Pd / NiCoOx catalyst, preparation method and method for catalytically hydrogenating furan aldehyde alcohol compound

Abstract

The invention belongs to the field of catalysts, and discloses a Pd / NiCoOx catalyst, a preparation method and a method for catalytically hydrogenating furan aldehyde alcohol compounds, in the Pd / NiCoOx catalyst, NiCoOx represents a composite carrier of Ni oxide and Co oxide, and Pd is loaded on the composite carrier; the catalyst can be prepared by an ascorbic acid (VC) assisted solid phase grinding-air atmosphere calcination process; the method for catalytically hydrogenating the furan aldehyde alcohol compound comprises the following steps: adding the furan aldehyde alcohol compound, water and a Pd / NiCoOx catalyst into a reaction container, sealing the reaction container, filling pure hydrogen into the reaction container, and carrying out hydrogenation reaction to obtain a hydrogenation product. By means of the catalyst, a simpler hydrogenation reaction system for catalytic hydrogenation of furan aldehyde alcohol compounds can be constructed, and compared with an alcohol solvent and high-temperature complex reaction conditions needed by an existing process, the reaction system involved in the method is more environmentally friendly and mild, and the catalytic efficiency is higher.

Description

Technical Field

[0001] The present invention belongs to the field of catalysts, and specifically relates to a Pd / NiCoO x A catalyst, a preparation method and a method for catalytically hydrogenating furan aldehyde alcohol compounds. Background Art

[0002] Hydrogenation of renewable biomass-derived feedstocks is of particular importance in the sustainable production of biofuels and fine chemicals. Among various biomass-derived platform chemicals, 5-hydroxymethylfurfural (HMF) contains various functional groups (C=O, C=C and CO bonds) that are chemically active for hydrogenation. The hydrogenation reduction of HMF leads to a series of versatile products such as 2,5-furan dimethanol (BHMF), furfuryl alcohol (FA), tetrahydrofurfuryl alcohol (THFA), 5-methylfurfural (5-MF), 5-methylfurfural (MFA) and 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF). Compared with unsaturated furanic compounds, BHMTHF can be used as a green solvent and monomer. In addition, it can be hydrogenated to 2,5-dimethyltetrahydrofuran as a potential biofuel. It can also be used to prepare polyols such as 1,2,6-hexanetriol and 1,6-hexanediol through ring-opening hydrogenolysis, which are used as monomers for polyurethanes. Since there are multiple side reactions in the hydrogenation process that affect the production efficiency and selectivity of BHMTHF, it is a great challenge to convert high-concentration HMF into BHMTHF with high selectivity in a single pot or through BHMF catalysis.

[0003] Currently, the reported mono- or bimetallic catalysts tend to preferentially hydrogenate the CO bond to form 2,5-furan dimethanol (BHMF), and the subsequent hydrogenation of the CC bond is considered to be the rate-determining step for the complete hydrogenation of HMF to BHMTHF. Therefore, BHMF or BHMTHF is usually reported in the literature as the main product of HMF hydrogenation, while 5-hydroxymethyltetrahydrofuran carboxaldehyde (5-HMTHFF) is rarely achieved as the main product, which is due to the inherent difficulty in controlling the preferential hydrogenation of the CC bond. Hydrogenolysis of the hydroxymethyl group plays a dominant role in the side reactions, and polycondensation reactions are also inevitable at high substrate concentrations. 5-HMTHFF, as the main intermediate in the complete hydrogenation of HMF, is expected to inhibit the occurrence of side reactions because C=O bonds are generally easier to reduce than C-OH bonds in hydrogenation from the perspective of kinetics and thermodynamics. Therefore, in order to achieve efficient selective hydrogenation reactions, it is necessary to rationally design catalysts for HMF conversion under mild conditions, which is of great significance for laboratory scale and industrial applications.

[0004] Although HMF can obtain high yield (95-99%) of BHMTHF in both noble metal (such as platinum, palladium and ruthenium) and non-noble metal (such as nickel, cobalt) based catalytic systems (Appl. Catal. B: Environ. 2025, 361, 124578; Angew. Chem. Int. Ed. 2011, 50, 7083-7087; Chem Sus Chem 2016, 9, 521-531; ACSSustainable Chem. Eng. 2014, 2, 173-180), for example, Pd / MIL-101(Al)-NH 2 At 30℃, 1MPa H 2 After 12 hours of catalysis under the reaction conditions, a 96% BHMTHF yield was obtained (ACS Catal., 2015, 5, 722-733). Under low hydrogen pressure (0.5MPa) and room temperature conditions, after 3 hours of reaction with Ru / MSN-Zr-20 as catalyst, the BHMTHF yield reached 85% (ChemCatChem, 2013, 5, 2822-2826). Low-cost non-precious metal catalysts are attractive alternatives, but harsh conditions are required in the process of hydrogenating HMF to BHMTHF. Likozar et al. used Ni-Ce / Al in 1-butanol 2 O 3 Catalyst, at 190°C, 50 bar H 2 Under the same conditions, a BHMTHF yield of 88% was achieved (Green Chem., 2021, 23, 7996-8002). 2 O 3 At 60 °C and 60 bar H 2 Under the above conditions, a 100% HMF conversion rate and a 96.2% BHMTHF yield can be provided (Green Chem., 2015, 17, 2504-2514). However, most of the catalytic systems reported above can only catalyze the synthesis of BHMTHF at a relatively low HMF concentration (below 7%) in the aqueous phase. Under conditions of a higher HMF concentration, the selectivity and yield of the product are significantly reduced, which greatly hinders large-scale industrial applications. Summary of the invention

[0005] The purpose of the present invention is to improve the selectivity and yield of a method for hydrogenating furan aldehydes under mild reaction conditions, especially under conditions of higher raw material concentration.

[0006] The first aspect of the present invention is to provide a Pd / NiCoO x Catalyst, the NiCoO xShown is a composite support of Ni oxide and Co oxide, on which Pd is supported.

[0007] The catalyst of the present invention is a composite catalyst, and the carrier therein is a composite component carrier, the chemical composition of the carrier is a mixture of nickel oxide and cobalt oxide, and therefore it is defined as a composite carrier of Ni oxide and Co oxide in the present invention.

[0008] In a preferred embodiment of the present invention, the catalyst is composed of Pd and NiCoO x The total mass is calculated as 100%, and the mass percentage of Pd is 0.1-2wt%; in the composite carrier, the molar ratio of Ni element to Co element is 1:(1-6); the morphology of Pd is nanoparticles with an average particle size of 2-5nm, and the composite carrier corresponds to a mixed oxide with a spinel structure, which is a black powder.

[0009] Among them, Pd is evenly dispersed on the composite carrier in the form of nanoparticles, and the content of Pd is relatively small, which plays a catalytic role together with the dual oxide component of the composite carrier.

