embodiments of the present application. It should be apparent that the described embodiments are only some of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Example 1
(1) Preparation of methylfuran by furfural hydrodeoxygenation
The furfural hydrogenation catalyst is prepared by an impregnation method, and a proper amount of nickel nitrate is dissolved in water. Mixing SiO2Adding the powder into the solution, wherein the total metal amount is SiO215% of the mass of (a). The mixture was stirred to dryness, dried overnight at 80 ℃ and ground to a powder. Calcining the powder at 450 ℃ in air, and then reducing the calcined powder with hydrogen at the same temperature to obtain the furfural hydrogenation catalyst.
Adding 1g of hydrogenation catalyst into a reaction kettle, adding 10g of furfural, and adding 80ml of anhydrous methanol as a solvent. After the reaction kettle is sealed, N is firstly used2Replacing air in the reaction kettle, and recharging 4MPa of H2. The reaction kettle is heated to 200 ℃ and reacts for 10 hours.
After the reaction is finished, the kettle 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. Instrument information: shimadzu QP-2010 Ultra; information on the chromatographic column: rtx-5 Sil MS (30 m.times.0.25 mm.times.0.25 μm). Setting a chromatographic program: after heating to 280 ℃ at 10 ℃ per minute from 100 ℃, the temperature was maintained for 20 minutes. The chromatographic analysis result shows that the conversion rate of the furfural reaches 100 percent and the yield of the methylfuran reaches 93 percent. The solvent was removed by distillation under reduced pressure to give methylfuran.
(2) Acetylation of methylfuran to prepare 5-methyl-2-acetylfuran
The acetylation of the methylfuran is carried out in a fixed bed at atmospheric pressure. 4g of HSUY catalyst was tableted and shaped, and then sieved to obtain catalyst particles having a particle size of 20-60 mesh. The catalyst is loaded in the reactor. Then 5g of methylfuran and 15.5g of acetic anhydride were weighed out and dissolved in 1, 2-dichloroethane. And heating the reactor to 80 ℃, introducing the reaction mixed liquor into the reactor through a constant flow pump, and reacting for 3 hours.
After the reaction is finished, the kettle 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. Instrument information: shimadzu QP-2010 Ultra; information on the chromatographic column: rtx-5 Sil MS (30 m.times.0.25 mm.times.0.25 μm). Setting a chromatographic program: after heating to 280 ℃ at 10 ℃ per minute from 100 ℃, the temperature was maintained for 20 minutes. The chromatographic analysis result shows that the conversion rate of the methylfuran reaches 99 percent, and the yield of the 5-methyl-2-acetylfuran reaches 99 percent. The solvent was removed by distillation under reduced pressure to give 5-methyl-2-acetylfuran.
(3) Preparation of 2-methyl-5-ethyl furan by hydrodeoxygenation of 5-methyl-2-acetylfuran
The 5-methyl-2-acetylfuran hydrogenation catalyst is prepared by a hydrothermal method. Dissolving Co precursor cobalt nitrate into a certain amount of water, adding a certain amount of ammonium chloride and ammonia water, and fully dissolving. A certain amount of SiO2Adding into the mixed solution, the metal is SiO2100% by mass. After the mixed solution is stirred for 2 hours, the mixed solution is transferred into a self-pressure hydrothermal kettle, and the hydrothermal kettle is placed in a 120 ℃ oven for reaction for 6 hours. The resulting catalyst was washed with water and oven dried at 60 ℃ overnight. The obtained solid was ground and calcined at 450 ℃ for 4 hours in an air atmosphere, followed by reduction at the same temperature for 4 hours in a hydrogen atmosphereObtaining the hydrogenation catalyst.
0.5g of hydrogenation catalyst was added to the reaction vessel, and 5g of 5-methyl-2-acetylfuran and 50ml of 1, 4-dioxane were added. After the reaction kettle is sealed, N is firstly used2Replacing air in the reaction kettle, and recharging 3MPa of H2. The reaction kettle is heated to 220 ℃ and reacted for 5 hours. After the reaction is finished, the kettle 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. Instrument information: shimadzu QP-2010 Ultra; information on the chromatographic column: rtx-5 Sil MS (30 m.times.0.25 mm.times.0.25 μm). Setting a chromatographic program: after heating to 280 ℃ at 10 ℃ per minute from 100 ℃, the temperature was maintained for 20 minutes. The chromatographic analysis result shows that the conversion rate of the 5-methyl-2-acetylfuran reaches 99 percent, and the yield of the 2-methyl-5-ethylfuran reaches 97 percent. The solvent was removed by rotary evaporation to give 2-methyl-5-ethylfuran.
