Non-noble metal composite oxide catalyst as well as preparation method and application thereof

Abstract

The invention discloses a non-noble metal composite oxide catalyst as well as a preparation method and application thereof. The method comprises the steps that soluble salt of metal A and soluble salt of metal B are dissolved in water, a solution 1 is obtained, the metal A is selected from one of cobalt or manganese, and the metal B is selected from one of titanium, vanadium, iron or nickel; dissolving a template agent and an oxime compound in water, and adjusting the pH value to 9-11 to obtain a solution 2; dropwise adding the solution 1 into the solution 2, and aging the obtained mixed solution after dropwise adding is completed; and filtering, and washing, drying, grinding and roasting the obtained solid to obtain the metal composite oxide catalyst. According to the invention, two transition metals are used as raw materials, and the catalyst with high reaction activity and stability is prepared through the synergistic effect between metal ions and the chelation between the oxime compound and the metal ions. The method is green and environment-friendly in process and low in cost, and has a very good industrial application prospect in preparation of 2, 5-furandicarboxylic acid.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of chemical technology, and particularly relates to a non-noble metal composite oxide catalyst and a preparation method and application thereof. BACKGROUND

[0002] At present, with the utilization of fossil resources bringing increasingly serious environmental problems to the society, finding renewable biomass resources to replace petrochemical resources has become a development trend. The U.S. Department of Energy screened 12 kinds of bio-based "platform compounds" in 2024, and 2,5-furan dicarboxylic acid (FDCA) is the only platform compound containing an aromatic ring structure, which can replace existing petrochemical benzene ring-based products, and has received widespread attention from all walks of life. Therefore, efficient preparation of FDCA is of great significance.

[0003] At present, the preparation processes of FDCA mainly include stoichiometric oxidation method, noble metal oxidation method, AMOCO oxidation method, etc. The stoichiometric oxidation method mainly uses nitric acid and potassium permanganate oxidation, which has low yield and high preparation cost. The AMOCO oxidation method has high FDCA yield, and is carried out in acetic acid under high temperature and high pressure, which has great safety hazards and high requirements for equipment and safety. The noble metal oxidation method mainly uses gold, palladium, platinum and other noble metals as catalysts to obtain FDCA with high yield, but there is a problem of noble metal loss in the use process. Since the noble metal is expensive, it is not suitable for large-scale production.

[0004] CN108712931A discloses a catalyst for preparing 2,5-furan dicarboxylic acid. The catalyst is a catalyst for carboxylating a furan compound or a derivative thereof containing a hydroxyl group and a carbonyl group and is configured such that noble metal nanoparticles are incorporated into a spinel support, the noble metal being selected from at least one of platinum, palladium and ruthenium. However, due to the use of noble metal, the cost of the catalyst is high, and there is a problem of noble metal loss in the use process, which reduces the activity of the catalyst. In order to reduce the cost of the catalyst, it is of great significance to design and develop a non-noble metal catalyst for preparing 2,5-furan dicarboxylic acid.

[0005] CN106565647A discloses a method for preparing 2,5-FDCA by catalytic oxidation of HMF using a non-noble metal cerium-based composite oxide as a catalyst. The method prepares a composite catalyst of manganese, iron, copper, titanium and other metal oxides and cerium oxide, and effectively catalyzes the oxidation of HMF to prepare 2,5-FDCA under the conditions of using oxygen or air as an oxidant and adding an alkaline additive. However, the yield of 2,5-FDCA prepared by using the catalyst of the invention is only 86.7% at most.

[0006] CN117417315A discloses a synthesis method of 2,5-furan dicarboxylic acid, comprising: under the protection of nitrogen, 5-hydroxymethyl furfural and Cu / Mn catalyst are added into a high-pressure reaction kettle, and the reaction is carried out under heating conditions, while the pH value of the system is adjusted to be alkaline by adding lye, and nitrogen is continuously introduced to maintain the pressure in the kettle basically unchanged. The invention uses Cu / Mn bimetallic catalyst to catalyze 5-hydroxymethyl furfural to synthesize 2,5-furan dicarboxylic acid, which improves the yield of 2,5-furan dicarboxylic acid to a certain extent, but the highest yield of 2,5-furan dicarboxylic acid is still not more than 90%.