[0010] The second aspect of the present invention is to provide the Pd / NiCoO x The method for preparing the catalyst comprises the following steps:

[0011] (1) Mix the solid powders of Co salt and Ni salt evenly and calcine them in a high temperature oxygen atmosphere to form NiCoO x Composite carrier;

[0012] (2) Dispersing Pd salt and NiCoO in solvent x The composite support is uniform, and then the solvent is removed to obtain NiCoO x A solid mixture of a composite support and a Pd salt;

[0013] (3) calcining the solid mixture in a high temperature oxygen-containing atmosphere to obtain a catalyst precursor;

[0014] (4) subjecting the catalyst precursor to a reduction reaction in a high temperature hydrogen-containing atmosphere to obtain the catalyst.

[0015] Through step (1), the Co and Ni salts are first mixed evenly, and then calcined in a high-temperature oxygen atmosphere to convert the two salts into Co and Ni oxides, thereby obtaining a composite carrier, in which any one of the Co and Ni oxides is evenly dispersed.

[0016] The Pd salt is dispersed in NiCoO x On the composite support; through step (3), the Pd salt is converted into Pd oxide dispersed on NiCoOx On the composite carrier; Pd metal is uniformly dispersed in NiCoO obtained by step (4) x on a composite carrier.

[0017] In a preferred embodiment of the present invention, the mixing process of step (1) further includes mixing ascorbic acid with solid powders of Co salt and Ni salt; the total molar ratio of ascorbic acid to nickel and cobalt elements in the metal salt is defined as a, a≤0.4.

[0018] The role of the ascorbic acid is to generate gas by high-temperature decomposition during high-temperature calcination, so that the composite carrier has a porous shape, resulting in an increase in specific surface area and total pore volume. At the same time, it can also effectively increase the content of oxygen vacancies on the catalyst surface, which is beneficial to the adsorption of substrates and the adsorption-activation of hydrogen during hydrogenation.

[0019] In a preferred embodiment of the present invention, the nickel salt and the cobalt salt in step (1) are nickel nitrate and cobalt nitrate respectively; the calcination temperature in step (1) is 400-600°C and the time is 4-6 hours, and the oxygen-containing atmosphere is air; the palladium salt in step (3) is palladium acetate or palladium chloride, the calcination temperature in step (3) is 400-600°C and the time is 4-6 hours, and the oxygen-containing atmosphere is air; the high temperature in step (4) is 150-250°C and the time is 1-2 hours, and the hydrogen-containing atmosphere is a combination of hydrogen / inert gas.

[0020] The third aspect of the present invention is to provide a method for catalytic hydrogenation of furan aldehyde alcohol compounds, comprising the following steps: adding furan aldehyde alcohol compounds, water and Pd / NiCoOx catalyst into a reaction container, sealing the reaction container and filling it with pure hydrogen for hydrogenation reaction to obtain a hydrogenation product; the Pd / NiCoOx catalyst is added to a reaction container, wherein the reaction container is sealed and filled with pure hydrogen for hydrogenation reaction to obtain a hydrogenation product; x The catalyst is Pd / NiCoO x The catalyst may be Pd / NiCoO obtained according to the preparation method of the second aspect of the present invention. x catalyst.

[0021] In the preferred embodiment of the present invention, the hydrogenation reaction conditions are as follows: the hydrogen required for the reaction is added non-continuously, the hydrogen pressure in the reaction container is 0.5-6MPa, the temperature is room temperature-60°C, and the reaction time is 1-4 hours.

[0022] In a preferred embodiment of the present invention, the hydrogen required for the reaction is added once or at least twice in a discontinuous manner.

[0023] In a preferred embodiment of the present invention, the furan aldehyde alcohol compound includes one of furfuryl alcohol, furfural, 5-methylfurfural, 5-methylfurfuryl alcohol, 2,5-furan dimethanol and 5-hydroxymethylfurfural, and the concentration of the furan aldehyde alcohol compound is 1-60wt%; the products are one of tetrahydrofurfuryl alcohol, tetrahydro-5-methyl-2-furanmethanol and 2,5-bis(hydroxymethyl)tetrahydrofuran.

[0024] In a preferred embodiment of the present invention, the concentration of the furan aldehyde alcohol compound is more than 10 wt %.

[0025] In a preferred embodiment of the present invention, the Pd / NiCoO x The amount of catalyst used: the molar ratio of the furan aldehyde alcohol compound to the Pd element is: (100-1000):1.

[0026] Compared with the prior art, a certain embodiment of the present invention has at least one of the following beneficial effects:

[0027] (1) The present invention provides a Pd / NiCoO with high catalytic activity x The preparation method of the catalyst is simple and easy to implement. The oxygen-rich vacancy nickel-cobalt bimetallic oxide NiCoO is prepared by ascorbic acid (VC)-assisted solid phase grinding-air atmosphere calcination process x The catalyst has a very stable and high catalytic activity in catalytic hydrogenation of biomass-based furan aldehydes such as HMF to synthesize tetrahydrofuran alcohol compounds, and has the potential for industrial application.

[0028] (2) With the aid of the catalyst of the present invention, a simpler catalytic hydrogenation reaction system for furan aldehyde alcohol compounds can be constructed, that is, high-selectivity catalytic hydrogenation of furan aldehyde alcohol compounds to synthesize tetrahydrofuran alcohol compounds can be achieved in green solvent water at room temperature or at a relatively low heating temperature. Compared with the complex reaction conditions of alcohol solvents and high temperatures required by the existing process, the reaction system of the present invention is more environmentally friendly and mild.

[0029] (3) With the aid of the catalyst of the present invention, the product generation rate of catalytic hydrogenation of HMF to synthesize BHMTHF is as high as 395.3 mol BHMTHF mol Pd -1 h -1 , this value is significantly higher than the catalytic effect of existing catalysts.

[0030] (4) The present invention establishes a method for catalyzing the hydrogenation of high-concentration HMF to synthesize BHMTHF under mild reaction conditions, showing excellent catalytic activity. The catalyst can also perform highly selective hydrogenation reactions on high-concentration HMF (up to 60wt%) and crude HMF (20wt%) under mild reaction conditions, and the BHMTHF yield reaches 83.1-93.8%. This excellent performance is reported for the first time, highlighting the high efficiency of our catalyst material and its reasonable design strategy, and solving the problem that the crude product HMF is difficult to purify. It has important promoting significance for the large-scale production of BHMTHF, and also solves the problem that the current catalyst cannot be used to catalyze the efficient and selective hydrogenation of high-concentration HMF to prepare BHMTHF due to its low catalytic efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 The high-resolution TEM image and particle size distribution of the catalyst obtained in Example 7.

[0032] Figure 2 The figure is a reaction route diagram for producing 2,5-bis(hydroxymethyl)tetrahydrofuran from 5-hydroxymethylfurfural in a specific embodiment.

[0033] Figure 3 The XRD pattern of the catalyst obtained in the example.

[0034] Figure 4 The results of electron paramagnetic resonance (EPR) analysis of the carrier and catalyst of Example 6 and Example 7 are shown.