(4) Preparation of 2, 5-furandicarboxylic acid by oxidation of 2-methyl-5-ethylfuran
0.5g of 2-methyl-5-ethyl furan and a proper amount of KMnO are sequentially added into a reaction kettle with a polytetrafluoroethylene lining4And 10ml of a 1mol/L aqueous sulfuric acid solution, and the reaction vessel was sealed. The reaction kettle is heated to 70 ℃ to react for 1 hour.
After the reaction is finished, cooling the kettle to room temperature, filtering to separate out solids, washing with ice water for three times, and drying in an oven at 60 ℃ for 12 hours. The white solid was subjected to composition analysis by high performance liquid chromatography. Instrument information: the Shimadzu high performance liquid chromatograph has a UV-VIS detector with the model of SPD-16, a liquid delivery pump with the model of LC-16 and a column incubator with the model of CTO-16; information on the chromatographic column: wondasil C18-WR5um (5 μm × 4.6mm I.D. × 150 mm); in the test conditions, the mobile phase: methanol/1% acetic acid solution 10:90 at a flow rate of 1mL/min, a column temperature of 30 ℃, a detection wavelength of 264nm, and a sample injection volume of 10 μ L. The chromatographic analysis showed a 2, 5-furandicarboxylic acid content of 98.5% giving a yield of 92% in the oxidation step by calculation.
Example 2
(1) Preparation of methylfuran by furfural hydrodeoxygenation
The furfural hydrogenation catalyst is prepared by an impregnation method by mixing copper nitrate withNickel nitrate was dissolved in water at a molar ratio of Cu to Ni of 2 to 8. Mixing SiO2Adding the powder into the solution, wherein the total metal amount is SiO220% of the mass of (a). The mixture was stirred to dryness, dried overnight at 80 ℃ and ground to a powder. Calcining the powder at 450 ℃ in air, and then reducing the calcined powder with hydrogen at the same temperature to obtain the furfural hydrogenation catalyst.
Adding 0.5g of hydrogenation catalyst into a reaction kettle, adding 8g of furfural, and adding 80ml of absolute ethyl alcohol as a solvent. After the reaction kettle is sealed, N is firstly used2Replacing air in the reaction kettle, and recharging 3MPa of H2. The reaction kettle is heated to 240 ℃ and reacted for 6 hours.
After the reaction is finished, the kettle 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. Instrument information: shimadzu QP-2010 Ultra; information on the chromatographic column: rtx-5 Sil MS (30 m.times.0.25 mm.times.0.25 μm). Setting a chromatographic program: after heating to 280 ℃ at 10 ℃ per minute from 100 ℃, the temperature was maintained for 20 minutes. The chromatographic analysis result shows that the conversion rate of the furfural reaches 96 percent, and the yield of the methylfuran reaches 94 percent. The solvent was removed by distillation under reduced pressure to give methylfuran.
(2) Acetylation of methylfuran to prepare 5-methyl-2-acetylfuran
The acetylation of the methylfuran is carried out in a fixed bed at atmospheric pressure. 4g of HBEA catalyst was tableted and formed, and then sieved to obtain catalyst particles having a particle size of 20-60 mesh. The catalyst is loaded in the reactor. Then 6g of methylfuran and 11.2g of acetic anhydride were weighed out and dissolved in 1, 2-dichloroethane. Heating the reactor to 50 ℃, introducing the reaction mixed liquor into the reactor through a constant flow pump, and reacting for 2 hours.
After the reaction is finished, the kettle 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. Instrument information: shimadzu QP-2010 Ultra; information on the chromatographic column: rtx-5 Sil MS (30 m.times.0.25 mm.times.0.25 μm). Setting a chromatographic program: after heating to 280 ℃ at 10 ℃ per minute from 100 ℃, the temperature was maintained for 20 minutes. The chromatographic analysis result shows that the conversion rate of the methylfuran reaches 96 percent, and the yield of the 5-methyl-2-acetylfuran reaches 91 percent. The solvent was removed by distillation under reduced pressure to give 5-methyl-2-acetylfuran.