[0007] In summary, it is of great significance to develop a catalyst with low cost, high selectivity and stability for preparing 2,5-furan dicarboxylic acid. SUMMARY

[0008] In order to overcome the defects of the prior art, the present application provides a non-noble metal composite oxide catalyst, a preparation method and application thereof. The method uses double transition metals as raw materials, and simultaneously adds an oxime compound during the preparation process, so that the finally prepared catalyst has high catalytic activity and stability, and can be used for efficiently catalyzing the oxidation of furan compounds to prepare 2,5-furan dicarboxylic acid.

[0009] The first aspect of the present application provides a preparation method of a non-noble metal composite oxide catalyst, comprising the following steps:

[0010] (1) dissolving soluble salts of metal A and metal B in water to obtain solution 1, wherein metal A is selected from one of cobalt or manganese, and metal B is selected from one of titanium, vanadium, iron or nickel;

[0011] (2) dissolving a template agent and an oxime compound in water, adjusting the pH to 9-11 to obtain solution 2;

[0012] (3) adding solution 1 dropwise to solution 2, and aging the obtained mixture after the dropwise addition is completed;

[0013] (4) filtering the product obtained in step (3), washing, drying and grinding the obtained solid, and then calcining in an air atmosphere to obtain the non-noble metal composite oxide catalyst.

[0014] The present application uses two kinds of soluble salts of transition metals as raw materials, and there is a synergistic effect between the two kinds of metal ions, which can significantly improve the activity of the catalyst. The addition of the template agent can increase the specific surface area of the catalyst, increase the contact area between the metal ions and the raw materials. At the same time, the chelation of the oxime compound and the metal ion forms a complex with a specific structure, which can increase the reaction active site of the catalyst and improve the catalytic activity of the catalyst. After calcination in an air atmosphere, the template agent and the oxime compound are all removed by combustion, and finally a non-noble metal composite oxide catalyst with high catalytic activity and stability is obtained.

[0015] Preferably, the molar ratio of metal ion A and metal ion B in the soluble salt of metal A and the soluble salt of metal B is 1:1-3. With the increase of the proportion of metal ion A, the specific surface area of the catalyst decreases and the pore size increases. The catalyst formed in this proportion range can promote the shape-selective catalysis of the catalyst and the transfer of the substrate and the product in the catalyst, thereby improving the activity of the catalyst.

[0016] Preferably, the soluble salt of metal A includes cobalt acetate tetrahydrate, cobalt nitrate hexahydrate, manganese acetate tetrahydrate or manganese nitrate tetrahydrate.

[0017] Preferably, the soluble salt of metal B includes sodium titanate, iron sulfate, vanadyl sulfate or nickel nitrate hexahydrate.

[0018] Preferably, the template agent is cetyltrimethylammonium bromide, polyethylene glycol, n-butylamine, tetraethylammonium hydroxide, sodium dodecyl sulfate, ethylenediaminetetraacetic acid, sucrose fatty acid ester, etc.

[0019] Preferably, the mass of the template agent is 0.5-3 times the total mass of the metal soluble salt. The addition of the template agent can increase the specific surface area of the catalyst and improve the contact area between the substrate and the catalyst.

[0020] Preferably, the oxime compound is acetone oxime, butanone oxime, cyclohexanone oxime, octanoyl hydroxamic acid, 2,5-furandimethylfurfural oxime, 5-hydroxymethyl-2-furfural oxime, butanedione oxime, etc.

[0021] Preferably, the molar amount of the oxime compound is 0.1-1 times the molar amount of the metal ion. The oxime group in the oxime compound can be complexed with the metal ion to form a metal complex with a specific structure similar to formula (I) or formula (II), improve the ordered arrangement of the metal ion, increase the catalyst site, and improve the activity of the catalyst.

