Metal organic coordination porous polymer derivative catalyst for preparing 2, 5-dimethylfuran through hydrogenation of 5-hydroxymethylfurfural

Abstract

The invention discloses a metal organic coordination porous polymer derivative catalyst for preparing 2, 5-dimethylfuran through hydrogenation of 5-hydroxymethylfurfural, and the catalyst is prepared by calcining and deriving after anchoring a metal active component by a metal organic coordination porous polymer, the metal organic coordination porous polymer is formed by coordination of one or two metals selected from cerium and zirconium and an organic carboxylic acid ligand; the metal active component is at least one of copper, nickel and cobalt. The invention discloses an application of a catalyst in preparation of 2, 5-dimethylfuran by hydrogenation of 5-hydroxymethylfurfural. According to the invention, the anchoring capability of uncoordinated carboxylic acid of an organic carboxylic acid ligand in the metal organic coordination porous polymer is utilized to stabilize the metal active component, the agglomeration phenomenon in the calcining and reaction process is obviously inhibited, and meanwhile, the mass transfer path of reactants is optimized through ordered pore channels of the metal organic coordination porous polymer. The catalyst provided by the invention improves the conversion rate of 5-hydroxymethylfurfural and the selectivity of 2, 5-dimethylfuran.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of catalytic materials, and relates to a metal organic coordination porous polymer derivative catalyst for preparing 2,5-dimethylfuran by hydrogenation of 5-hydroxymethylfurfural, in particular to a metal organic coordination porous polymer derivative supported metal catalyst and a method for producing 2,5-dimethylfuran by hydrogenation of 5-hydroxymethylfurfural under the action of the metal organic coordination porous polymer derivative supported metal catalyst. BACKGROUND

[0002] Energy is an important pillar industry of the national economy, and plays an indispensable basic role in the development of modern society. However, the overexploitation of fossil energy has led to a series of environmental and ecological problems such as air pollution and greenhouse effect. Biomass energy, as the most abundant renewable resource on earth, provides a feasible and promising development path to solve the energy crisis and environmental pollution.

[0003] 5-hydroxymethylfurfural (HMF) is a key component of the biomass platform and can be obtained by cellulose hydrolysis and dehydration. 5-hydroxymethylfurfural contains furan ring, aldehyde group and hydroxymethyl group, and can produce high-value chemicals and liquid biofuel oils such as 2,5-dimethylfuran (2,5-DMF), 2,5-bishydroxymethylfuran, gamma-valerolactone, 2,5-diformylfuran and 2,5-furandicarboxylic acid through catalytic hydrogenation, oxidation and condensation. Therefore, 5-hydroxymethylfurfural is considered as an important link between the bio-refining industry and biomass raw materials. 5-hydroxymethylfurfural can be produced into 2,5-dimethylfuran by hydrogenation deoxidization, and 2,5-dimethylfuran has excellent properties such as suitable boiling point (93℃), high energy density (31.5MJ·L -1 ), high octane number (119) and low volatility, and thus becomes a new biomass liquid fuel that can replace ethanol.

[0004] Currently, noble metal catalysts such as Pd (Angew. Chem. Int. Ed. 2021, 60, 6807-6815), Pt (ACS Catal. 2021, 11, 15, 9204-9209) and Ru (Green Chem., 2018, 20, 2894-2902) are widely used in the reaction of catalyzing HMF to prepare 2,5-DMF. However, the high cost of noble metal catalysts limits its large-scale industrial application. To solve this problem, researchers have begun to focus on non-noble metal Ni-based catalysts (Appl. Catal. B, 2021, 295, 120270-120282), Co (Chem. Eng. J., 505:159602), Cu (ACS Catal. 2024, 14, 9, 6623-6632) and Fe (Green Chem., 2019, 21, 6390-6406) which are more affordable. Chinese invention patent CN105289619A synthesizes Ni-based hydrotalcite, then calcines and reduces to obtain highly dispersed NiMAl catalyst. The NiMAl catalyst is used for the hydrogenation of HMF to prepare 2,5-dimethylfuran, and the yield of 2,5-dimethylfuran is 95.4% after 20h of reaction at 180℃. Chinese invention patent application CN118237057A discloses an oxygen vacancy regulated supported nickel phosphide-based catalyst, and it is used for the hydrogenation and deoxidation of 5-hydroxymethylfurfural. At a reaction temperature of 180℃, the selectivity of 2,5-DMF is 97%. Chinese patent CN109503525A provides a HCP-Co mesoporous nanosheet catalyst, and the yield of 2,5-DMF can reach 95.1% under the reaction condition of 180℃.