[0035] Figure 5 Ni obtained in Example 6 and Example 7 respectively 1 Co 2 O x -500 and Ni 1 Co 2 O x -0.2 Specific surface area map (a) and pore size distribution map (b) of VC-500 carrier. DETAILED DESCRIPTION

[0036] The present invention will be described in detail below through examples.

[0037] In order to explain the technical content, structural features, achieved objectives and effects of the technical solution in detail, the following is a detailed description in conjunction with specific embodiments and accompanying drawings.

[0038] Pd(a) / Ni in the examples 1 Co b O x-dVC-w catalyst, where a plus the percentage symbol % represents the mass percentage of palladium element calculated based on the total mass of nickel cobalt oxide supported palladium catalyst as 100%; b represents the ratio of the molar number of cobalt element to nickel element in nickel cobalt oxide; d represents the ratio of VC to the total molar amount of nickel and cobalt elements, d is between 0-0.4; w plus the temperature symbol ℃ represents the calcination temperature of the nickel cobalt oxide carrier, w is between 300-600℃; VC represents ascorbic acid. The contents of Pd, Ni and Co elements in the catalyst are determined by inductively coupled plasma-mass spectrometry.

[0039] After the catalytic reaction was completed, the contents of various substances in the sample were detected by high performance liquid chromatography. The calculation formulas for HMF conversion (%) and the yields of BHMTHF and intermediate products were as follows:

[0040]

[0041] Example 1

[0042] Preparation of Pd catalyst: First, 0.1 g of palladium acetate was calcined at 500 °C for 4 h in air atmosphere, and the resulting mixture was heated to 10 v / v% H 2 / N 2 The Pd catalyst can be obtained by calcining at 200°C in an atmosphere for 1 hour.

[0043] 0.0501 g of 5-hydroxymethylfurfural and 5.0010 g of deionized water were added to a reaction kettle (25 mL), and then 0.005 g of Pd catalyst was added. The reaction kettle was sealed and filled with 2 MPa of pure hydrogen (99.999%). The reaction kettle was placed in a 30° C. oil bath and vigorously stirred at 500 rpm for 3 hours to terminate the reaction. The reaction mixture was taken out and tested. The test results are listed in Table 1.

[0044] Example 2

[0045] Pd(1) / NiO x Preparation of NiO-500 catalyst: First, 5 g of nickel nitrate hexahydrate was ground for 5 minutes and then calcined at 500 °C for 4 hours in an air atmosphere to obtain NiO x -500; then 1.0102g NiO x -500 and 0.0204 g of palladium acetate were mixed and dissolved in 10 mL of acetone, the mixture was stirred at 60 ° C overnight and the acetone was removed, the solid obtained after drying was ground into powder, and then calcined at 400 ° C for 4 hours in an air atmosphere to obtain a precursor; the precursor was heated to 10 v / v% H 2 / N 2 Pd(1) / NiO was obtained by calcining at 200℃ for 1 hour in a molten-gas atmosphere. x -500 catalyst.

[0046] 0.0505 g 5-hydroxymethylfurfural and 5.0005 g deionized water were added to a reaction kettle (25 mL), and then 0.0503 g Pd(1) / NiO was added. x -500 catalyst, seal the reactor and fill it with 2MPa pure hydrogen (99.999%), place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 3 hours to terminate the reaction, take out the reaction mixture and detect it. The test results are listed in Table 1.

[0047] Example 3

[0048] Pd(1) / NiO x Preparation of -0.2VC-500 catalyst: First, 4.3685g nickel nitrate hexahydrate and 0.5277g ascorbic acid were mixed and ground for 5 minutes, and then calcined at 500°C for 4 hours in an air atmosphere to obtain NiO x -0.2VC-500; then 1.0011g NiO x -0.2g VC-500 and 0.0206g palladium acetate were mixed and dissolved in 10mL acetone, the mixture was stirred at 60°C overnight and the acetone was removed, the solid obtained after drying was ground into powder, and then calcined at 400°C for 4 hours in air atmosphere to obtain a precursor; the precursor was heated to 10v / v% H 2 / N 2 Pd(1) / NiO was obtained by calcining at 200℃ for 1 hour in a molten-gas atmosphere. x -0.2VC-500 catalyst.

[0049] 0.0501 g 5-hydroxymethylfurfural and 5.0120 g deionized water were added to a reaction kettle (25 mL), and then 0.0506 g Pd(1) / NiO was added. x -0.2VC-500 catalyst, seal the reactor and fill it with 2MPa pure hydrogen (99.999%), place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 3 hours to terminate the reaction, take out the reaction mixture and detect it. The test results are listed in Table 1.

[0050] Example 4

[0051] Pd(1) / CoO x Preparation of -500 catalyst: First, 5 g of cobalt nitrate hexahydrate was ground for 5 minutes and then calcined at 500 °C for 4 hours in an air atmosphere to obtain CoO x -500; then 1.0106g CoO x-500 and 0.0201 g of palladium acetate were mixed and dissolved in 10 mL of acetone, the mixture was stirred at 60 ° C overnight and the acetone was removed, the solid obtained after drying was ground into powder, and then calcined at 400 ° C for 4 hours in an air atmosphere to obtain a precursor; the precursor was heated to 10 v / v% H 2 / N 2 Pd(1) / CoO was obtained by calcining at 200℃ for 1 hour in a molten-gas atmosphere. x -500 catalyst.

[0052] 0.0502 g 5-hydroxymethylfurfural and 5.0100 g deionized water were added to a reaction kettle (25 mL), and then 0.0500 g Pd(1) / CoO x -500 catalyst, seal the reactor and fill it with 2MPa pure hydrogen (99.999%), place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 3 hours to terminate the reaction, take out the reaction mixture and detect it. The test results are listed in Table 1.

[0053] Example 5

[0054] Pd(1) / CoO x Preparation of -0.2VC-500 catalyst: First, 4.3325 g of cobalt nitrate hexahydrate and 0.5243 g of ascorbic acid were mixed and ground for 5 minutes, and then calcined at 500 °C for 4 hours in an air atmosphere to obtain CoO x -0.2VC-500; then 1.0001g CoO x -0.2 VC-500 and 0.0201 g palladium acetate were mixed and dissolved in 10 mL acetone. The mixture was stirred at 60 ° C overnight and the acetone was removed. The solid obtained after drying was ground into powder, and then calcined at 400 ° C for 4 hours in an air atmosphere to obtain a precursor; the precursor was heated to 10 v / v% H 2 / N 2 Pd(1) / CoO was obtained by calcining at 200℃ for 1 hour in a molten-gas atmosphere. x -0.2VC-500 catalyst.

[0055] 0.0500 g 5-hydroxymethylfurfural and 5.0100 g deionized water were added to a reaction kettle (25 mL), and then 0.0501 g Pd(1) / CoO x -0.2VC-500 catalyst, seal the reactor and fill it with 2MPa pure hydrogen (99.999%), place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 3 hours to terminate the reaction, take out the reaction mixture and detect it. The test results are listed in Table 1.