[0022]

[0023] Further preferably, the metal A is manganese (Mn), the metal B is nickel (Ni), and the molar ratio of manganese to nickel is 1:1-2. Within this ratio range, sufficient Mn can be incorporated into the crystal lattice of NiO, and Mn atoms occupy the Ni 2+ The vacancy and the interaction between Mn-Ni weaken the bonding ability of Mn-O, thereby increasing the electron transfer rate. When the Mn content is too high, the growth and aggregation of the crystal grains are inhibited, the crystal lattice structure is destroyed, the specific surface area of the catalyst is reduced, the pore size is increased, and thus the active sites are reduced.

[0024] More preferably, the metal A is manganese (Mn), the metal B is nickel (Ni), and the molar ratio of manganese, nickel to the oxime compound is 1:1.9:1.5. Within this range, the catalyst prepared has a better catalytic effect.

[0025] Preferably, in step (2), the pH is adjusted to 9-11 using a basic solution, and the basic solution is an aqueous solution of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, or the like.

[0026] Preferably, the aging temperature is 80-150°C, and the time is 2-6h.

[0027] Preferably, the calcination temperature is 450-700°C, and the time is 2-6h.

[0028] The second aspect of the present application provides a non-noble metal composite oxide catalyst prepared by the above preparation method, and the active component of the non-noble metal composite oxide catalyst has a general formula ABxOy, wherein A is selected from one of cobalt or manganese, B is selected from one of titanium, vanadium, iron or nickel, 1≤x≤3, and 2≤y≤8.

[0029] The active component of the catalyst of the present application has a general formula ABxOy. Since the metal A is doped into the crystal lattice of the metal B oxide, the presence of the B metal weakens the bonding ability of the A metal and oxygen, accelerates the transfer of electrons, and is conducive to the generation and regeneration of oxygen vacancies in the catalyst. The construction of the A-O-B bond provides a new electron transfer channel, accelerates the transfer of electrons, and is conducive to the rapid regeneration of oxygen vacancies in the catalyst, thereby realizing efficient oxidation of furan compounds to 2,5-furan dicarboxylic acid.

[0030] The third aspect of the present application provides the use of the non-noble metal composite oxide catalyst in the preparation of 2,5-furan dicarboxylic acid by catalytic oxidation. The catalyst of the present application can improve the interaction between oxygen and the substrate through the synergistic effect between the two metals, and realize efficient heterogeneous oxidation to prepare FDCA. The use of the catalyst of the present application to catalyze the oxidation of furan compounds to prepare 2,5-furan dicarboxylic acid has a substrate conversion rate of 100%, and the selectivity and yield of 2,5-furan dicarboxylic acid are both above 95%.

[0031] Preferably, the method for preparing 2,5-furan dicarboxylic acid by catalytic oxidation using the non-noble metal composite oxide catalyst is as follows: dissolving a furan compound in a solvent, adding the non-noble metal composite oxide catalyst, introducing an oxygen source, and heating to perform a reaction to obtain a 2,5-furan dicarboxylic acid solution.

[0032] Preferably, the furan compound is 5-hydroxymethylfurfural, 2,5-diformylfuran, 5-formyl-2-furan carboxylic acid, or 5-hydroxymethyl-2-furan carboxylic acid.

[0033] Preferably, the solvent is water.

[0034] Preferably, the amount of the non-noble metal composite oxide catalyst is 5-20% of the mass of the furan compound.

[0035] Preferably, the oxygen source is air or pure oxygen.

[0036] Preferably, the reaction temperature is 100-200°C, the reaction pressure is 0.5-2Mpa, the pH of the reaction system is 7-11, and the reaction time is 2-12h.