[0005] Therefore, it can be seen that the existing catalysts for the hydrogenation and deoxidation of 5-hydroxymethylfurfural are mainly single metal or conventional carriers (such as alumina, silica, titanium oxide, etc.), and there are generally problems such as poor dispersion of active metal, limited oxygen vacancy regulation ability, and unsatisfactory reaction selectivity and catalytic stability. In addition, traditional carriers are difficult to effectively anchor active components, leading to easy agglomeration of metal particles, reduced exposure of active sites, easy irreversible deactivation of the catalyst, and affecting its industrial application prospects. Therefore, developing a new type of catalyst that can synergistically regulate active species and carrier channels, realize high dispersion of active metal loading, and efficiently catalyze the hydrogenation and deoxidation of 5-hydroxymethylfurfural under mild conditions has become an important direction that needs to be solved in this field. SUMMARY

[0006] In view of the technical problems of harsh reaction conditions, easy metal particle agglomeration, reduced active site exposure, and unsatisfactory catalyst stability in the reaction of preparing 2,5-dimethylfuran by hydrogenation of 5-hydroxymethylfurfural with a 5-hydroxymethylfurfural hydrogenation catalyst, the present application provides a catalyst for producing 2,5-dimethylfuran by hydrogenation of 5-hydroxymethylfurfural, which is a metal-organic coordination porous polymer derived supported metal catalyst with highly dispersed active metal sites and rich pore structures. The catalyst is prepared by using the rich pore structures of the metal-organic coordination porous polymer to limit the aggregation of metal active species, improving the nucleation, growth and agglomeration of the active components on the catalyst carrier, thereby optimizing the particle size and distribution state, and further preparing a catalyst with high stability, high 5-hydroxymethylfurfural conversion rate and excellent 2,5-dimethylfuran selectivity. The catalyst has stable catalytic activity at low temperature and low pressure, and has high activity and stability in the reaction of preparing 2,5-dimethylfuran by hydrogenation of 5-hydroxymethylfurfural.

[0007] The object of the present application is achieved by the following technical solutions:

[0008] The metal-organic coordination porous polymer derived catalyst for preparing 2,5-dimethylfuran by hydrogenation of 5-hydroxymethylfurfural is derived from a metal-organic coordination porous polymer anchoring metal active components and then calcining.

[0009] The metal-organic coordination porous polymer derived catalyst for preparing 2,5-dimethylfuran by hydrogenation of 5-hydroxymethylfurfural is prepared by the following method: dispersing a metal-organic coordination porous polymer in a dispersion liquid to obtain a metal-organic coordination porous polymer dispersion liquid, adding a soluble metal salt solution of a metal active component to the metal-organic coordination porous polymer dispersion liquid, stirring, and solid-liquid separation to obtain a catalyst precursor; calcining the catalyst precursor in an air atmosphere to obtain the catalyst.

[0010] The catalyst uses a material derived from calcination of a metal-organic coordination porous polymer formed by coordination of one metal selected from cerium and zirconium or two metals with an organic carboxylic acid ligand as a carrier.

[0011] Another object of the present application is to provide a preparation method of the metal-organic coordination porous polymer derived catalyst for preparing 2,5-dimethylfuran by hydrogenation of 5-hydroxymethylfurfural, which comprises: dispersing a metal-organic coordination porous polymer in a dispersion liquid to obtain a metal-organic coordination porous polymer dispersion liquid, adding a soluble metal salt solution of a metal active component to the metal-organic coordination porous polymer dispersion liquid, stirring at a temperature of 40-80°C for 2-12h, and solid-liquid separation to obtain a catalyst precursor; and calcining the catalyst precursor in an air atmosphere at 500-900°C for 2-12h to obtain a catalyst with rich pore structures and highly dispersed active sites.

[0012] The metal-organic coordination porous polymer is a metal-organic coordination porous polymer formed by coordination of one metal or two metals selected from cerium and zirconium and one or two organic carboxylic acid ligands selected from terephthalic acid, 2-nitroterephthalic acid, and 2-amino terephthalic acid.