[0056] Example 6

[0057] Pd(1) / Ni 1 Co 2 O x Preparation of Ni-500 catalyst: First, 2.1801 g of nickel nitrate hexahydrate and 4.3642 g of cobalt nitrate hexahydrate were mixed and ground for 5 minutes, and then calcined at 500 °C for 4 hours in an air atmosphere to obtain Ni 1 Co 2 O x -500; then 1.0005g Ni 1 Co 2 O x -500 and 0.0206 g of palladium acetate were mixed and dissolved in 10 mL of acetone, the mixture was stirred at 60 ° C overnight and the acetone was removed, the solid obtained after drying was ground into powder, and then calcined at 400 ° C for 4 hours in an air atmosphere to obtain a precursor; the precursor was heated to 10 v / v% H 2 / N 2 Pd(1) / Ni was obtained by calcining at 200℃ for 1 hour in a 1 Co 2 O x -500 catalyst.

[0058] 0.0505 g 5-hydroxymethylfurfural and 5.0025 g deionized water were added to a reaction kettle (25 mL), and then 0.0512 g Pd(1) / Ni 1 Co 2 O x -500 catalyst, seal the reactor and fill it with 2MPa pure hydrogen (99.999%), place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 3 hours to terminate the reaction, take out the reaction mixture and detect it. The test results are listed in Table 1.

[0059] Example 7

[0060] Pd(1) / Ni 1 Co 2 O x Preparation of -0.2VC-500 catalyst: First, 2.1808 g nickel nitrate hexahydrate, 4.3665 g cobalt nitrate hexahydrate and 0.7931 g ascorbic acid were mixed and ground for 5 minutes, and then calcined at 500 °C for 4 hours in air atmosphere to obtain Ni 1 Co 2 O x -0.2VC-500; then 1.0010g Ni 1 Co 2 O x-0.2g VC-500 and 0.0202g palladium acetate were mixed and dissolved in 10mL acetone, the mixture was stirred at 60°C overnight and the acetone was removed, the solid obtained after drying was ground into powder, and then calcined at 400°C for 4 hours in air atmosphere to obtain a precursor; the precursor was heated to 10v / v% H 2 / N 2 Pd(1) / Ni was obtained by calcining at 200℃ for 1 hour in a 1 Co 2 O x -0.2VC-500 catalyst.

[0061] 0.0501 g 5-hydroxymethylfurfural and 5.0011 g deionized water were added to a reaction kettle (25 mL), and then 0.0510 g Pd(1) / Ni 1 Co 2 O x -0.2VC-500 catalyst, seal the reactor and fill it with 2MPa pure hydrogen (99.999%), place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 3 hours to terminate the reaction, take out the reaction mixture and detect it. The test results are listed in Table 1.

[0062] Example 8

[0063] Pd(1) / Ni 1 Co 2 O x Preparation of -0.1VC-500 catalyst: First, 2.1812g nickel nitrate hexahydrate, 4.3655g cobalt nitrate hexahydrate and 0.3963g ascorbic acid were mixed and ground for 5 minutes, and then calcined at 500°C for 4 hours in an air atmosphere to obtain Ni 1 Co 2 O x -0.1VC-500; then 1.0005g Ni 1 Co 2 O x -0.1g VC-500 and 0.0206g palladium acetate were mixed and dissolved in 10mL acetone, the mixture was stirred at 60°C overnight and the acetone was removed, the solid obtained after drying was ground into powder, and then calcined at 400°C for 4 hours in air atmosphere to obtain a precursor; the precursor was heated to 10v / v% H 2 / N 2 Pd(1) / Ni was obtained by calcining at 200℃ for 1 hour in a 1 Co 2 O x -0.1VC-500 catalyst.

[0064] 0.0506 g 5-hydroxymethylfurfural and 5.0002 g deionized water were added to a reaction kettle (25 mL), and then 0.0503 g Pd(1) / Ni 1 Co 2 O x -0.1VC-500 catalyst, seal the reactor and fill it with 2MPa pure hydrogen (99.999%), place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 3 hours to terminate the reaction, take out the reaction mixture and detect it. The test results are listed in Table 2.

[0065] Example 9

[0066] Pd(1) / Ni 1 Co 2 O x Preparation of -0.3VC-500 catalyst: First, 2.1812 g nickel nitrate hexahydrate, 4.3651 g cobalt nitrate hexahydrate and 1.1892 g ascorbic acid were mixed and ground for 5 minutes, and then calcined at 500 °C for 4 hours in an air atmosphere to obtain Ni 1 Co 2 O x -0.3VC-500; then 1.0012g Ni 1 Co 2 O x -0.3g VC-500 and 0.0206g palladium acetate were mixed and dissolved in 10mL acetone, the mixture was stirred at 60°C overnight and the acetone was removed, the solid obtained after drying was ground into powder, and then calcined at 400°C for 4 hours in air atmosphere to obtain a precursor; the precursor was heated to 10v / v% H 2 / N 2 Pd(1) / Ni was obtained by calcining at 200℃ for 1 hour in a 1 Co 2 O x -0.3VC-500 catalyst.

[0067] 0.0501 g 5-hydroxymethylfurfural and 5.0005 g deionized water were added to a reaction kettle (25 mL), and then 0.0500 g Pd(1) / Ni 1 Co 2 O x -0.3VC-500 catalyst, seal the reactor and fill it with 2MPa pure hydrogen (99.999%), place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 3 hours to terminate the reaction, take out the reaction mixture and test it. The test results are listed in Table 2.

[0068] Example 10

[0069] Pd(1) / Ni 1 Co 2 O x Preparation of -0.4VC-500 catalyst: First, 2.1820g nickel nitrate hexahydrate, 4.3657g cobalt nitrate hexahydrate and 1.5851g ascorbic acid were mixed and ground for 5 minutes, and then calcined at 500°C for 4 hours in air atmosphere to obtain Ni 1 Co 2 O x -0.4VC-500; then 1.0016g Ni 1 Co 2 O x -0.4g VC-500 and 0.0206g palladium acetate were mixed and dissolved in 10mL acetone, the mixture was stirred at 60°C overnight and the acetone was removed, the solid obtained after drying was ground into powder, and then calcined at 400°C for 4 hours in air atmosphere to obtain a precursor; the precursor was heated to 10v / v% H 2 / N 2 Pd(1) / Ni was obtained by calcining at 200℃ for 1 hour in a 1 Co 2 O x -0.4VC-500 catalyst.

[0070] 0.0509 g 5-hydroxymethylfurfural and 5.0008 g deionized water were added to a reaction kettle (25 mL), and then 0.0500 g Pd(1) / Ni 1 Co 2 O x -0.4VC-500 catalyst, seal the reactor and fill it with 2MPa pure hydrogen (99.999%), place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 3 hours to terminate the reaction, take out the reaction mixture and test it. The test results are listed in Table 2.