[0037] In the process for preparing 2,5-furan dicarboxylic acid, water, which is more safe and environmentally friendly, is used as the solvent, air or oxygen is used as the oxygen source, and the reaction system is weakly alkaline, so that the 2,5-furan dicarboxylic acid is salted, easy to separate, and the active metal of the catalyst is not lost, thereby improving the stability and cycle number of the catalyst.

[0038] Compared with the prior art, the present application has at least the following beneficial effects:

[0039] (1) The non-noble metal composite oxide catalyst prepared in the present application uses non-noble metals in the preparation process, has low preparation cost, and has obvious improved catalytic activity due to the synergistic effect between metal ions in the bimetallic oxide composite catalyst; the addition of a template improves the specific surface area of the catalyst and increases the contact area between metal ions and raw materials; at the same time, the chelation between the oxime compound and the metal ions forms a complex with a specific structure, which increases the active sites of the catalyst and improves the catalytic activity of the catalyst.

[0040] (2) The non-noble metal composite oxide catalyst catalyzes the oxidation of a furan compound to prepare 2,5-furan dicarboxylic acid in a weakly alkaline aqueous solution, so that the 2,5-furan dicarboxylic acid is salted, easy to separate, and the active metal of the catalyst is not lost under weakly alkaline conditions, thereby improving the stability and cycle number of the catalyst.

[0041] (3) The process for preparing 2,5-furan dicarboxylic acid in the application is more safe and environment-friendly, using water as solvent and air or oxygen as oxygen source, and has the advantages of green process, high safety, low cost, high product selectivity and good industrial application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0042] Figure 1 Raman spectrum of the non-noble metal composite oxide catalyst prepared in Example 4. DETAILED DESCRIPTION

[0043] The technical solutions of the application will be described in detail below with specific examples, so that the technical solutions of the application can be better understood and implemented by the skilled in the art. The specific functional details disclosed herein should not be interpreted as limiting, but only as a basis for the claims and for teaching the skilled in the art to employ the representative basis of the application in different ways in any appropriate detailed implementation.

[0044] Example 1

[0045] Preparation of the catalyst: 1.17 g of titanium acid and 1.33 g of cobalt acetate tetrahydrate were dissolved in water to obtain solution 1. 3.7 g of tetraethylammonium hydroxide and 1.92 g of acetone oxime were dissolved in water, and the pH was adjusted to 9.0 using sodium carbonate to obtain solution 2. Under stirring, solution 1 was slowly added to solution 2, heated to 80℃ and aged for 6 h, and the solid was filtered, washed with water, dried and crushed, then added to a muffle furnace, heated to 700℃ at a rate of 5℃ / min and calcined for 4 h to obtain the catalyst CoTi 1.9 O 4.0 .

[0046] 0.5 g of the above catalyst, 10 g of 2,5-diformylfuran and 100 g of water were added to a reaction kettle, 15 g of sodium bicarbonate was added, the reaction kettle was sealed, heated to 200℃ in an air atmosphere, air was introduced at a rate of 1 L / min, and the reaction pressure was maintained at 2 MPa, and the reaction was carried out for 20 min. The concentration of 2,5-furan dicarboxylic acid in the solution was detected after cooling, and the yield was calculated to be 96.2%.

[0047] Example 2

[0048] Preparation of catalyst: 5 g of cobalt nitrate hexahydrate and 5 g of iron sulfate were dissolved in 100 ml of water to obtain solution 1. 30 ml of polyethylene glycol 400 and 1.37 g of 2,5-furandicarboxylic acid oxime were dissolved in water, and the pH of the solution was adjusted to about 11 using sodium hydroxide to obtain solution 2. Solution 1 was slowly added to solution 2, and heating was performed to 150°C for 2 h. After filtration, the solid was obtained, and then water washing, drying, and crushing were performed, and the solid was added to a muffle furnace, and heating was performed to 600°C at a rate of 5°C / min for 3 h to obtain the catalyst CoFe 1.4 O 2.7 .