[0013] Preferably, the metal-organic coordination porous polymer is one of Ce-UiO-66 (CAS: 1801427-51-9), Zr-UiO-66 (CAS: 1260119-00-3), UiO-66 (Zr / Ce = 1:1), UiO-66-NH2 (Ce), UiO-66-NH2 (Zr) (CAS: 1260119-00-3), UiO-66-NH2 (Zr / Ce = 1:1), Ce-UiO-66-NO2, and UiO-66-NO2 (Zr).

[0014] Zr / Ce = 1:1 in UiO-66 (Zr / Ce = 1:1) and UiO-66-NH2 (Zr / Ce = 1:1) means that the molar ratio of Zr to Ce is 1:1.

[0015] More preferably, the metal-organic coordination porous polymer is UiO-66 (Zr / Ce = 1:1) and UiO-66-NH2 (Zr / Ce = 1:1).

[0016] Most preferably, the metal-organic coordination porous polymer is UiO-66-NH2 (Zr / Ce = 1:1).

[0017] The metal active component is at least one of copper, nickel, and cobalt, and preferably copper.

[0018] The soluble metal salt of the metal active component is at least one of an acetate salt, a nitrate salt, or a chloride salt.

[0019] Preferably, the soluble metal salt of the metal active component is one of copper acetate, copper nitrate, copper chloride, nickel nitrate, nickel chloride, nickel acetate, cobalt nitrate, cobalt chloride, and cobalt acetate.

[0020] More preferably, the soluble metal salt of the metal active component is copper acetate, nickel acetate, and cobalt acetate.

[0021] Most preferably, the soluble metal salt of the metal active component is copper acetate.

[0022] The mass ratio of the soluble metal salt of the metal active component to the metal-organic coordination porous polymer is 0.01:1 to 0.4:1, and preferably 0.02:1 to 0.2:1.

[0023] The dispersion liquid is one of water, ethylene glycol, ethanol, or a mixture of two in equal volume.

[0024] Specifically, the water, the equal-volume mixed solvent of water and ethylene glycol, the equal-volume mixed solvent of ethanol and ethylene glycol, or the equal-volume mixed solvent of water and ethanol.

[0025] The hydroxyl group of ethylene glycol can form a dynamic hydrogen bond network with water molecules, which helps to stabilize the solvation layer of metal ions and provides moderate steric hindrance to inhibit particle agglomeration. At the same time, considering the viscosity of the dispersion liquid, a medium viscosity environment not only ensures the diffusion mass transfer rate, but also inhibits the Ostwald ripening process through viscous resistance, therefore, the dispersion liquid is preferably an equal-volume mixed solvent of water and ethylene glycol.

[0026] The mass-to-volume ratio of the metal-organic coordination porous polymer to the dispersion liquid is 1:20-1:100 g / mL, preferably 1:30-1:80 g / mL, and more preferably 1:40-1:60 g / mL.

[0027] The concentration of the metal salt in the soluble metal salt solution of the metal active component is 0.01-1 mol / L, preferably 0.05-0.5 mol / L.

[0028] The soluble metal salt solution of the metal active component is an aqueous solution of the soluble metal salt of the metal active component.

[0029] Preferably, the soluble metal salt solution of the metal active component is added dropwise to the metal-organic coordination porous polymer dispersion liquid while stirring.

[0030] If the stirring temperature is low (such as 40℃ or 45℃), it will lead to uneven dispersion of the active component; if the temperature is high (such as 80℃), it will not have a significant impact on the effect of the catalyst, but will increase the energy consumption. If the stirring time is short, the mixing of the reactants and the uniform dispersion of the active component cannot be completed, leading to poor catalyst performance; if the stirring time is too long, although it may be beneficial to mixing, it increases the energy consumption and production cycle, and long-time stirring may lead to excessive reaction or structure damage of part of the components, affecting the stability of the catalyst. Under the premise of ensuring excellent catalyst performance, in order to realize the economy and stability of the process, preferably, the stirring temperature is 50-70℃, and the stirring time is 6-8h.

[0031] The solid-liquid separation is centrifugation.

[0032] Preferably, after the solid-liquid separation, the solid is washed with methanol and dried to obtain the catalyst precursor.

[0033] Preferably, the calcination temperature is 600-700 DEG C, and the calcination time is 5-8h.