[0071] Embodiment 11

[0072] Pd(1) / Ni 1 Co 2 O x Preparation of -0.2VC-300 catalyst: First, 2.1810 g nickel nitrate hexahydrate, 4.3651 g cobalt nitrate hexahydrate and 0.7922 g ascorbic acid were mixed and ground for 5 minutes, and then calcined at 300 °C for 4 hours in air atmosphere to obtain Ni 1 Co 2 O x -0.2VC-300; then 1.0010g Ni 1 Co 2 O x-0.2 VC-300 and 0.0201 g palladium acetate were mixed and dissolved in 10 mL acetone. The mixture was stirred at 60 ° C overnight and the acetone was removed. The solid obtained after drying was ground into powder, and then calcined at 400 ° C for 4 hours in an air atmosphere to obtain a precursor; the precursor was heated to 10 v / v% H 2 / N 2 Pd(1) / Ni was obtained by calcining at 200℃ for 1 hour in a 1 Co 2 O x -0.2VC-300 catalyst.

[0073] 0.0501 g 5-hydroxymethylfurfural and 5.0000 g deionized water were added to a reaction kettle (25 mL), and then 0.0502 g Pd(1) / Ni 1 Co 2 O x -0.2VC-300 catalyst, seal the reactor and fill it with 2MPa pure hydrogen (99.999%), place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 3 hours to terminate the reaction, take out the reaction mixture and test it. The test results are listed in Table 3.

[0074] Example 12

[0075] Pd(1) / Ni 1 Co 2 O x Preparation of -0.2VC-400 catalyst: First, 2.1801 g nickel nitrate hexahydrate, 4.3601 g cobalt nitrate hexahydrate and 0.7922 g ascorbic acid were mixed and ground for 5 minutes, and then calcined at 400 °C for 4 hours in an air atmosphere to obtain Ni 1 Co 2 O x -0.2VC-400; then 1.0002g Ni 1 Co 2 O x -0.2g VC-400 and 0.0206g palladium acetate were mixed and dissolved in 10mL acetone, the mixture was stirred at 60°C overnight and the acetone was removed, the solid obtained after drying was ground into powder, and then calcined at 400°C for 4 hours in air atmosphere to obtain a precursor; the precursor was heated to 10v / v% H 2 / N 2 Pd(1) / Ni was obtained by calcining at 200℃ for 1 hour in a 1 Co 2 O x -0.2VC-400 catalyst.

[0076] 0.0510 g 5-hydroxymethylfurfural and 5.0056 g deionized water were added to a reaction kettle (25 mL), and then 0.0509 g Pd(1) / Ni 1 Co 2 O x -0.2VC-400 catalyst, seal the reactor and fill it with 2MPa pure hydrogen (99.999%), place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 3 hours to terminate the reaction, take out the reaction mixture and test it. The test results are listed in Table 3.

[0077] Embodiment 13

[0078] Pd(1) / Ni 1 Co 2 O x Preparation of -0.2VC-600 catalyst: First, 2.1808 g nickel nitrate hexahydrate, 4.3612 g cobalt nitrate hexahydrate and 0.7926 g ascorbic acid were mixed and ground for 5 minutes, and then calcined at 600 °C for 4 hours in an air atmosphere to obtain Ni 1 Co 2 O x -0.2VC-600; then 1.0008g Ni 1 Co 2 O x -0.2 VC-600 and 0.0209 g palladium acetate were mixed and dissolved in 10 mL acetone. The mixture was stirred at 60 ° C overnight and the acetone was removed. The solid obtained after drying was ground into powder and then calcined at 400 ° C for 4 hours in an air atmosphere to obtain a precursor. The precursor was heated to 10 v / v% H 2 / N 2 Pd(1) / Ni was obtained by calcining at 200℃ for 1 hour in a 1 Co 2 O x -0.2VC-600 catalyst.

[0079] 0.0505 g 5-hydroxymethylfurfural and 5.0005 g deionized water were added to a reaction kettle (25 mL), and then 0.0501 g Pd(1) / Ni 1 Co 2 O x -0.2VC-600 catalyst, seal the reactor and fill it with 2MPa pure hydrogen (99.999%), place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 3 hours to terminate the reaction, take out the reaction mixture and test it. The test results are listed in Table 3.

[0080] Embodiment 14

[0081] Pd(1) / Ni 1 Co 1 O x Preparation of -0.2VC-500 catalyst: First, 3.2721 g nickel nitrate hexahydrate, 3.2787 g cobalt nitrate hexahydrate and 0.7919 g ascorbic acid were mixed and ground for 5 minutes, and then calcined at 500 °C for 4 hours in an air atmosphere to obtain Ni 1 Co 1 O x -0.2VC-500; then 1.0011g Ni 1 Co 1 O x -0.2g VC-500 and 0.0206g palladium acetate were mixed and dissolved in 10mL acetone, the mixture was stirred at 60°C overnight and the acetone was removed, the solid obtained after drying was ground into powder, and then calcined at 400°C for 4 hours in air atmosphere to obtain a precursor; the precursor was heated to 10v / v% H 2 / N 2 Pd(1) / Ni was obtained by calcining at 200℃ for 1 hour in a 1 Co 1 O x -0.2VC-500 catalyst.

[0082] 0.0509 g 5-hydroxymethylfurfural and 5.0001 g deionized water were added to a reaction kettle (25 mL), and then 0.0505 g Pd(1) / Ni 1 Co 1 O x -0.2VC-500 catalyst, seal the reactor and fill it with 2MPa pure hydrogen (99.999%), place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 3 hours to terminate the reaction, take out the reaction mixture and test it. The test results are listed in Table 4.

[0083] Embodiment 15

[0084] Pd(1) / Ni 1 Co 4 O x Preparation of -0.2VC-500 catalyst: First, 1.3097g nickel nitrate hexahydrate, 5.2366g cobalt nitrate hexahydrate and 0.7928g ascorbic acid were mixed and ground for 5 minutes, and then calcined at 500°C for 4 hours in an air atmosphere to obtain Ni 1 Co 4 O x -0.2VC-500; then 1.0006g Ni 1 Co 4 O x-0.2g VC-500 and 0.0208g palladium acetate were mixed and dissolved in 10mL acetone, the mixture was stirred at 60°C overnight and the acetone was removed, the solid obtained after drying was ground into powder, and then calcined at 400°C for 4 hours in air atmosphere to obtain a precursor; the precursor was heated to 10v / v% H 2 / N 2 Pd(1) / Ni was obtained by calcining at 200℃ for 1 hour in a 1 Co 4 O x -0.2VC-500 catalyst.

[0085] 0.0501 g 5-hydroxymethylfurfural and 5.0011 g deionized water were added to a reaction kettle (25 mL), and then 0.0501 g Pd(1) / Ni 1 Co 4 O x -0.2VC-500 catalyst, seal the reactor and fill it with 2MPa pure hydrogen (99.999%), place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 3 hours to terminate the reaction, take out the reaction mixture and test it. The test results are listed in Table 4.