[0049] The above catalyst 2.0 g, 10.2 g of 5-formyl-2-furancarboxylic acid, 9.0 g of sodium carbonate, and 100 g of water were added to a reaction kettle, the reaction kettle was sealed, and heating was performed to 150°C in the range of air, air was introduced at a rate of 1 L / min, the pressure of the reaction kettle was maintained at 1.5 MPa, and reaction was performed for 1 h. After cooling, the concentration of 2,5-furandicarboxylic acid in the solution was detected, and the yield was calculated to be 97.6%.

[0050] Example 3

[0051] Preparation of catalyst: 2.1 g of manganese acetate tetrahydrate and 5.05 g of vanadyl sulfate hydrate were dissolved in water to obtain solution 1. 15 g of ethylenediaminetetraacetic acid and 0.55 g of 5-hydroxymethyl-2-furancarboxylic acid oxime were dissolved in water, and the pH of the solution was adjusted to 10 using potassium carbonate to obtain solution 2. Solution 1 was added to solution 2, and then added to a hydrothermal reactor, and heating was performed to 120°C for 4 h. After filtration, the solid was obtained, and then water washing, drying, and crushing were performed, and the solid was added to a muffle furnace, and heating was performed to 700°C at a rate of 5°C / min for 2 h to obtain the catalyst MnV 2.3 O 6.5 .

[0052] The above catalyst 1.0 g, 10.2 g of 5-hydroxymethyl-2-furancarboxylic acid, 10.1 g of potassium bicarbonate, and 100 g of water were added to a reaction kettle, the reaction kettle was sealed, and heating was performed to 120°C in the range of oxygen, oxygen was introduced at a rate of 100 ml / min, the pressure of the reaction was maintained at 0.5 MPa, and reaction was performed for 2 h. After cooling, the concentration of 2,5-furandicarboxylic acid in the solution was detected, and the yield was calculated to be 98.3%.

[0053] Example 4

[0054] Catalyst preparation: 1.6 g of manganese nitrate tetrahydrate and 4.6 g of nickel nitrate hexahydrate were dissolved in water to obtain solution 1. 20 g of sodium dodecyl sulfate and 1.29 g of dimethylglyoxime were dissolved in water, and the pH of the solution was adjusted to 10 using sodium carbonate to obtain solution 2. Solution 1 was added to solution 2, and then added to a hydrothermal reactor, where it was heated to 100 °C and aged for 4 h. The solid obtained was filtered, washed with water, dried, and pulverized, then added to a Maverick reactor and calcined at 550 °C for 3 h at a rate of 5 °C / min to obtain the catalyst MnNi. 2.5 O 4.8 .

[0055] Weigh 0.8g of the above catalyst and 13.6g of 5-hydroxymethylfurfural and add them to 100g of water, along with 11.1g of potassium carbonate. Seal the reactor and heat it to 100℃ in an oxygen-rich environment. Pour oxygen in at 100ml / min and maintain the reaction pressure at 0.5MPa. React for 4 hours, then cool the solution and measure the concentration of 2,5-furandicarboxylic acid. The yield was calculated to be 96.8%.

[0056] The Raman spectrum of the non-noble metal composite oxide catalyst prepared in this embodiment is as follows: Figure 1 As shown, by Figure 1 It can be seen that at 512cm -1 and 1067cm -1 There is obvious Ni at this location 2+ -O tensile vibration peak, while at 375cm -1 and 692cm -1 No obvious Ni was observed at the site. 3 + The -O tensile vibration peak indicates that the introduction of Mn leads to the Ni 3+ The decrease in Ni content indicates that the Ni–Mn interaction inhibits the growth of Ni in NiO. 3+ The generation; 633cm -1 The peak value at 633 cm⁻¹ represents the tensile vibration peak of Mn-O, which is higher than that of MnOx. -1 The spectral band shifts to a lower wavenumber, indicating that the Ni–Mn interaction weakens the Mn-O bond interaction.

[0057] Catalyst recycling experiment:

[0058] The solution after the reaction in this embodiment was filtered, washed with water, dried and the catalyst was recovered. The recovered catalyst was used for a recycling experiment, and the results are shown in Table 1.