[0034] Specifically, the metal-organic coordination porous polymer is dispersed in the dispersion liquid by ultrasonic to obtain a metal-organic coordination porous polymer dispersion liquid; a solution of a soluble metal salt of the metal active component is added dropwise into the metal-organic coordination porous polymer dispersion liquid, and the active metal is anchored in the pores of the metal-organic coordination porous polymer by stirring; solid-liquid separation is performed, the solid is washed with methanol, and drying is performed to obtain a catalyst precursor; and the catalyst precursor is calcined in an air atmosphere to obtain the catalyst.

[0035] Another object of the present application is to provide the use of the metal-organic coordination porous polymer derived catalyst for preparing 2,5-dimethylfuran by hydrogenation of 5-hydroxymethylfurfural.

[0036] A method for preparing 2,5-dimethylfuran by hydrogenation of 5-hydroxymethylfurfural, comprising: using the metal-organic coordination porous polymer derived catalyst for preparing 2,5-dimethylfuran by hydrogenation of 5-hydroxymethylfurfural as a catalyst, mixing 5-hydroxymethylfurfural, the catalyst and a reaction solvent, placing in a hydrogen atmosphere, and performing hydrogenation reaction under heating and stirring to prepare 2,5-dimethylfuran; after the reaction is completed, cooling and recovering the catalyst by filtration.

[0037] The mass of the metal-organic coordination porous polymer derived catalyst for preparing 2,5-dimethylfuran by hydrogenation of 5-hydroxymethylfurfural is 2%-20% of the mass of 5-hydroxymethylfurfural, preferably 8%-12%, and more preferably 10%-12%; the temperature of the hydrogenation reaction is 100-200 DEG C, preferably 120-180 DEG C, and more preferably 150 DEG C; the pressure of the hydrogenation reaction is 1.0-3.0 MPa, preferably 1.5-2.5 MPa, and more preferably 1.5 MPa; and the time of the hydrogenation reaction is 1-12h, preferably 3-6h.

[0038] Specifically, a method for preparing 2,5-dimethylfuran by hydrogenation of 5-hydroxymethylfurfural, comprising: adding 5-hydroxymethylfurfural, a metal-organic coordination porous polymer derived catalyst for preparing 2,5-dimethylfuran by hydrogenation of 5-hydroxymethylfurfural and a reaction solvent into a reactor, replacing the air in the reactor with nitrogen, and then replacing the nitrogen with hydrogen; heating to a set hydrogenation reaction temperature, continuously charging hydrogen and maintaining the pressure of the hydrogenation reaction during the reaction, and performing hydrogenation reaction under stirring; after the reaction is completed, cooling, and recovering the catalyst by filtration.

[0039] In the present application, the pressures are all absolute pressures.

[0040] The beneficial effects of the present application are embodied in:

[0041] The catalyst of the present application is a non-noble metal catalyst, low in cost and simple in synthesis method. The anchoring ability of the uncoordinated carboxylic acid of the metal-organic coordination porous polymer to the organic carboxylic acid ligand stabilizes the metal active component, significantly inhibits the agglomeration phenomenon in the calcination and reaction processes, realizes the high dispersion of the active metal component, optimizes the nucleation, growth and distribution state of the metal active component, thereby preparing a catalyst with high stability and high activity. Meanwhile, the ordered pore channel of the metal-organic coordination porous polymer optimizes the mass transfer path of the reactants, strengthens the mass transfer process of the reactants in the catalyst, and improves the catalytic reaction performance.

[0042] The catalyst of the present application has highly dispersed metal active sites and stable pore channel structure. The metal-organic coordination porous polymer has rich oxygen vacancies, which strengthens the mass transfer, adsorption and activation processes of the reactants in the catalyst, and has the characteristics of good activity, high stability and environmental friendliness in the 5-hydroxymethylfurfural hydrogenation reaction.

[0043] The catalyst of the present application strengthens the mass transfer process of the reactants in the catalyst, can catalyze the production of 2,5-dimethylfuran from 5-hydroxymethylfurfural under mild conditions in a short time, improves the conversion rate of 5-hydroxymethylfurfural and the selectivity of 2,5-dimethylfuran in the 5-hydroxymethylfurfural hydrogenation reaction process, and the conversion rate of 5-hydroxymethylfurfural is more than 97%, and the selectivity of 2,5-dimethylfuran is more than 97%. The catalyst of the present application has industrial application prospect in the production of 2,5-dimethylfuran from 5-hydroxymethylfurfural hydrogenation. BRIEF DESCRIPTION OF DRAWINGS

[0044] Figure 1 It is the XRD pattern of the unused catalyst 1.

