A catalyst and a preparation method thereof, and a method for preparing 2,5-furandicarboxylic acid using the catalyst

Abstract

The present invention provides a CoCu x O y Catalyst and preparation method thereof and method for preparing 2,5-furandicarboxylic acid by using the catalyst. x O y The molar ratio of Co, Cu and O in the catalyst is 1:(0.2-1):(3-4). The catalyst preparation method comprises: adding a solution of calcium perchlorate in N,N-diethylacrylamide dropwise to a mixed aqueous solution of copper nitrate and cobalt nitrate, filtering after aging to obtain a black cake-like precipitate, and calcining at 180°C to obtain CoCu x O y The present invention also provides CoCu prepared by the above method. x O y A method for preparing 2,5-furandicarboxylic acid with a catalyst. x O y The preparation method of the catalyst is simple to operate and the conditions are mild; the prepared catalyst has high catalytic efficiency; and the use of the catalyst to prepare 2,5-furandicarboxylic acid has the characteristics of high efficiency, easy separation, low cost, less pollution, etc.

Description

Technical Field

[0001] The present invention belongs to the field of biomass energy, and specifically relates to a CoCu x O y A catalyst and a preparation method thereof, and a method for preparing 2,5-furandicarboxylic acid by catalyzing the catalyst. Background Art

[0002] As the only renewable carbon resource, biomass can be converted into high-value-added fuels and chemicals, and can play an important role in solving energy and environmental problems. 2,5-Furandicarboxylic acid (FDCA) is one of the potential bio-based platform compounds. At present, the preparation methods of FDCA are mainly divided into the following categories: furoic acid is prepared by disproportionation reaction, chloromethylation reaction or CO2 solid phase reaction; hexanoic acid is prepared by oxidative dehydration reaction; diglycolic acid is used as raw material, reacted with methanol and thionyl chloride to obtain dimethyl diglycolate, and then prepared by dehydration condensation with trimer glyoxal; 2,5-dimethylfuran, 2-methyl-5-acetylfuran or 5-methyl-2-furfural are used as raw materials; 5-hydroxymethylfurfural (HMF) obtained by hydrolysis of hexose is prepared by oxidation. The structure of HMF has similar functional group positions to FDCA, so the preparation of FDCA from HMF is currently the most studied and optimal raw material choice, and is the most potential route for the preparation of FDCA.

[0003] At present, 2,5-furandicarboxylic acid is mainly prepared by oxidation of 5-hydroxymethylfurfural (HMF), which generally requires the addition of a catalyst, and the catalyst is divided into heterogeneous catalysts and homogeneous catalysts. Homogeneous catalysts are mainly transition metal salts such as Co and Mn. For example, the Grushin research group used cobalt salts to homogeneously catalyze the oxidation of HMF. The initial concentration of HMF was about 8%. In 7MPa air, at 125°C, Co / Mn / Br / Zr catalyzed the reaction for 3 hours, and the FDCA yield was 60% (W. Partenheimer, VV Grushin, Adv. Synth. Catal., 2001, 343: 102-111). The homogeneous catalytic reaction system has the disadvantages of low yield, difficult separation of metal salts, and serious bromine environmental pollution. In contrast, the heterogeneous catalytic method has the advantages of high selectivity, environmental protection, and easy separation of products. For the heterogeneous catalytic oxidation of HMF, two major categories of noble metal catalysts and non-noble metal catalysts are mainly used. Precious metal catalysts include Pt, Au, Pd, etc. For example, Han Xuewang et al. used carbon-magnesium oxide as an alkaline carrier to load the precious metal Pt. Under alkaline-free conditions, the FDCA yield can reach 95% (Xuewang Han, Liang Geng, Green Chemistry, 2015, 14: 4-17). Lin Lu et al. in their patent (201010228459) used Pt, Au, Pd loaded C or CuO-Ag2O as a catalyst to catalyze the oxidation of HMF in an alkaline solution to prepare FDCA, and obtained a higher FDCA yield. Existing non-precious metal heterogeneous catalysts generally have the problems of low selectivity and poor stability under oxygen or air conditions. For example, Zhang Zehui's research group used nano-Fe3O4-CoO x The catalytic oxidation of HMF to prepare FDCA can achieve a 68.6% FDCA yield using tert-butyl peroxide as an oxidant, but the FDCA yield is only 4.2% if oxygen is used as an oxidant (Shuguo Wang, Zehui Zhang, ACSSustainable Chem. Eng. 2015, 3: 406-412). Summary of the invention

[0004] In order to solve the above problems, the present invention aims to provide a CoCu x O y A catalyst and a preparation method thereof, and a method for preparing 2,5-furandicarboxylic acid using the catalyst. The preparation of 2,5-furandicarboxylic acid using the catalyst has the characteristics of high efficiency, easy separation, low cost, less pollution, etc.

[0005] To achieve the above object, the present invention provides a CoCu x O y catalyst, wherein the CoCu x O yThe molar ratio of Co, Cu and O in the catalyst is 1:(0.2-1):(3-4).