[0086] Example 16

[0087] Pd(1) / Ni 1 Co 6 O x Preparation of -0.2VC-500 catalyst: First, 0.9327g nickel nitrate hexahydrate, 5.6177g cobalt nitrate hexahydrate and 0.7941g ascorbic acid were mixed and ground for 5 minutes, and then calcined at 500°C for 4 hours in an air atmosphere to obtain Ni 1 Co 6 O x -0.2VC-500; then 1.0008g Ni 1 Co 6 O x -0.2 VC-500 and 0.0201 g palladium acetate were mixed and dissolved in 10 mL acetone. The mixture was stirred at 60 ° C overnight and the acetone was removed. The solid obtained after drying was ground into powder, and then calcined at 400 ° C for 4 hours in an air atmosphere to obtain a precursor; the precursor was heated to 10 v / v% H 2 / N 2 Pd(1) / Ni was obtained by calcining at 200℃ for 1 hour in a 1 Co 6 O x -0.2VC-500 catalyst.

[0088] 0.0500 g 5-hydroxymethylfurfural and 5.0000 g deionized water were added to a reaction kettle (25 mL), and then 0.0500 g Pd(1) / Ni 1 Co 6 O x -0.2VC-500 catalyst, seal the reactor and fill it with 2MPa pure hydrogen (99.999%), place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 3 hours to terminate the reaction, take out the reaction mixture and test it. The test results are listed in Table 4.

[0089] Embodiment 17

[0090] Pd(0.5) / Ni 1 Co 2 O x Preparation of -0.2VC-500 catalyst: First, Ni 1 Co 2 O x -0.2VC-500 preparation procedure is the same as in Example 7; then 1.0008g Ni 1 Co 2 O x -0.2g VC-500 and 0.0102g palladium acetate were mixed and dissolved in 10mL acetone, the mixture was stirred at 60°C overnight and the acetone was removed, the solid obtained after drying was ground into powder, and then calcined at 400°C for 4 hours in air atmosphere to obtain a precursor; the precursor was heated to 10v / v% H 2 / N 2 Pd(0.5) / Ni was obtained by calcining at 200℃ for 1 hour in a 1 Co 2 O x -0.2VC-500 catalyst.

[0091] 0.0501 g 5-hydroxymethylfurfural and 5.0006 g deionized water were added to a reaction kettle (25 mL), and then 0.1005 g Pd(0.5) / Ni 1 Co 2 O x -0.2VC-500 catalyst, seal the reactor and fill it with 2MPa pure hydrogen (99.999%), place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 3 hours to terminate the reaction, take out the reaction mixture and test it. The test results are listed in Table 5.

[0092] Embodiment 18

[0093] Pd(2) / Ni 1 Co 2 O xPreparation of -0.2VC-500 catalyst: First, Ni 1 Co 2 O x -0.2VC-500 preparation procedure is the same as in Example 7; then 1.0000g Ni 1 Co 2 O x -0.2g VC-500 and 0.0403g palladium acetate were mixed and dissolved in 10mL acetone, the mixture was stirred at 60°C overnight and the acetone was removed, the solid obtained after drying was ground into powder, and then calcined at 400°C for 4 hours in air atmosphere to obtain a precursor; the precursor was heated to 10v / v% H 2 / N 2 Pd(2) / Ni was obtained by calcining at 200℃ for 1 hour in a 1 Co 2 O x -0.2VC-500 catalyst.

[0094] 0.0506 g 5-hydroxymethylfurfural and 5.0000 g deionized water were added to a reaction kettle (25 mL), and then 0.0251 g Pd(2) / Ni 1 Co 2 O x -0.2VC-500 catalyst, seal the reactor and fill it with 2MPa pure hydrogen (99.999%), place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 3 hours to terminate the reaction, take out the reaction mixture and test it. The test results are listed in Table 5.

[0095] Embodiment 19

[0096] Ru(1) / Ni 1 Co 2 O x Preparation of -0.2VC-500 catalyst: First, Ni 1 Co 2 O x -0.2VC-500 preparation procedure is the same as in Example 7; then 0.5046g Ni 1 Co 2 O x -0.2 VC-500 and 0.0205 g of ruthenium acetylacetonate were mixed and dissolved in 10 mL of acetone. The mixture was stirred overnight at 60 ° C and the acetone was removed. The solid obtained after drying was ground into powder and then calcined at 400 ° C for 4 hours in an air atmosphere to obtain a precursor. The precursor was heated to 10 v / v% H 2 / N 2 Ru(1) / Ni was obtained by calcining at 200℃ for 1 hour in a 1 Co2 O x -0.2VC-500 catalyst.

[0097] 0.0505 g 5-hydroxymethylfurfural and 5.0001 g deionized water were added to a reaction kettle (25 mL), and then 0.0098 g Ru(1) / Ni 1 Co 2 O x -0.2VC-500 catalyst, seal the reactor and fill it with 2MPa pure hydrogen (99.999%), place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 3 hours to terminate the reaction, take out the reaction mixture and test it. The test results are listed in Table 5.

[0098] Embodiment 20

[0099] Pt(1) / Ni 1 Co 2 O x Preparation of -0.2VC-500 catalyst: First, Ni 1 Co 2 O x -0.2VC-500 was prepared in the same manner as in Example 7; then 0.5027 g Ni 1 Co 2 O x -0.2 VC-500 and 0.0097 g of platinum acetylacetonate were mixed and dissolved in 10 mL of acetone. The mixture was stirred overnight at 60 ° C and the acetone was removed. The solid obtained after drying was ground into powder and then calcined at 400 ° C for 4 hours in an air atmosphere to obtain a precursor. The precursor was heated to 10 v / v% H 2 / N 2 Pt(1) / Ni was obtained by calcining at 200℃ for 1 hour in a 1 Co 2 O x -0.2VC-500 catalyst.

[0100] 0.0500 g 5-hydroxymethylfurfural and 5.0000 g deionized water were added to a reaction kettle (25 mL), and then 0.0181 g Pt (1.0) / Ni 1 Co 2 O x -0.2VC-500 catalyst, seal the reactor and fill it with 2MPa pure hydrogen (99.999%), place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 3 hours to terminate the reaction, take out the reaction mixture and test it. The test results are listed in Table 5.

[0101] Embodiment 21

[0102] The preparation method of the catalyst is the same as that of Example 7.

[0103] 0.0502 g 5-hydroxymethylfurfural and 5.0006 g deionized water were added to a reaction kettle (25 mL), and then 0.0061 g Pd(1) / Ni 1 Co 2 O x -0.2VC-500 catalyst, seal the reactor and fill it with 1MPa hydrogen, place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 4 hours to end the reaction, take out the reaction mixture and test it. The test results are listed in Table 5.

[0104] Embodiment 22

[0105] The preparation method of the catalyst is the same as that of Example 7.