[0045] Figure 2 It is the pore size distribution graph of the unused catalyst 1.

[0046] Figure 3 It is the XRD pattern of the catalyst 1 after reaction.

[0047] Figure 4 It is the pore size distribution graph of the catalyst 1 after reaction.

[0048] Figure 5 It is the 5-hydroxymethylfurfural conversion rate and 2,5-dimethylfuran selectivity of the catalyst 1 after 5 cycles. DETAILED DESCRIPTION

[0049] The present application is further described below through implementation examples. The experimental methods in the following examples, which do not mark specific experimental conditions, are usually according to the known means in the art.

[0050] Conversion = (amount of raw material converted / total amount of raw material) x 100%.

[0051] Selectivity = (amount of raw material consumed to convert into the target product / amount of raw material converted) x 100%.

[0052] Example 1

[0053] Into a beaker, 25 mL of ethylene glycol and 25 mL of deionized water were added and mixed to prepare a dispersion, 1.0 g of UiO-66-NH2(Zr / Ce = 1:1) was added to the dispersion and ultrasonically dispersed to prepare a dispersion of metal-organic coordination porous polymer. Subsequently, 10 mL of 0.1 mol / L aqueous copper acetate solution was slowly added to the dispersion of metal-organic coordination porous polymer while stirring, and after the addition was completed, the temperature was increased to 60°C while stirring, and the stirring diffusion was maintained at 60°C for 7 h. After centrifugation, the solid was washed twice with methanol and dried to obtain a catalyst precursor. The catalyst precursor was calcined at 650°C in an air atmosphere for 6 h, and after cooling, catalyst 1 was obtained. The XRD pattern of catalyst 1 is shown in Figure 1 , and the pore size distribution is shown in Figure 2 From Figure 1 it can be seen that the active sites of the catalyst are highly dispersed, and there is no diffraction peak of the metal active species, indicating that the particle size of the metal active component is small. From Figure 2 it can be seen that the catalyst has a rich pore structure.

[0054] Example 2

[0055] Performance test: 2.522 g of 5-hydroxymethylfurfural, 0.252 g of catalyst 1 and 10 g of tetrahydrofuran (reaction solvent) were added to a 50 mL stainless steel high-pressure reaction kettle, the air in the kettle was replaced with N2, and then the N2 in the kettle was replaced with H2. The heating was turned on, the temperature was increased to 150°C, and the pressure in the kettle was increased to 1.5 MPa by introducing hydrogen, and the pressure was maintained at 1.5 MPa during the reaction. The reaction was stirred for 3 h. After the reaction was completed, the reaction liquid was collected, the catalyst in the reaction liquid was removed by filtration, and the reaction liquid was analyzed by gas chromatography. The conversion of 5-hydroxymethylfurfural was 100%, and the selectivity of 2,5-dimethylfuran was 99.60%.

[0056] The XRD pattern and the pore size distribution of catalyst 1 after one performance test are shown in Figure 3 , Figure 4 Compared with the XRD pattern Figure 1 and the pore size distribution Figure 2 of the unused catalyst 1, there is no significant difference, indicating that the catalyst still maintains a good structure and the active component has not been lost.

[0057] Repeatability test of catalyst. The catalyst 1 was subjected to stability test according to the performance test conditions of the present example, a total of 5 tests were conducted, and the results of the 1st to 5th reactions were compared. Figure 5 It was found that the results of the 2nd to 5th reactions were not significantly different from the 1st, indicating that the catalyst had stable catalytic activity.

[0058] Example 3

[0059] According to the method of Reference Example 1, catalysts 2 to 25 were prepared by changing the type of metal-organic coordination porous polymer, the type of metal salt, the type of dispersion liquid, the mass ratio of metal-organic coordination porous polymer to dispersion liquid, the mass ratio of metal salt to metal-organic coordination porous polymer, the stirring diffusion temperature, the diffusion time, the calcination temperature and the calcination time in Table 1.