[0006] The present invention also provides the CoCu x O y A method for preparing a catalyst comprises the following steps:

[0007] Cobalt nitrate and copper nitrate are dispersed in deionized water at a mass ratio of 1:1-2, and the total mass concentration of the two is controlled to be below 10%; then calcium perchlorate and N,N-diethylacrylamide solution (preferably 20 mL) with a mass concentration of 10% are measured and added dropwise to the mixed aqueous solution of copper nitrate and cobalt nitrate at a flow rate of 2-5 drops / second. After the addition is completed, the mixture is aged for 4-6 hours, filtered to obtain a black cake-like precipitate, and calcined in an air atmosphere to obtain CoCu x O y catalyst.

[0008] In the above preparation method, preferably, the mass ratio of calcium perchlorate to N,N-diethylacrylamide is 1:1.

[0009] In the above preparation method, preferably, the amount of calcium perchlorate and N,N-diethylacrylamide solution used is 20 mL.

[0010] In the above preparation method, preferably, the calcination temperature is 180° C. and the calcination time is 1.5-2.5 hours.

[0011] The present invention also provides a method for preparing 2,5-furandicarboxylic acid by catalytic oxidation, which is to use the CoCu x O y The catalyst performs a catalytic reaction, and the method comprises the following steps:

[0012] Using 5-hydroxymethylfurfural as raw material, water, CoCu x O y The catalyst and the oxidant are mixed in a reactor in a certain proportion, reacted at 20-90° C. for 10-600 minutes, and then returned to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution. The reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 (preferably 1) to obtain a precipitate, which is centrifuged or filtered, and then filtered and vacuum dried to obtain 2,5-furandicarboxylic acid.

[0013] In the above preparation method, preferably, the oxidant is one or a combination of two or more of NaClO, KClO, ClO2.

[0014] In the above preparation method, preferably, the mass concentration of the 5-hydroxymethylfurfural (relative to the oxidant) is 0.5-25%, preferably 10-20%.

[0015] In the above preparation method, preferably, the mass ratio of the catalyst to 5-hydroxymethylfurfural is 1:1.

[0016] In the above preparation method, preferably, the molar ratio of the oxidant to 5-hydroxymethylfurfural is (1-20):1, preferably (3-10):1.

[0017] In the above preparation method, preferably, the acid used to adjust the pH is one or a combination of two or more of hydrochloric acid, sulfuric acid and phosphoric acid.

[0018] In the above preparation method, preferably, the acid concentration used for adjusting the pH is an aqueous solution with a mass concentration of 50%.

[0019] In the above preparation method, preferably, the reaction temperature is 25-35°C.

[0020] In the above preparation method, preferably, the reaction time is 20-180 minutes.

[0021] According to a specific embodiment of the present invention, the above preparation method can be carried out according to the following specific steps:

[0022] Using biomass platform compound 5-hydroxymethylfurfural as raw material, water, CoCu x O y The catalyst and the oxidant are mixed in a reactor in a certain proportion, reacted at 25-70° C. for 60-300 minutes, and then cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution. The reaction solution is filtered, and then a proper amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, the precipitate is washed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder.

[0023] According to a specific embodiment of the present invention, preferably, the above preparation method is carried out according to the following specific steps:

[0024] Using biomass platform compound 5-hydroxymethylfurfural as raw material, water, CoCu x O y The catalyst and the oxidant are mixed in a reactor in a certain proportion, reacted at 30° C. for 180 minutes, and then cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution. The reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, the precipitate is rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder.

[0025] The method for preparing 2,5-furandicarboxylic acid by the catalyst provided by the present invention has the following beneficial effects:

[0026] The catalyst dosage is small, the catalytic reaction system is simple and efficient, the reaction conditions are mild, there are few by-products, and the conversion rate exceeds 99% through chromatographic analysis. The purity of the product after separation and purification is as high as 99.5%. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The product 2,5-furandicarboxylic acid separated from Example 17 of the present invention 1 H-NMR (DMSO-d6) nuclear magnetic resonance spectrum.

[0028] Figure 2 The product 2,5-furandicarboxylic acid separated from Example 17 of the present invention 13 C-NMR (DMSO-d6) nuclear magnetic resonance spectrum. DETAILED DESCRIPTION

[0029] In order to enable those skilled in the art to better understand the technical solutions in this application, the present invention will be described more clearly and completely below in conjunction with specific embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0030] CoCu x O y Catalyst Preparation Example

[0031] Embodiment 1:

[0032] Cobalt nitrate and copper nitrate were dispersed in deionized water, wherein the mass concentration of cobalt nitrate was 5% and the mass concentration of copper nitrate was 5%. Then 20 ml of 10% calcium perchlorate and N,N-diethylacrylamide solution were measured and added to the mixed aqueous solution of copper nitrate and cobalt nitrate at a flow rate of 3 drops / second. After the addition was completed, the mixture was aged for 4 hours, filtered to obtain a black cake-like precipitate, and calcined at 180°C in air for 2 hours to obtain CoCu x O y catalyst.

[0033] Through analysis and characterization, the molar ratio of Co, Cu and O in the catalyst is 1:0.8:3.5.