[0106] 0.0500 g 5-hydroxymethylfurfural and 5.0001 g deionized water were added to a reaction kettle (25 mL), and then 0.0060 g Pd(1) / Ni 1 Co 2 O x -0.2VC-500 catalyst, seal the reactor and fill it with 1MPa hydrogen, place the reactor in a 60℃ oil bath and vigorously stir at 500rpm and maintain for 1.5 hours to end the reaction, take out the reaction mixture and test it. The test results are listed in Table 5.

[0107] Embodiment 23

[0108] The preparation method of the catalyst is the same as that of Example 7.

[0109] 0.0474 g furfural and 5.0656 g deionized water were added to a reaction kettle (25 mL), and then 0.0062 g Pd(1) / Ni 1 Co 2 O x -0.2VC-500 catalyst, seal the reactor and fill it with 1MPa hydrogen, place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 4 hours to end the reaction, take out the reaction mixture and test it. The test results are listed in Table 6.

[0110] Embodiment 24

[0111] The preparation method of the catalyst is the same as that of Example 7.

[0112] 0.0480 g furfuryl alcohol and 5.0158 g deionized water were added to a reaction kettle (25 mL), and then 0.0064 g Pd(1) / Ni 1 Co 2 O x-0.2VC-500 catalyst, seal the reactor and fill it with 1MPa hydrogen, place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 4 hours to end the reaction, take out the reaction mixture and test it. The test results are listed in Table 6.

[0113] Embodiment 25

[0114] The preparation method of the catalyst is the same as that of Example 7.

[0115] 0.0481 g 5-methylfurfural and 5.1611 g deionized water were added to a reaction kettle (25 mL), and then 0.0060 g Pd(1) / Ni 1 Co 2 O x -0.2VC-500 catalyst, seal the reactor and fill it with 1MPa hydrogen, place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 4 hours to end the reaction, take out the reaction mixture and test it. The test results are listed in Table 6.

[0116] Embodiment 26

[0117] The preparation method of the catalyst is the same as that of Example 7.

[0118] 0.0475 g 5-methylfurfuryl alcohol and 5.1529 g deionized water were added to a reaction kettle (25 mL), and then 0.0065 g Pd(1) / Ni 1 Co 2 O x -0.2VC-500 catalyst, seal the reactor and fill it with 1MPa hydrogen, place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 4 hours to end the reaction, take out the reaction mixture and test it. The test results are listed in Table 6.

[0119] Embodiment 27

[0120] The preparation method of the catalyst is the same as that of Example 7.

[0121] 0.0472 g 2,5-furan dimethanol and 5.0269 g deionized water were added to a reaction kettle (25 mL), and then 0.0063 g Pd(1) / Ni 1 Co 2 O x -0.2VC-500 catalyst, seal the reactor and fill it with 1MPa hydrogen, place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 4 hours to end the reaction, take out the reaction mixture and test it. The test results are listed in Table 6.

[0122] Embodiment 28

[0123] The preparation method of the catalyst is the same as that of Example 7.

[0124] 0.2557 g 5-hydroxymethylfurfural and 4.7609 g deionized water were added to a reaction kettle (25 mL), and then 0.0316 g Pd(1) / Ni 1 Co 2 O x -0.2VC-500 catalyst, seal the reactor and fill it with 2MPa pure hydrogen (99.999%), place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 7 hours to terminate the reaction, take out the reaction mixture and test it. The test results are listed in Table 7.

[0125] Embodiment 29

[0126] The preparation method of the catalyst is the same as that of Example 7.

[0127] 0.7502 g 5-hydroxymethylfurfural and 4.2455 g deionized water were added to a reaction kettle (25 mL), and then 0.0917 g Pd(1) / Ni 1 Co 2 O x -0.2VC-500 catalyst, seal the reactor and fill it with 3MPa hydrogen, place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 15 hours to end the reaction, take out the reaction mixture and test it. The test results are listed in Table 7.

[0128] Embodiment 30

[0129] The preparation method of the catalyst is the same as that of Example 7.

[0130] 1.5033 g 5-hydroxymethylfurfural and 3.5314 g deionized water were added to a reaction kettle (25 mL), and then 0.1814 g Pd(1) / Ni 1 Co 2 O x -0.2VC-500 catalyst, seal the reactor and fill it with 5MPa hydrogen, place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 20 hours to end the reaction, take out the reaction mixture and test it. The test results are listed in Table 7.

[0131] Embodiment 31

[0132] The preparation method of the catalyst is the same as that of Example 7.

[0133] 2.9937 g 5-hydroxymethylfurfural and 2.0381 g deionized water were added to a reaction kettle (25 mL), and then 0.3619 g Pd(1) / Ni 1 Co 2 Ox -0.2VC-500 catalyst, seal the reactor and fill it with 6MPa hydrogen, place the reactor in a 30℃ oil bath and vigorously stir at 500rpm and maintain for 25 hours to end the reaction, take out the reaction mixture and test it. The test results are listed in Table 7.

[0134] Embodiment 32

[0135] The preparation method of the catalyst is the same as that of Example 7.

[0136] 3.0105 g 5-hydroxymethylfurfural and 2.0025 g deionized water were added to a reaction kettle (25 mL), and then 0.3623 g Pd(1) / Ni 1 Co 2 O x -0.2VC-500 catalyst, seal the reactor and fill it with 3MPa hydrogen, place the reactor in a 60℃ oil bath and stir vigorously at 500rpm, when the reaction is carried out to 3 hours, 6 hours and 9 hours, after the reaction mixture is cooled to room temperature, replenish the hydrogen pressure in the reactor to 3MPa, and terminate the reaction after a total of 18 hours. Take out the reaction mixture and test it. The test results are listed in Table 7.

[0137] Embodiment 33

[0138] The preparation method of the catalyst is the same as that of Example 7.

[0139] 0.41 g 5-hydroxymethylfurfural (refined or unrefined, the unrefined content is 61 wt%, crude HMF product purchased from Zhongke Guosheng (Hangzhou) Technology Co., Ltd.) and 4.6000 g deionized water were added to a reaction kettle (25 mL), and then 0.0306 g Pd(1) / Ni 1 Co 2 O x -0.2VC-500 catalyst, seal the reactor and fill it with 1.5MPa hydrogen, place the reactor in a 60℃ oil bath and stir vigorously at 500rpm. After the reaction mixture is cooled to room temperature for 4 hours, take out the reaction mixture and test it. The test results are listed in Table 7.

[0140] Embodiment 34

[0141] The preparation method of the catalyst is the same as that of Example 7.

[0142] 0.82 g of 5-hydroxymethylfurfural (refined or unrefined, the unrefined content is 61 wt%, HMF crude product purchased from Zhongke Guosheng (Hangzhou) Technology Co., Ltd.) and 4.1801 g of deionized water were added to a reaction kettle (25 mL), and then 0.0601 g of Pd(1) / Ni1 Co 2 O x -0.2VC-500 catalyst, seal the reactor and fill it with 2MPa pure hydrogen (99.999%), place the reactor in a 60℃ oil bath and stir vigorously at 500rpm. After the reaction mixture is cooled to room temperature for 7 hours, take out the reaction mixture and test it. The test results are listed in Table 7.