(3) Preparation of 2-methyl-5-ethyl furan by hydrodeoxygenation of 5-methyl-2-acetylfuran
The 5-methyl-2-acetylfuran hydrogenation catalyst is prepared by a hydrothermal method. Dissolving nickel nitrate into a certain amount of water, adding a certain amount of ammonium chloride and ammonia water, and fully dissolving. A certain amount of SiO2Adding into the mixed solution, the metal is SiO230% of the mass. After the mixed solution is stirred for 2 hours, the mixed solution is transferred into a self-pressure hydrothermal kettle, and the hydrothermal kettle is placed in a 120 ℃ oven for reaction for 6 hours. The resulting catalyst was washed with water and oven dried at 60 ℃ overnight. The obtained solid was ground and calcined at 450 ℃ for 4 hours in an air atmosphere, followed by reduction at the same temperature for 4 hours in a hydrogen atmosphere, to obtain a hydrogenation catalyst.
0.5g of a hydrogenation catalyst was charged into a reaction vessel, and 8g of 5-methyl-2-acetylfuran and 50ml of tetrahydrofuran were added. After the reaction kettle is sealed, N is firstly used2Replacing air in the reaction kettle, and recharging 2MPa of H2. The reaction kettle is heated to 260 ℃ and reacted for 4 hours. After the reaction is finished, the kettle 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. Instrument information: shimadzu QP-2010 Ultra; information on the chromatographic column: rtx-5 Sil MS (30 m.times.0.25 mm.times.0.25 μm). Setting a chromatographic program: after heating to 280 ℃ at 10 ℃ per minute from 100 ℃, the temperature was maintained for 20 minutes. The chromatographic analysis result shows that the conversion rate of the 5-methyl-2-acetylfuran reaches 99 percent, and the yield of the methylfuran reaches 93 percent. The solvent was removed by rotary evaporation to give 2-methyl-5-ethylfuran.
(4) Preparation of 2, 5-furandicarboxylic acid by oxidation of 2-methyl-5-ethylfuran
2g of 2-methyl-5-ethyl furan, 10ml of water and a proper amount of H are sequentially added into a reaction kettle with a polytetrafluoroethylene lining2O2And sealing the reaction kettle. The reaction kettle is heated to 60 ℃ to react for 3 hours.
After the reaction is finished, cooling the kettle to room temperature, filtering to separate out solids, washing with ice water for three times, and drying in an oven at 60 ℃ for 12 hours. The white solid was subjected to composition analysis by high performance liquid chromatography. Instrument information: the Shimadzu high performance liquid chromatograph has a UV-VIS detector with the model of SPD-16, a liquid delivery pump with the model of LC-16 and a column incubator with the model of CTO-16; information on the chromatographic column: wondasil C18-WR5um (5 μm × 4.6mm I.D. × 150 mm); in the test conditions, the mobile phase: methanol/1% acetic acid solution 10:90 at a flow rate of 1mL/min, a column temperature of 30 ℃, a detection wavelength of 264nm, and a sample injection volume of 10 μ L. The chromatographic analysis showed a 2, 5-furandicarboxylic acid content of 97% giving a yield of 95.3% by calculation of the oxidation step.
Example 3
(1) Preparation of methylfuran by furfural hydrodeoxygenation
The furfural hydrogenation catalyst was prepared by an impregnation method, in which appropriate amounts of copper nitrate and nickel nitrate were dissolved in water in a molar ratio of Fe to Ni of 1 to 9. Adding aluminum oxide powder into the solution, wherein the total metal accounts for SiO218% of the mass of (a). The mixture was stirred to dryness, dried overnight at 80 ℃ and ground to a powder. Calcining the powder at 450 ℃ in air, and then reducing the calcined powder with hydrogen at the same temperature to obtain the furfural hydrogenation catalyst.
Adding 1g of hydrogenation catalyst into a reaction kettle, adding 15g of furfural, and adding 80ml of absolute ethyl alcohol as a solvent. After the reaction kettle is sealed, N is firstly used2Replacing air in the reaction kettle, and recharging 4MPa of H2. The reaction kettle is heated to 240 ℃ and reacted for 10 hours.