[0034] Embodiment 2:

[0035] Cobalt nitrate and copper nitrate were dispersed in deionized water, wherein the mass concentration of cobalt nitrate was 3% and the mass concentration of copper nitrate was 6%. Then 20 ml of 10% calcium perchlorate and N,N-diethylacrylamide solution were measured and added to the mixed aqueous solution of copper nitrate and cobalt nitrate at a flow rate of 2 drops / second. After the addition was completed, the mixture was aged for 4 hours and filtered to obtain a black cake-like precipitate. The mixture was calcined at 180°C in air for 2 hours to obtain CoCu x O y catalyst.

[0036] Through analysis and characterization, the molar ratio of Co, Cu and O in the catalyst is 1:0.9:3.9.

[0037] Embodiment 3:

[0038] Cobalt nitrate and copper nitrate were dispersed in deionized water, wherein the mass concentration of cobalt nitrate was 3% and the mass concentration of copper nitrate was 6%. Then 20 ml of 10% calcium perchlorate and N,N-diethylacrylamide solution were measured and added dropwise to the mixed aqueous solution of copper nitrate and cobalt nitrate at a flow rate of 4 drops / second. After the addition was completed, the mixture was aged for 6 hours and filtered to obtain a black cake-like precipitate. The mixture was calcined at 180°C for 1.5 hours in an air atmosphere to obtain CoCu x O y catalyst.

[0039] Through analysis and characterization, the molar ratio of Co, Cu and O in the catalyst is 1:0.7:3.2.

[0040] Embodiment 4:

[0041] Cobalt nitrate and copper nitrate were dispersed in deionized water, wherein the mass concentration of cobalt nitrate was 3% and the mass concentration of copper nitrate was 4%. Then 20 ml of 10% calcium perchlorate and N,N-diethylacrylamide solution were measured and added dropwise to the mixed aqueous solution of copper nitrate and cobalt nitrate at a flow rate of 4 drops / second. After the addition was completed, the mixture was aged for 5 hours and filtered to obtain a black cake-like precipitate. The mixture was calcined at 180°C for 2.5 hours in an air atmosphere to obtain CoCu x O y catalyst.

[0042] Through analysis and characterization, the molar ratio of Co, Cu and O in the catalyst is 1:0.9:3.1.

[0043] Embodiment 5:

[0044] Cobalt nitrate and copper nitrate were dispersed in deionized water, wherein the mass concentration of cobalt nitrate was 1% and the mass concentration of copper nitrate was 2%. Then 20 ml of 10% calcium perchlorate and N,N-diethylacrylamide solution were measured and added to the mixed aqueous solution of copper nitrate and cobalt nitrate at a flow rate of 2 drops / second. After the addition was completed, the mixture was aged for 4 hours and filtered to obtain a black cake-like precipitate. The mixture was calcined at 180°C in air for 1.5 hours to obtain CoCu x O y catalyst.

[0045] Through analysis and characterization, the molar ratio of Co, Cu and O in the catalyst is 1:0.6:3.0.

[0046] Embodiment 6:

[0047] Cobalt nitrate and copper nitrate were dispersed in deionized water, wherein the mass concentration of cobalt nitrate was 3% and the mass concentration of copper nitrate was 6%. Then 20 ml of 10% calcium perchlorate and N,N-diethylacrylamide solution were measured and added dropwise to the mixed aqueous solution of copper nitrate and cobalt nitrate at a flow rate of 5 drops / second. After the addition was completed, the mixture was aged for 6 hours and filtered to obtain a black cake-like precipitate. The mixture was calcined at 180°C for 2.5 hours in an air atmosphere to obtain CoCu x O y catalyst.

[0048] Through analysis and characterization, the molar ratio of Co, Cu and O in the catalyst is 1:0.9:3.4.

[0049] Embodiment 7:

[0050] Cobalt nitrate and copper nitrate were dispersed in deionized water, wherein the mass concentration of cobalt nitrate was 5% and the mass concentration of copper nitrate was 5%. Then 20 ml of 10% calcium perchlorate and N,N-diethylacrylamide solution were measured and added to the mixed aqueous solution of copper nitrate and cobalt nitrate at a flow rate of 2 drops / second. After the addition was completed, the mixture was aged for 6 hours and filtered to obtain a black cake-like precipitate. The mixture was calcined at 180°C for 1.5 hours in an air atmosphere to obtain CoCu x O y catalyst.

[0051] Through analysis and characterization, the molar ratio of Co, Cu and O in the catalyst is 1:0.4:3.0.

[0052] Example of Preparation of 2,5-Furandicarboxylic Acid

[0053] Embodiment 8:

[0054] The preparation of 2,5-furandicarboxylic acid provided in this embodiment is carried out by the following steps: 0.25 g of 5-hydroxymethylfurfural, 0.125 g of catalyst CoCux O y (Co / Cu / O molar ratio is 1:0.8:3.5), 50 ml of sodium hypochlorite solution with a mass concentration of 5.7% is added to a 100 ml round-bottom flask, and the reaction is carried out at 0°C for 300 minutes at a speed of 400 r / min. After the reaction, the reaction solution is cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, it is rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the conversion rate of 5-hydroxymethylfurfural is 100%, and the mass yield of 2,5-furandicarboxylic acid is 118.1%.