[0060] Table 1. Preparation conditions of catalysts 1 to 18

[0061]

[0062]

[0063] Note: The volume ratio of anhydrous ethanol to anhydrous ethanol and water in water is 1:1; the volume ratio of water to ethylene glycol in water is 1:1; the volume ratio of anhydrous ethanol to ethylene glycol in anhydrous ethanol is 1:1; the dosage ratio of metal-organic coordination porous polymer to dispersion liquid is the mass-volume ratio (g / mL) of metal-organic coordination porous polymer to dispersion liquid.

[0064] Example 4

[0065] Performance test of catalyst

[0066] 2.522 g of 5-hydroxymethylfurfural, catalyst and 10 g of tetrahydrofuran (reaction solvent) were added to a 50 mL stainless steel high-pressure reaction kettle, the air in the kettle was replaced with N2 first, then the N2 in the kettle was replaced with H2, the heating was started, the temperature was raised to the reaction temperature, the hydrogen was introduced to raise the pressure in the kettle to the reaction pressure and maintain the reaction pressure, the stirring was started, and the reaction was started. The reaction temperature, reaction pressure, catalyst dosage and reaction time are shown in Table 2. After the reaction was completed, the reaction liquid was collected, the catalyst in the reaction liquid was removed by filtration, and the conversion rate of 5-hydroxymethylfurfural and the selectivity of 2,5-dimethylfuran were analyzed by gas chromatograph.

[0067] Table 2. Performance test conditions and results of catalyst

[0068]

[0069] Note: The catalyst dosage refers to the mass of the catalyst as a percentage of the mass of 5-hydroxymethylfurfural.

[0070] Example 5

[0071] Catalyst 26 was prepared according to the method of Example 1. During the preparation, only the UiO-66-NH2(Zr / Ce = 1 : 1) in Example 1 was replaced by equal mass of Ce-UiO-66, and other conditions were unchanged.

[0072] Catalyst 27 was prepared according to the method of Example 1. During the preparation, only the UiO-66-NH2(Zr / Ce = 1 : 1) in Example 1 was replaced by equal mass of Zr-UiO-66, and other conditions were unchanged.

[0073] Catalyst 28 was prepared according to the method of Example 1. During the preparation, only the UiO-66-NH2(Zr / Ce = 1 : 1) in Example 1 was replaced by equal mass of UiO-66(Zr / Ce = 1 : 1), and other conditions were unchanged.

[0074] Catalyst 29 was prepared according to the method of Example 1. During the preparation, only the UiO-66-NH2(Zr / Ce = 1 : 1) in Example 1 was replaced by equal mass of UiO-66-NH2(Ce), and other conditions were unchanged.

[0075] Catalyst 30 was prepared according to the method of Example 1. During the preparation, only the UiO-66-NH2(Zr / Ce = 1 : 1) in Example 1 was replaced by equal mass of UiO-66-NH2(Zr), and other conditions were unchanged.

[0076] Catalyst 31 was prepared according to the method of Example 1. During the preparation, only the UiO-66-NH2(Zr / Ce = 1 : 1) in Example 1 was replaced by equal mass of UiO-66-NH2(Zr / Ce = 1 : 1), and other conditions were unchanged.

[0077] Catalyst 32 was prepared according to the method of Example 1. During the preparation, only the UiO-66-NH2(Zr / Ce = 1 : 1) in Example 1 was replaced by equal mass of Ce-UiO-66-NO2, and other conditions were unchanged.

[0078] Catalyst 33 was prepared according to the method of Example 1. During the preparation, only the UiO-66-NH2(Zr / Ce = 1 : 1) in Example 1 was replaced by equal mass of UiO-66-NO2(Zr), and other conditions were unchanged.

[0079] Catalyst 34 was prepared according to the method of Example 1. During the preparation, only the copper acetate in Example 1 was replaced by equal mass of nickel acetate, and other conditions were unchanged.

[0080] Catalyst 35 was prepared according to the method of Example 1. During the preparation, only the copper acetate in Example 1 was replaced with an equal amount of cobalt acetate, and other conditions were unchanged.

[0081] Table 3. Preparation conditions of catalysts 26-35

[0082]

[0083] The catalysts 26-35 were tested for activity according to the performance test conditions of Example 2, and the analysis results are shown in Table 4.