[0059] Table 1. Experimental results of catalyst recycling

[0060] Number of applications 1 2 3 4 5 FDCA yield (%) 96.8 96.5 95.7 96.3 95.6

[0061] From Table 1, it can be seen that the catalytic activity of the catalyst does not decrease significantly after five times of reuse, and the catalyst can be reused.

[0062] Example 5

[0063] Preparation of the catalyst: 1.8 g of manganese acetate tetrahydrate and 4.1 g of nickel nitrate hexahydrate were dissolved in water to obtain solution 1. 15 g of sucrose fatty acid ester and 0.9 g of 2,5-furandicarboxaldehyde oxime were dissolved in water, and the pH of the solution was adjusted to 11 using sodium hydroxide to obtain solution 2. Solution 1 was added dropwise to solution 2, and then added to a hydrothermal reactor, which was heated to 100°C for aging for 3 h. The solid obtained was filtered, washed with water, dried, and crushed, and then added to a muffle furnace, which was heated to 700°C at a rate of 5°C / min for calcination for 3 h to obtain the catalyst MnNi 1.9 O 3.9 .

[0064] The above catalyst 0.8 g, 13.6 g of 5-hydroxymethyl-2-furancarboxylic acid, 10.8 g of potassium bicarbonate were added to 100 g of water, and the reaction kettle was sealed, heated to 130°C in the oxygen range, and oxygen was introduced at a rate of 100 ml / min, and the reaction pressure was maintained at 1.2 MPa, and the reaction was carried out for 2 h. The concentration of 2,5-furandicarboxylic acid in the solution was detected after cooling, and the yield was calculated to be 99.2%.

[0065] Example 6

[0066] Preparation of the catalyst: 1.8 g of manganese acetate tetrahydrate and 4.1 g of nickel nitrate hexahydrate were dissolved in water to obtain solution 1. 15 g of sucrose fatty acid ester and 0.9 g of 2,5-furandicarboxaldehyde oxime were dissolved in water, and the pH of the solution was adjusted to 11 using sodium hydroxide to obtain solution 2. Solution 1 was added dropwise to solution 2, and then added to a hydrothermal reactor, which was heated to 100°C for aging for 3 h. The solid obtained was filtered, washed with water, dried, and crushed, and then added to a muffle furnace, which was heated to 700°C at a rate of 5°C / min for calcination for 3 h to obtain the catalyst MnNi 2.1 O 3.6 .

[0067] The above catalyst 0.8 g, 13.6 g of 5-hydroxymethyl-2-furancarboxylic acid, 10.8 g of potassium bicarbonate were added to 100 g of water, and the reaction kettle was sealed, heated to 130°C in the oxygen range, and oxygen was introduced at a rate of 100 ml / min, and the reaction pressure was maintained at 1.2 MPa, and the reaction was carried out for 2 h. The concentration of 2,5-furandicarboxylic acid in the solution was detected after cooling, and the yield was calculated to be 99.2%.

[0068] Comparative Example 1

[0069] Similar to Example 4, except that the mass of nickel nitrate was increased to 9.5 g to obtain the catalyst MnNi 5.1 O8.1 The catalyst was used to oxidize 5-hydroxymethylfurfural to prepare 2,5-furan dicarboxylic acid, and the yield was 58.3%. It is illustrated that when the ratio of nickel to manganese is greater than 3, due to the decrease of manganese ions and the increase of nickel ions, less Mn enters the NiO crystal lattice, and the electronic transfer rate between Ni-O-Mn is slow, resulting in the decrease of catalytic activity.