[0055] The mass yield calculation formula of 2,5-furandicarboxylic acid is:

[0056] 5-Hydroxymethylfurfural conversion (C_HMF, mol%) = (1-HMF mass in product / HMF initial mass) × 100%

[0057] Yield of 2,5-furandicarboxylic acid (Y_X, mol%) = mass of 2,5-furandicarboxylic acid in the product / (initial mass of 5-hydroxymethylfurfural) × 100%

[0058] Embodiment 9:

[0059] The preparation of 2,5-furandicarboxylic acid provided in this embodiment is carried out by the following steps: 0.5 g of 5-hydroxymethylfurfural, 0.3 g of catalyst CoCu x O y (Co / Cu / O molar ratio is 1:0.8:3.5), 50 ml of sodium hypochlorite solution with a mass concentration of 5.7% is added to a 100 ml round-bottom flask, and the reaction is carried out at 5° C. for 270 minutes at a speed of 400 r / min. After the reaction is completed, the reaction solution is cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, it is rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate is 100%, and the mass yield of 2,5-furandicarboxylic acid is 119.2% (the calculation method is the same as that in Example 1).

[0060] Embodiment 10:

[0061] The preparation of 2,5-furandicarboxylic acid provided in this embodiment is carried out by the following steps: 0.75 g of 5-hydroxymethylfurfural, 0.525 g of catalyst CoCu x O y(Co / Cu / O molar ratio is 1:0.7:3.2), 50 ml of sodium hypochlorite solution with a mass concentration of 8.3% is added to a 100 ml round-bottom flask, and the reaction is carried out at 10° C. for 240 minutes at a speed of 400 r / min. After the reaction is completed, the reaction solution is cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, it is rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate is 100%, and the mass yield of 2,5-furandicarboxylic acid is 114.0% (the calculation method is the same as that in Example 1).

[0062] Embodiment 11:

[0063] The preparation of 2,5-furandicarboxylic acid provided in this embodiment is carried out by the following steps: 1.0 g of 5-hydroxymethylfurfural, 0.8 g of catalyst CoCu x O y (Co / Cu / O molar ratio is 1:0.9:3.9), 50 ml of sodium hypochlorite solution with a mass concentration of 10.6% is added to a 100 ml round-bottom flask, and the reaction is carried out at 15° C. for 200 minutes at a speed of 400 r / min. After the reaction is completed, the reaction solution is cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid, and finally rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate is 100%, and the mass yield of 2,5-furandicarboxylic acid is 115.7% (the calculation method is the same as that in Example 1).

[0064] Embodiment 12:

[0065] The preparation of 2,5-furandicarboxylic acid provided in this embodiment is carried out by the following steps: 1.25 g of 5-hydroxymethylfurfural, 1.125 g of catalyst CoCu x O y(Co / Cu / O molar ratio is 1:0.9:3.1), 50 ml of sodium hypochlorite solution with a mass concentration of 12.8% is added to a 100 ml round-bottom flask, and the reaction is carried out at 17.5° C. for 180 minutes at a speed of 400 r / min. After the reaction is completed, the reaction solution is cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, it is rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate is 100%, and the mass yield of 2,5-furandicarboxylic acid is 116.7% (the calculation method is the same as that in Example 1).

[0066] Embodiment 13:

[0067] The preparation of 2,5-furandicarboxylic acid provided in this embodiment is carried out by the following steps: 1.5 g of 5-hydroxymethylfurfural, 1.5 g of catalyst CoCu x O y (Co / Cu / O molar ratio is 1:0.6:3.0), 50 ml of sodium hypochlorite solution with a mass concentration of 14.8% is added to a 100 ml round-bottom flask, and the reaction is carried out at 20° C. for 150 minutes at a speed of 400 r / min. After the reaction is completed, the reaction solution is cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, it is rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate is 100%, and the mass yield of 2,5-furandicarboxylic acid is 114.9% (the calculation method is the same as that in Example 1).

[0068] Embodiment 14:

[0069] The preparation of 2,5-furandicarboxylic acid provided in this embodiment is carried out by the following steps: 1.75 g of 5-hydroxymethylfurfural, 1.93 g of catalyst CoCu x O y(Co / Cu / O molar ratio is 1:0.9:3.4), 50 ml of sodium hypochlorite solution with a mass concentration of 16.5% is added to a 100 ml round-bottom flask, and the reaction is carried out at 22.5° C. for 120 minutes at a speed of 400 r / min. After the reaction is completed, the reaction solution is cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, it is rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate is 100%, and the mass yield of 2,5-furandicarboxylic acid is 119.2% (the calculation method is the same as that in Example 1).

[0070] Embodiment 15:

[0071] The preparation of 2,5-furandicarboxylic acid provided in this embodiment is carried out by the following steps: 2.0 g of 5-hydroxymethylfurfural, 2.4 g of catalyst CoCu x O y (Co / Cu / O molar ratio is 1:0.6:3.0), 50 ml of sodium hypochlorite solution with a mass concentration of 18.2% is added to a 100 ml round-bottom flask, and the reaction is carried out at 60° C. for 10 minutes at a speed of 400 r / min. After the reaction is completed, the reaction solution is cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, it is rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate is 100%, and the mass yield of 2,5-furandicarboxylic acid is 118.6% (the calculation method is the same as that in Example 1).