[0084] Table 4. Performance test results of catalysts 26-32

[0085]

[0086] Comparative Example 1

[0087] Into a beaker, 25 mL of ethylene glycol and 25 mL of deionized water were added and mixed to prepare a dispersion, 1.0 g of zirconium oxide (commercial product) was added and ultrasonically dispersed to prepare a metal-organic coordination porous polymer dispersion. Subsequently, 10 mL of 0.1 mol / L aqueous copper acetate solution was slowly added to the metal-organic coordination porous polymer dispersion while stirring, and stirred at 60°C for 7 h, centrifuged to obtain a solid, which was washed twice with methanol and dried to obtain a catalyst precursor; the catalyst precursor was calcined at 650°C for 6 h in an air atmosphere, and cooled to obtain comparative catalyst 1.

[0088] Into a 50 mL stainless steel high-pressure reaction kettle, 2.522 g of 5-hydroxymethylfurfural, 0.252 g of comparative catalyst 1 and 10 g of tetrahydrofuran (reaction solvent) were added, the air in the kettle was replaced with N2, and then the N2 in the kettle was replaced with H2, heating was started, the temperature was raised to the reaction temperature of 150°C, hydrogen was introduced to raise the pressure in the kettle to 1.5 MPa and maintain the pressure at 1.5 MPa during the reaction, and stirring was performed for 3 h. After the reaction was completed, the reaction liquid was collected, the catalyst in the reaction liquid was removed by filtration, and gas chromatography was used for analysis, the conversion rate of 5-hydroxymethylfurfural was 81.21%, and the selectivity of 2,5-dimethylfuran was 34.89%. Under the same reaction conditions, using catalyst 1, the conversion rate of 5-hydroxymethylfurfural was 100%, and the selectivity of 2,5-dimethylfuran was 99.20%.

[0089] Comparative Example 2

[0090] Into a beaker, 25 mL of ethylene glycol and 25 mL of deionized water were added and mixed to form a dispersion, 1.0 g of cerium oxide (commercial product) was added and ultrasonically dispersed to form a dispersion of metal-organic coordination porous polymer. Subsequently, 10 mL of 0.1 mol / L aqueous copper acetate solution was slowly added to the dispersion of metal-organic coordination porous polymer with stirring, and the mixture was stirred at 60°C for 7 h, centrifuged to obtain a solid, which was washed twice with methanol and dried to obtain a catalyst precursor; the catalyst precursor was calcined at 650°C for 6 h in an air atmosphere, and cooled to obtain comparative catalyst 2.

[0091] Into a 50 mL stainless steel autoclave, 2.522 g of 5-hydroxymethylfurfural, 0.252 g of comparative catalyst 2 and 10 g of tetrahydrofuran (reaction solvent) were added, the autoclave was first replaced with N2, then with H2, heating was started, the temperature was raised to 150°C, and the pressure in the autoclave was raised to 1.5 MPa by introducing H2, and the pressure was maintained at 1.5 MPa during the reaction, and the reaction was stirred for 3 h. After the reaction was completed, the reaction liquid was collected, the catalyst in the reaction liquid was removed by filtration, and the reaction liquid was analyzed by gas chromatography, the conversion of 5-hydroxymethylfurfural was 76.21%, and the selectivity of 2,5-dimethylfuran was 44.89%. Under the same reaction conditions, using catalyst 1, the conversion of 5-hydroxymethylfurfural was 100%, and the selectivity of 2,5-dimethylfuran was 99.20%.

Claims

1. A metal-organic coordination porous polymer derived catalyst for the hydrogenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran, characterized in that: The catalyst is derived from calcination of metal-organic coordination porous polymers after anchoring metal active components.

2. The metal-organic coordination porous polymer derived catalyst for the hydro- hydrogenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran according to claim 1, characterized in that: The catalyst is prepared by dispersing metal-organic coordination porous polymers in a dispersion to obtain a metal-organic coordination porous polymer dispersion, adding a solution of a soluble metal salt of a metal active component to the metal-organic coordination porous polymer dispersion, heating and continuously stirring, solid-liquid separation to obtain a catalyst precursor; calcining the catalyst precursor in an air atmosphere to obtain the catalyst.