After the reaction is finished, the kettle 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. Instrument information: shimadzu QP-2010 Ultra; information on the chromatographic column: rtx-5 Sil MS (30 m.times.0.25 mm.times.0.25 μm). Setting a chromatographic program: after heating to 280 ℃ at 10 ℃ per minute from 100 ℃, the temperature was maintained for 20 minutes. The chromatographic analysis result shows that the conversion rate of the furfural reaches 98 percent and the yield of the methylfuran reaches 95 percent. The solvent was removed by distillation under reduced pressure to give methylfuran.
(2) Acetylation of methylfuran to prepare 5-methyl-2-acetylfuran
The acetylation of the methylfuran is carried out in a fixed bed at atmospheric pressure. 6g of HBEA catalyst was tableted and formed, and then sieved to obtain catalyst particles having a particle size of 20-60 mesh. The catalyst is loaded in the reactor. Then 8g of methylfuran and 22.4g of acetic anhydride were weighed out and dissolved in 1, 2-dichloroethane. And heating the reactor to 100 ℃, introducing the reaction mixed liquor into the reactor through a constant flow pump, and reacting for 8 hours.
After the reaction is finished, the kettle 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. Instrument information: shimadzu QP-2010 Ultra; information on the chromatographic column: rtx-5 Sil MS (30 m.times.0.25 mm.times.0.25 μm). Setting a chromatographic program: after heating to 280 ℃ at 10 ℃ per minute from 100 ℃, the temperature was maintained for 20 minutes. The chromatographic analysis result shows that the conversion rate of the methyl furan reaches 93 percent, and the yield of the 5-methyl-2-acetylfuran reaches 89 percent. The solvent was removed by distillation under reduced pressure to give 5-methyl-2-acetylfuran.
(3) Preparation of 2-methyl-5-ethyl furan by hydrodeoxygenation of 5-methyl-2-acetylfuran
The 5-methyl-2-acetylfuran hydrogenation catalyst is prepared by a hydrothermal method. Dissolving nickel nitrate into a certain amount of water, adding a certain amount of ammonium chloride and ammonia water, and fully dissolving. A certain amount of SiO2Adding into the mixed solution, the metal is SiO230% of the mass. After the mixed solution is stirred for 2 hours, the mixed solution is transferred into a self-pressure hydrothermal kettle, and the hydrothermal kettle is placed in a 120 ℃ oven for reaction for 6 hours. The resulting catalyst was washed with water and oven dried at 60 ℃ overnight. The obtained solid was ground and calcined at 450 ℃ for 4 hours in an air atmosphere, followed by reduction at the same temperature for 4 hours in a hydrogen atmosphere, to obtain a hydrogenation catalyst.
1g of a hydrogenation catalyst was charged into a reaction vessel, and 15g of 5-methyl-2-acetylfuran and 80ml of tetrahydrofuran were added. After the reaction kettle is sealed, N is firstly used2Replacing air in the reaction kettle, and recharging 4MPa of H2. The reaction kettle is heated to 250 ℃ and reacts for 4 hours. After the reaction is finished, the kettle 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. Instrument information: shimadzu QP-2010 Ultra;information on the chromatographic column: rtx-5 Sil MS (30 m.times.0.25 mm.times.0.25 μm). Setting a chromatographic program: after heating to 280 ℃ at 10 ℃ per minute from 100 ℃, the temperature was maintained for 20 minutes. The chromatographic analysis result shows that the conversion rate of the 5-methyl-2-acetylfuran reaches 96 percent, and the yield of the methylfuran reaches 92 percent. The solvent was removed by rotary evaporation to give 2-methyl-5-ethylfuran.
(4) Preparation of 2, 5-furandicarboxylic acid by oxidation of 2-methyl-5-ethylfuran
2g of 2-methyl-5-ethyl furan, a proper amount of NaBr and MnCl are sequentially added into a reaction kettle with a polytetrafluoroethylene lining2And 10mL of acetic acid, sealing the reaction vessel, and adding N2Replacing air in the reaction kettle, and recharging 0.5MPa of O2. The reaction kettle is heated to 160 ℃ and reacted for 5 hours.