[0072] Embodiment 16:

[0073] The preparation of 2,5-furandicarboxylic acid provided in this embodiment is carried out by the following steps: 2.25 g of 5-hydroxymethylfurfural, 2.8 g of catalyst CoCu x O y(Co / Cu / O molar ratio is 1:0.7:3.2), 50 ml of sodium hypochlorite solution with a mass concentration of 19.5% is added to a 100 ml round-bottom flask, and the reaction is carried out at 57.5° C. for 13 minutes at a speed of 400 r / min. After the reaction is completed, the reaction solution is cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, it is rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate is 100%, and the mass yield of 2,5-furandicarboxylic acid is 120.8% (the calculation method is the same as that in Example 1).

[0074] Embodiment 17:

[0075] The preparation of 2,5-furandicarboxylic acid provided in this embodiment is carried out by the following steps: 2.5 g of 5-hydroxymethylfurfural, 3.25 g of catalyst CoCu x O y (Co / Cu / O molar ratio is 1:0.8:3.5), 50 ml of sodium hypochlorite solution with a mass concentration of 20.7% is added to a 100 ml round-bottom flask, and the reaction is carried out at 55° C. for 15 minutes at a speed of 400 r / min. After the reaction is completed, the reaction solution is cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, it is rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder. The conversion rate of 5-hydroxymethylfurfural is 100%, and the mass yield of 2,5-furandicarboxylic acid is 122.4% (the calculation method is the same as that in Example 1). The 2,5-furandicarboxylic acid obtained in this example 1 H-NMR diagram Figure 1 , 13 C-NMR diagram Figure 2 .

[0076] Embodiment 18:

[0077] The preparation of 2,5-furandicarboxylic acid provided in this embodiment is carried out by the following steps: 2.75 g of 5-hydroxymethylfurfural, 1.35 g of catalyst CoCu x O y(Co / Cu / O molar ratio is 1:0.9:3.9), 50 ml of sodium hypochlorite solution with a mass concentration of 21.8% is added to a 100 ml round-bottom flask, and the reaction is carried out at 52.5° C. for 18 minutes at a speed of 400 r / min. After the reaction is completed, the reaction solution is cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, it is rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate is 100%, and the mass yield of 2,5-furandicarboxylic acid is 112.6% (the calculation method is the same as that in Example 1).

[0078] Embodiment 19:

[0079] The preparation of 2,5-furandicarboxylic acid provided in this embodiment is carried out by the following steps: 3.0 g of 5-hydroxymethylfurfural, 4.2 g of catalyst CoCu x O y (Co / Cu / O molar ratio is 1:0.9:3.9), 50 ml of sodium hypochlorite solution with a mass concentration of 22.5% is added to a 100 ml round-bottom flask, and the reaction is carried out at 50° C. for 20 minutes at a speed of 400 r / min. After the reaction is completed, the reaction solution is cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, it is rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate is 100%, and the mass yield of 2,5-furandicarboxylic acid is 113.9% (the calculation method is the same as that in Example 1).

[0080] Embodiment 20:

[0081] The preparation of 2,5-furandicarboxylic acid provided in this embodiment is carried out by the following steps: 3.25 g of 5-hydroxymethylfurfural, 4.7 g of catalyst CoCu x O y(Co / Cu / O molar ratio is 1:0.9:3.1), 50 ml of sodium hypochlorite solution with a mass concentration of 23.0% is added to a 100 ml round-bottom flask, and the reaction is carried out at 47.5° C. for 16 minutes at a speed of 400 r / min. After the reaction is completed, the reaction solution is cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, it is rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate is 100%, and the mass yield of 2,5-furandicarboxylic acid is 115.5% (the calculation method is the same as that in Example 1).

[0082] Embodiment 21:

[0083] The preparation of 2,5-furandicarboxylic acid provided in this embodiment is carried out by the following steps: 3.5 g of 5-hydroxymethylfurfural, 5.25 g of catalyst CoCu x O y (Co / Cu / O molar ratio is 1:0.8:3.5), 50 ml of sodium hypochlorite solution with a mass concentration of 23.6% is added to a 100 ml round-bottom flask, and the reaction is carried out at 45 ° C for 14 minutes at a speed of 400 r / min. After the reaction is completed, the reaction solution is cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, it is rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate is 100%, and the mass yield of 2,5-furandicarboxylic acid is 113.0% (the calculation method is the same as that in Example 1).

[0084] Embodiment 22:

[0085] The preparation of 2,5-furandicarboxylic acid provided in this embodiment is carried out by the following steps: 3.75 g of 5-hydroxymethylfurfural, 5.8 g of catalyst CoCu x O y(Co / Cu / O molar ratio is 1:0.8:3.5), 50 ml of sodium hypochlorite solution with a mass concentration of 23.7% is added to a 100 ml round-bottom flask, and the reaction is carried out at 40° C. for 22 minutes at a speed of 400 r / min. After the reaction is completed, the reaction solution is cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, it is rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate is 100%, and the mass yield of 2,5-furandicarboxylic acid is 111.3% (the calculation method is the same as that in Example 1).