3. Metal-organic coordination porous polymer derived catalyst for the hydro genation of 5-hydroxymethylfurfural to 2,5-dimethylfuran according to claim 1 or 2, characterized in that: The metal-organic coordination porous polymer is a metal-organic coordination porous polymer of one or two metals selected from cerium and zirconium and one or two organic carboxylic acid ligands selected from terephthalic acid, 2-nitroterephthalic acid and 2-amino terephthalic acid; the metal active component is at least one of copper, nickel and cobalt, preferably copper; and the soluble metal salt of the metal active component is at least one of acetate, nitrate and chloride.

4. The metal-organic coordination porous polymer derived catalyst for the hydro- hydrogenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran according to claim 3, characterized in that: The metal-organic coordination porous polymer is one of Ce-UiO-66 (CAS: 1801427-51-9), Zr-UiO-66 (CAS: 1260119-00-3), UiO-66 (Zr / Ce = 1:1), UiO-66-NH2 (Ce), UiO-66-NH2 (Zr) (CAS: 1260119-00-3), UiO-66-NH2 (Zr / Ce = 1:1), Ce-UiO-66-NO2 and UiO-66-NO2 (Zr), preferably UiO-66 (Zr / Ce = 1:1) and UiO-66-NH2 (Zr / Ce = 1:1), and most preferably UiO-66-NH2 (Zr / Ce = 1:1).

5. The metal-organic coordination porous polymer derived catalyst for the hydro- hydrogenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran according to claim 3, characterized in that: The soluble metal salt of the metal active component is one of copper acetate, copper nitrate, copper chloride, nickel nitrate, nickel chloride, nickel acetate, cobalt nitrate, cobalt chloride and cobalt acetate, preferably copper acetate, nickel acetate and cobalt acetate, and most preferably copper acetate.

6. The metal-organic coordination porous polymer derived catalyst for the hydro- hydrogenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran according to claim 1, characterized in that: The mass ratio of the soluble metal salt of the metal active component to the metal-organic coordination porous polymer is 0.01:1 to 0.4:1, preferably 0.02:1 to 0.2:

1.

7. A method for preparing a metal-organic coordination porous polymer derived catalyst for the hydrogenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran according to claim 1, characterized in that: The method comprises the following steps: The metal-organic coordination porous polymer is dispersed in a dispersion to obtain a metal-organic coordination porous polymer dispersion, a solution of a soluble metal salt of a metal active component is added dropwise to the metal-organic coordination porous polymer dispersion, stirring is performed at a temperature of 40-80°C for 2-12 hours, solid-liquid separation is performed to obtain a catalyst precursor; the catalyst precursor is calcined in an air atmosphere at a temperature of 500-900°C for 2-12 hours to obtain the catalyst.

8. The method for preparing a metal-organic coordination porous polymer derived catalyst for the 5-hydroxymethylfurfural hydrogenation to 2,5-dimethylfuran according to claim 7, characterized in that: The temperature of the stirring is 50-70°C, and the stirring time is 6-8 hours; the temperature of the calcination is 600-700°C, and the calcination time is 5-8 hours.

9. Use of the metal-organic coordination porous polymer derived catalyst of claim 1 in the hydrogenation of 5-hydroxymethylfurfural to prepare 2,5-dimethylfuran.

10. A process for the production of 2,5-dimethylfuran by hydrogenation of 5-hydroxymethylfurfural, characterized in that: The method comprises the following steps: The metal organic coordination porous polymer derived catalyst for preparing 2,5-dimethylfuran by hydrogenation of 5-hydroxymethylfurfural according to claim 1 is used as a catalyst, 5-hydroxymethylfurfural, the catalyst and a reaction solvent are mixed, and then the mixture is placed in a hydrogen atmosphere, and a hydrogenation reaction is carried out under the conditions of heating and stirring to prepare 2,5-dimethylfuran; after the reaction is completed, the catalyst is recovered by cooling and filtration; In the formula, the mass of the catalyst is 2% to 20% of the mass of 5-hydroxymethylfurfural, preferably 8% to 12%, and more preferably 10% to 12%; the temperature of the hydrogenation reaction is 100 to 200 DEG C, preferably 120 to 180 DEG C, and more preferably 150 DEG C; the pressure of the hydrogenation reaction is 1.0 to 3.0 MPa, preferably 1.5 to 2.5 MPa, and more preferably 1.5 MPa; and the time of the hydrogenation reaction is 1 to 12 h, and preferably 3 to 6 h.

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