[0070] Comparative Example 2

[0071] Similar to Example 4, except that the mass of manganese nitrate was increased to 6.8 g, and the catalyst MnNi 0.6 O 2.6 The catalyst was used to oxidize 5-hydroxymethylfurfural to prepare 2,5-furan dicarboxylic acid, and the yield was 65.6%. It is illustrated that when the ratio of manganese to nickel is greater than 1, the addition of a higher content of Mn leads to the high dispersion of Mn2O3 or NiMnO3 on the surface of NiO, which inhibits the growth and aggregation of NiO crystal grains during calcination, and inhibits the electronic transfer rate between Ni-O-Mn, resulting in the decrease of catalytic activity.

[0072] Comparative Example 3

[0073] Similar to Example 4, except that no butanedione oxime was added to obtain the catalyst MnNi 2.9 O 5.9 The catalyst was used to oxidize 5-hydroxymethylfurfural to prepare 2,5-furan dicarboxylic acid, and the yield was 83.9%. It is illustrated that the addition of oxime compounds reduces the activity of the catalyst.

[0074] The above is only a few embodiments of the present application, and does not limit the present application in any form. Although the above preferred embodiments are disclosed, they are not intended to limit the present application. Any skilled person in the art can make some changes or modifications to the above disclosed technical content without departing from the scope of the technical solution of the present application, and such changes or modifications are equivalent to equivalent embodiments, and are within the scope of the technical solution.

Claims

1. A method for producing a non-noble metal composite oxide catalyst, characterized by, The method comprises the following steps: (1) dissolving soluble salts of metal A and metal B in water to obtain solution 1, wherein metal A is selected from one of cobalt or manganese, and metal B is selected from one of titanium, vanadium, iron or nickel; (2) dissolving a template agent and an oxime compound in water, and adjusting pH to 9-11 to obtain solution 2; (3) adding solution 1 dropwise into solution 2, and aging the obtained mixture after the dropwise addition is completed; (4) filtering the product obtained in step (3), washing, drying and grinding the obtained solid, and then calcining in air atmosphere to obtain the non-noble metal composite oxide catalyst.

2. The production method according to claim 1, characterized by, The molar ratio of metal ion A to metal ion B in the soluble salt of metal A and the soluble salt of metal B is 1:1-3.

3. The production method according to claim 1 or 2, characterized by, The template agent is cetyltrimethylammonium bromide, polyethylene glycol, n-butylamine, tetraethylammonium hydroxide, sodium dodecyl sulfate, ethylenediaminetetraacetic acid or sucrose fatty acid ester; the mass of the template agent is 0.5-3 times the total mass of the metal soluble salts.

4. The production method according to claim 3, characterized by, The oxime compound is acetone oxime, butanone oxime, cyclohexanone oxime, octanoylhydroxamic acid, 2,5-furandicarboxaldehyde oxime, 5-hydroxymethyl-2-furancarboxaldehyde oxime or butanedione oxime; the molar amount of the oxime compound is 0.1-1 times the molar amount of the metal ions.

5. The preparation method according to claim 4, characterized in that, The aging temperature is 80-150℃, and the time is 2-6h.

6. The production method according to claim 5, characterized by, The calcination temperature is 450-700℃, and the time is 2-6h.

7. The non-noble metal composite oxide catalyst produced by the production method according to any one of claims 1 to 6, characterized by, The active component of the non-noble metal composite oxide catalyst has the general formula ABxOy, wherein A is selected from one of cobalt or manganese, B is selected from one of titanium, vanadium, iron or nickel, 1≤x≤3 and 2≤y≤8.

8. The non-noble metal composite oxide catalyst according to claim 7 is used in the preparation of 2,5-furandicarboxylic acid by catalytic oxidation.

9. Use according to claim 8, characterized in that, The application method is as follows: dissolving a furan compound in a solvent, adding the non-noble metal composite oxide catalyst, and passing an oxygen source, under the conditions of a reaction temperature of 100-200℃, a reaction pressure of 0.5-2Mpa, and a reaction system pH of 7-11, to react for 2-12h to obtain a 2,5-furandicarboxylic acid solution.

10. Use according to claim 9, characterized in that, The mass of the non-noble metal composite oxide catalyst is 5-20% of the mass of the furan compound.

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