[0086] Embodiment 23:

[0087] The preparation of 2,5-furandicarboxylic acid provided in this embodiment is carried out by the following steps: 4.0 g of 5-hydroxymethylfurfural, 6.4 g of catalyst CoCu x O y (Co / Cu / O molar ratio is 1:0.6:3.0), 50 ml of sodium hypochlorite solution with a mass concentration of 23.6% is added to a 100 ml round-bottom flask, and the reaction is carried out at 37.5° C. for 25 minutes at a speed of 400 r / min. After the reaction is completed, the reaction solution is cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, it is rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate is 100%, and the mass yield of 2,5-furandicarboxylic acid is 108.2% (the calculation method is the same as that in Example 1).

[0088] Embodiment 24:

[0089] The preparation of 2,5-furandicarboxylic acid provided in this embodiment is carried out by the following steps: 4.25 g of 5-hydroxymethylfurfural, 7.0 g of catalyst CoCu x O y(Co / Cu / O molar ratio is 1:0.6:3.0), 50 ml of sodium hypochlorite solution with a mass concentration of 22.6% is added to a 100 ml round-bottom flask, and the reaction is carried out at 35° C. for 30 minutes at a speed of 400 r / min. After the reaction is completed, the reaction solution is cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, it is rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate is 100%, and the mass yield of 2,5-furandicarboxylic acid is 107.3% (the calculation method is the same as that in Example 1).

[0090] Embodiment 25:

[0091] The preparation of 2,5-furandicarboxylic acid provided in this embodiment is carried out by the following steps: 4.5 g of 5-hydroxymethylfurfural, 7.65 g of catalyst CoCu x O y (Co / Cu / O molar ratio is 1:0.9:3.9), 50 ml of sodium hypochlorite solution with a mass concentration of 21.25% is added to a 100 ml round-bottom flask, and the reaction is carried out at 30° C. for 35 minutes at a speed of 400 r / min. After the reaction is completed, the reaction solution is cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, it is rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate is 100%, and the mass yield of 2,5-furandicarboxylic acid is 103.4% (the calculation method is the same as that in Example 1).

[0092] Embodiment 26:

[0093] The preparation of 2,5-furandicarboxylic acid provided in this embodiment is carried out by the following steps: 4.75 g of 5-hydroxymethylfurfural, 0.8.55 g of catalyst CoCu x O y(Co / Cu / O molar ratio is 1:0.9:3.9), 50 ml of sodium hypochlorite solution with a mass concentration of 19.6% is added to a 100 ml round-bottom flask, and the reaction is carried out at 27.5° C. for 40 minutes at a speed of 400 r / min. After the reaction is completed, the reaction solution is cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, it is rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate is 100%, and the mass yield of 2,5-furandicarboxylic acid is 102.0% (the calculation method is the same as that in Example 1).

[0094] Embodiment 27:

[0095] The preparation of 2,5-furandicarboxylic acid provided in this embodiment is carried out by the following steps: 5.0 g of 5-hydroxymethylfurfural, 10.0 g of catalyst CoCu x O y (Co / Cu / O molar ratio is 1:0.9:3.4), 50 ml of sodium hypochlorite solution with a mass concentration of 17.7% is added to a 100 ml round-bottom flask, and the reaction is carried out at 25° C. for 45 minutes at a speed of 400 r / min. After the reaction is completed, the reaction solution is cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid, and finally rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate is 100%, and the mass yield of 2,5-furandicarboxylic acid is 100.0% (the calculation method is the same as that in Example 1).

[0096] Embodiment 28:

[0097] The preparation of 2,5-furandicarboxylic acid provided in this embodiment is carried out by the following steps: 5.6 g of 5-hydroxymethylfurfural, 1.4 g of catalyst CoCu x O y(Co / Cu / O molar ratio is 1:0.9:3.4), 50 ml of sodium hypochlorite solution with a mass concentration of 5.6% is added to a 100 ml round-bottom flask, and the reaction is carried out at 30° C. for 42 minutes at a speed of 400 r / min. After the reaction is completed, the reaction solution is cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, it is rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate is 100%, and the mass yield of 2,5-furandicarboxylic acid is 121.4% (the calculation method is the same as that in Example 1).

[0098] Embodiment 29:

[0099] The preparation of 2,5-furandicarboxylic acid provided in this embodiment is carried out by the following steps: 0.8 g of 5-hydroxymethylfurfural, 1.375 g of catalyst CoCu x O y (Co / Cu / O molar ratio is 1:0.6:3.0), 50 ml of sodium hypochlorite solution with a mass concentration of 8.27% is added to a 100 ml round-bottom flask, and the reaction is carried out at 35 ° C for 50 minutes at a speed of 400 r / min. After the reaction is completed, the reaction solution is cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, it is rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate is 100%, and the mass yield of 2,5-furandicarboxylic acid is 120.0% (the calculation method is the same as that in Example 1).