After the reaction is finished, cooling the kettle to room temperature, filtering to separate out solids, washing with ice water for three times, and drying in an oven at 60 ℃ for 12 hours. The white solid was subjected to composition analysis by high performance liquid chromatography. Instrument information: the Shimadzu high performance liquid chromatograph has a UV-VIS detector with the model of SPD-16, a liquid delivery pump with the model of LC-16 and a column incubator with the model of CTO-16; information on the chromatographic column: wondasil C18-WR5um (5 μm × 4.6mm I.D. × 150 mm); in the test conditions, the mobile phase: methanol/1% acetic acid solution 10:90 at a flow rate of 1mL/min, a column temperature of 30 ℃, a detection wavelength of 264nm, and a sample injection volume of 10 μ L. The chromatographic analysis showed a content of 93% of 2, 5-furandicarboxylic acid, which was calculated to give a yield of 86% in the oxidation step.
The above description is only an example of the present application and is not intended to limit the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.
Claims (9)
1. A synthetic method of 2, 5-furandicarboxylic acid is characterized by comprising the following steps:
(1) mixing furfural, a hydrogenation catalyst and a solvent, adding the mixture into a reactor, wherein the hydrogenation catalyst is a supported catalyst containing one or more metals of Cu, Ni, Fe, Co and Ru, introducing inert gas to replace air in the reactor, subsequently introducing hydrogen to replace the inert gas, keeping the hydrogen pressure at 0.1-4MPa, heating the reactor to 180-280 ℃, continuously reacting for 0.1-24 hours, and separating to obtain methylfuran;
(2) mixing methylfuran with acetic anhydride, dissolving in a solvent, then introducing into a normal-pressure fixed bed reactor filled with a solid acid catalyst, wherein the solid acid catalyst is a solid molecular sieve, phosphotungstic acid, phosphomolybdic acid or a supported catalyst taking phosphotungstic acid or phosphomolybdic acid as an active center, the temperature of the reactor is 30-150 ℃, and separating to obtain 5-methyl-2-acetylfuran;
(3) adding 5-methyl-2-acetylfuran, a supported metal catalyst with an active center of one or more of Cu, Ni, Fe, Co and Ru and a solvent into a reactor, introducing inert gas to replace air in the reactor, subsequently introducing hydrogen to replace the inert gas, keeping the pressure of the hydrogen at 1-4MPa, heating the reactor to 180 ℃ and 280 ℃, continuously reacting for 5 minutes-24 hours, and separating to obtain 2-methyl-5-ethylfuran;
(4) adding 2-methyl-5-ethyl furan into a reactor with a polytetrafluoroethylene lining, reacting for 0.1-16 hours under the catalytic action of an oxidant, and separating to obtain 2, 5-furandicarboxylic acid.
2. The synthesis method of claim 1, wherein the total metal loading of the hydrogenation catalyst in step (1) accounts for 0.05-50% of the mass ratio of the carrier, and the carrier is one or more of activated carbon, carbon nanofiber, silica, titanium dioxide, alumina and pure silicon molecular sieve.
3. The synthesis method according to claim 1, wherein in the step (1), the mass ratio of the hydrogenation catalyst to the furfural is 5: 1 to 1: 20.
4. the method of claim 1, wherein the solvent in step (1) or step (3) is one or more of methanol, ethanol, tetrahydrofuran, n-hexane, and dodecane.
5. The synthesis method of claim 1, wherein the solid molecular sieve is one or more of ZSM-5, HBEA, HY, HSUY and HMOR.
6. The synthesis process according to claim 1, wherein the solvent in step (2) is a chlorinated alkane, which is ethyl chloride, dichloroethane, chloroform, chloropropane or dichloropropane.
7. The synthesis method of claim 1, wherein the total metal loading of the supported metal catalyst in the step (3) accounts for 0.05-50% of the mass ratio of the carrier, and the carrier is one or more of activated carbon, nano carbon fiber, silicon dioxide, titanium dioxide, aluminum oxide and pure silicon molecular sieve.
8. The method of claim 1, wherein the oxidizing agent used in step (4) is KMnO4Acid solution of (2) or H2O2And (3) solution.
9. The synthesis method according to claim 1, wherein the oxidant in step (4) is oxygen at 0.1-4Mpa, the metal salt of Co, the metal salt of Mn, the metal salt of Br or the solution of HBr is added into the reactor, wherein the content of Co, Mn or Br is 0.1-10% of the raw material of 2-methyl-5-ethylfuran by mole percent, and the reactor is further added with a solvent, wherein the solvent is acetonitrile, 1, 2-dichloroethane, chloroform, acetic acid, propionic acid or n-butyric acid.
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