[0100] Embodiment 30:

[0101] The preparation of 2,5-furandicarboxylic acid provided in this embodiment is carried out by the following steps: 0.9 g of 5-hydroxymethylfurfural is dissolved in 50 ml of aqueous solution in a 100 ml round-bottom flask, 1.3 g of catalyst CoCu x O y(Co / Cu / O molar ratio is 1:0.6:3.0), ClO2 with a molar amount of 5 times that of 5-hydroxymethylfurfural is introduced, the reaction is carried out at 20°C for 60 minutes at a speed of 400r / min. After the reaction, the reaction solution is cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid, and finally rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate is 100%, and the mass yield of 2,5-furandicarboxylic acid is 99.0% (the calculation method is the same as that in Example 1).

[0102] Embodiment 31:

[0103] The preparation of 2,5-furandicarboxylic acid provided in this embodiment is carried out by the following steps: 0.5 g of 5-hydroxymethylfurfural, 0.6 g of the catalyst CoCu prepared by coprecipitation x O y (Co / Cu / O molar ratio is 1:0.8:3.5), 50ml of sodium hypochlorite solution with a mass concentration of 4.2% is added to a 100ml round-bottom flask, and the reaction is carried out at 25°C for 60 minutes at a speed of 400r / min. After the reaction is completed, the reaction solution is cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, which is centrifuged or filtered to obtain 2,5-furandicarboxylic acid, and finally rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate is 70%, and the mass yield of 2,5-furandicarboxylic acid is 71% (the calculation method is the same as that in Example 1).

[0104] Comparative Example 1:

[0105] 0.5 g of 5-hydroxymethylfurfural, 0.6 g of catalyst CoO y , 50 ml of a 4.2% sodium hypochlorite solution was added to a 100 ml round-bottom flask, and the reaction was carried out at 25° C. for 60 minutes at a speed of 400 r / min. After the reaction, the reaction solution was cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution was filtered, and then an appropriate amount of acid was added to adjust the pH to 1-2 to obtain a precipitate, which was centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, the precipitate was washed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder. The conversion rate of 5-hydroxymethylfurfural was 63%, and the mass yield of 2,5-furandicarboxylic acid was 31% (the calculation method was the same as that in Example 1).

[0106] Comparative Example 2:

[0107] 0.5 g of 5-hydroxymethylfurfural, 0.6 g of catalyst CuOy , 50 ml of a sodium hypochlorite solution with a mass concentration of 4.2% was added to a 100 ml round-bottom flask, and the reaction was carried out at 25° C. for 60 minutes at a speed of 400 r / min. After the reaction was completed, the reaction solution was cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution was filtered, and then an appropriate amount of acid was added to adjust the pH to 1-2 to obtain a precipitate, and 2,5-furandicarboxylic acid was obtained by centrifugation or filtration. Finally, the 2,5-furandicarboxylic acid was rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate was 45%, and the mass yield of 2,5-furandicarboxylic acid was 14% (the calculation method is the same as that in Example 1).

[0108] Comparative Example 3:

[0109] 0.5 g of 5-hydroxymethylfurfural, 0.49 g of CuCl2, and 50 ml of a sodium hypochlorite solution with a mass concentration of 17.7% were added to a 100 ml round-bottom flask, and the reaction was carried out at 25° C. for 60 minutes at a speed of 400 r / min. After the reaction, the reaction solution was cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution was filtered, and then an appropriate amount of acid was added to adjust the pH to 1-2 to obtain a precipitate, which was centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, the mixture was rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder. The conversion rate of 5-hydroxymethylfurfural was 35%, and the mass yield of 2,5-furandicarboxylic acid was 34.6% (the calculation method was the same as that in Example 1).

[0110] Comparative Example 4:

[0111] 4.25 g of 5-hydroxymethylfurfural, 3.25 g of manganese-cobalt bimetallic oxide, and 50 ml of sodium hypochlorite solution with a mass concentration of 22.6% were added to a 100 ml round-bottom flask, and the reaction was carried out at 25° C. for 60 minutes at a speed of 400 r / min. After the reaction, the reaction solution was cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution was filtered, and then an appropriate amount of acid was added to adjust the pH to 1-2 to obtain a precipitate, which was centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, the mixture was rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder. The conversion rate of 5-hydroxymethylfurfural was 45.6%, and the mass yield of 2,5-furandicarboxylic acid was 29.7% (the calculation method was the same as that in Example 1).

[0112] Comparative Example 5:

[0113] 0.8 g of 5-hydroxymethylfurfural, 1.47 g of cerium-titanium composite oxide catalyst, and 50 ml of sodium hypochlorite solution with a mass concentration of 21.25% were added to a 100 ml round-bottom flask, and the reaction was carried out at 25° C. for 60 minutes at a speed of 400 r / min. After the reaction, the reaction solution was cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution was filtered, and then an appropriate amount of acid was added to adjust the pH to 1-2 to obtain a precipitate, which was centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, the mixture was rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder. The conversion rate of 5-hydroxymethylfurfural was 58.3%, and the mass yield of 2,5-furandicarboxylic acid was 32.6% (the calculation method was the same as that in Example 1).

[0114] Comparative Example 6:

[0115] 4.5 g of 5-hydroxymethylfurfural, 3.6 g of catalyst CoCu x O y (prepared with calcium perchlorate as an oxidant), 50 ml of a sodium hypochlorite solution with a mass concentration of 17.7% was added to a 100 ml round-bottom flask, and the reaction was carried out at 25° C. for 60 minutes at a speed of 400 r / min. After the reaction was completed, the reaction solution was cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution was filtered, and then an appropriate amount of acid was added to adjust the pH to 1-2 to obtain a precipitate, which was centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, it was rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate was 73%, and the mass yield of 2,5-furandicarboxylic acid was 36.9% (the calculation method was the same as that in Example 1).

[0116] Comparative Example 7:

[0117] 0.8 g of 5-hydroxymethylfurfural, 0.49 g of catalyst CoCu x O y (prepared with N,N-diethylacrylamide as an oxidant), 50 ml of a sodium hypochlorite solution with a mass concentration of 17.7% was added to a 100 ml round-bottom flask, and the reaction was carried out at 25° C. for 60 minutes at a speed of 400 r / min. After the reaction was completed, the reaction solution was cooled to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution was filtered, and then an appropriate amount of acid was added to adjust the pH to 1-2 to obtain a precipitate, which was centrifuged or filtered to obtain 2,5-furandicarboxylic acid. Finally, it was rinsed with deionized water, filtered, and vacuum dried to obtain a milky white 2,5-furandicarboxylic acid solid powder, the 5-hydroxymethylfurfural conversion rate was 65.3%, and the mass yield of 2,5-furandicarboxylic acid was 40.4% (the calculation method was the same as that in Example 1).

Claims

1. A method for preparing 2,5-furandicarboxylic acid by catalytic oxidation, comprising the following steps: Using 5-hydroxymethylfurfural as raw material, water, CoCu x O y The catalyst and the oxidant are mixed in a reactor in a certain proportion, reacted at 20-90° C. for 10-600 minutes, and then returned to room temperature to obtain a 2,5-furandicarboxylic acid reaction solution, the reaction solution is filtered, and then an appropriate amount of acid is added to adjust the pH to 1-2 to obtain a precipitate, centrifuged or filtered, and then filtered and vacuum dried to obtain 2,5-furandicarboxylic acid; The CoCu x O y The molar ratio of Co, Cu and O in the catalyst is 1:(0.2-0.9):(3-3.9).

2. The preparation method according to claim 1, wherein The CoCu x O y The preparation method of the catalyst comprises the following steps: Cobalt nitrate and copper nitrate are dispersed in water at a mass ratio of 1:1-2, and the total mass concentration of the two is controlled below 10%; then a certain mass concentration of calcium perchlorate and N,N-diethylacrylamide aqueous solution is measured and added dropwise to the mixed aqueous solution of copper nitrate and cobalt nitrate at a flow rate of 2-5 drops / second. After the addition is completed, aging is continued for 4-6 hours, and a black cake-like precipitate is obtained by filtering, and then CoCu is calcined in an air atmosphere to obtain x O y catalyst.

3. The preparation method according to claim 2, wherein The CoCu x O y In the preparation method of the catalyst, the calcination condition is calcination at 180° C. for 1.5-2.5 hours.

4. The preparation method according to claim 2, wherein The CoCu x O y In the preparation method of the catalyst, the mass ratio of calcium perchlorate to N,N-diethylacrylamide is 1:

1.

5. The preparation method according to claim 2, wherein: The CoCu x O y In the preparation method of the catalyst, the mass concentration of the calcium perchlorate and N,N-diethylacrylamide is 5-30%.

6. The preparation method according to claim 2, wherein: The CoCu x O y In the preparation method of the catalyst, the mass concentration of the calcium perchlorate and N,N-diethylacrylamide is 10-20%.

7. The preparation method according to claim 1, wherein The oxidant is one of NaClO, KClO, ClO2 or a combination of two or more thereof.

8. The preparation method according to claim 1, wherein Relative to the total mass of the reaction system, the mass concentration of the 5-hydroxymethylfurfural is 0.5-25%.

9. The preparation method according to claim 1, wherein Relative to the total mass of the reaction system, the mass concentration of the 5-hydroxymethylfurfural is 10-20%.

10. The preparation method according to claim 1, wherein: The CoCu x O y The mass ratio of the catalyst to 5-hydroxymethylfurfural is 1:

1.

11. The preparation method according to claim 1 or 7, wherein: The molar ratio of the oxidant to 5-hydroxymethylfurfural is (1-20):

1.

12. The preparation method according to claim 1 or 7, wherein: The molar ratio of the oxidant to 5-hydroxymethylfurfural is (3-10):

1.

13. The preparation method according to claim 1, wherein The acid used to adjust the pH is one or a combination of two or more of hydrochloric acid, sulfuric acid and phosphoric acid.

14. The preparation method according to claim 1, wherein: The acid used to adjust the pH is an aqueous solution with a mass concentration of 50%.

15. The preparation method according to claim 1, wherein: The reaction temperature is 25-35° C.; the reaction time is 20-180 minutes.

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