[0143] Embodiment 35

[0144] The preparation method of the catalyst is the same as that of Example 7.

[0145] 1.23 g 5-hydroxymethylfurfural (refined or unrefined, the unrefined content is 61 wt%, HMF crude product purchased from Zhongke Guosheng (Hangzhou) Technology Co., Ltd.) and 3.7712 g deionized water were added to a reaction kettle (25 mL), and then 0.0921 g Pd(1) / Ni 1 Co 2 O x -0.2VC-500 catalyst, seal the reactor and fill it with 2.5MPa hydrogen, place the reactor in a 60℃ oil bath and stir vigorously at 500rpm. After the reaction is carried out for 10 hours and the reaction mixture is cooled to room temperature, take out the reaction mixture and test it. The test results are listed in Table 7.

[0146] Embodiment 36

[0147] The preparation method of the catalyst is the same as that of Example 7.

[0148] 1.64 g 5-hydroxymethylfurfural (refined or unrefined, the unrefined content is 61 wt%, HMF crude product purchased from Zhongke Guosheng (Hangzhou) Technology Co., Ltd.) and 3.3602 g deionized water were added to a reaction kettle (25 mL), and then 0.1203 g Pd(1) / Ni 1 Co 2 O x -0.2VC-500 catalyst, seal the reactor and fill it with 3MPa hydrogen, place the reactor in a 60℃ oil bath and stir vigorously at 500rpm. After the reaction mixture is cooled to room temperature for 12 hours, take out the reaction mixture and test it. The test results are listed in Table 7.

[0149] Experimental results:

[0150] Depend on Figure 1 The high-resolution TEM image and particle size distribution of the catalyst obtained in Example 7 shown in the figure show that the catalyst carrier is a black powder. 1 Co 2 Ox Pd nanoparticles are distributed on the surface, and the average size of the Pd nanoparticles is 3.1nm. Figure 3 The XRD characterization results show that the carrier Ni 1 Co 2 O x and Ni 1 Co 2 O x -0.2VC all show spinel structure Ni 1 Co 2 O 4 Standard crystal form ( Figure 3 a); after loading Pd, the carrier crystal form of the two catalysts was transformed into a mixed crystal form of NiO and CoO ( Figure 3 a), further fitting of the two diffraction peaks at about 36° and 42° of the XRD diffraction peaks revealed that the diffraction peak at about 36° can be fitted to the (111) crystal plane of CoO and NiO, of which the CoO (111) crystal plane only accounts for 25.8-28.7%; and the diffraction peak at about 42° can be fitted to the (200) crystal plane of CoO and NiO, of which the CoO (200) crystal plane only accounts for 26.4-33.1%. Therefore, after loading Pd, the carrier crystal form of the two catalysts mainly presents NiO ( Figure 3 bc), no XRD diffraction peak of Pd was observed, which may be due to the low Pd loading and good dispersion of Pd on the catalyst surface.

[0151] The oxygen vacancy content (O v ).from Figure 4 The test results in the figure (the brackets correspond to the oxygen vacancy content of each catalyst) show that the addition of VC additive significantly increases the oxygen vacancy content on the surface of the nickel-cobalt bimetallic oxide support. In addition, after loading Pd, the oxygen vacancy content of the catalyst is further improved. Figure 5 As shown in the figure, the addition of VC additive significantly increases the specific surface area and total pore volume of the nickel-cobalt bimetallic oxide support, in which the specific surface area of ​​the composite support is mainly composed of Ni 1 Co 2 O x -500 of 3.5m 2 / g -1 Increase to Ni 1 Co 2 O x -0.2VC-5007.1m 2 / g -1 (like Figure 5 a); The total pore volume of the composite support is composed of Ni 1 Co 2O x -500 0.02cm 3 / g -1 Increase to Ni 1 Co 2 O x -0.200.04cm for VC-500 3 / g -1 (like Figure 5 b).

[0152] Table 1 Test results of Examples 1-7

[0153]

[0154] From the test results in Table 1, it can be seen that in Example 1, when Pd alone is used as a catalyst to catalyze the hydrogenation of HMF to synthesize BHMTHF, the HMF conversion rate is only 38.5%, and the yield of BHMTHF is only 8.8%. The experimental results of Example 2 show that when palladium supported on nickel oxide is used as a catalyst, the HMF conversion rate is increased to 57.1%, while the yield of BHMTHF remains basically unchanged (9.7%), and the intermediate product (2,5-furan dimethanol, the yield is 35.2%) is mainly formed. The experimental results of Example 3 show that the palladium catalyst supported on the nickel oxide carrier obtained with the assistance of VC, the HMF conversion rate is further increased to 79.7%, and the yield of BHMTHF is also increased to 22.2%. Changing the metal element of the carrier to cobalt, the experimental results in Example 4 show that the palladium catalyst supported on cobalt oxide alone can only provide 49.7% HMF conversion rate and a small amount of BHMTHF (2.1%). The experimental results in Example 5 show that the HMF conversion rate of the palladium catalyst supported on the cobalt oxide carrier obtained with the assistance of VC reached 99.9%, and the yield of BHMTHF was also increased to 30.5%. The experimental results in Example 6 show that the HMF conversion rate and BHMTHF yield of the palladium catalyst supported on the nickel cobalt oxide carrier did not show an improvement in hydrogenation performance compared with the single metal Pd (Example 1). The experimental results in Example 7 show that the palladium catalyst supported on the nickel cobalt oxide carrier obtained with the assistance of VC (Pd(1) / Ni 1 Co 2 O x -0.2VC-500) catalyzed HMF hydrogenation, the HMF conversion rate and BHMTHF yield increased to 99.9% and 80.1%, respectively. 1 Co 2 O x The element contents of Pd, Ni and Co in -0.2VC-500 were determined by inductively coupled plasma-mass spectrometry and were 1.09wt%, 23.08wt% and 45.33wt%, respectively.

[0155] Table 2 Test results of Examples 6-10

[0156]

[0157] In addition, the effect of the amount of VC used in the catalyst preparation process on the catalytic performance of the catalyst was further evaluated. From the experimental results in Examples 6-10, it can be seen that the HMF conversion rate and BHMTHF yield of the palladium catalyst supported by the nickel cobalt oxide carrier obtained without the assistance of VC are only 46.9% and 7.3% respectively (Table 2, Example 6). The catalytic performance of the catalyst prepared by adding VC during the catalyst synthesis process is significantly improved, and the BHMTHF yield and VC dosage show a "volcano-type" relationship, especially when the amount of VC is 0.2 relative to the total molar amount of nickel and cobalt elements, the yield of BHMTHF reaches a maximum value (80.1%, Table 2, Example 7).

[0158] Table 3 Test results of Examples 7, 11-13

[0159]

[0160] The effect of the calcination temperature of the nickel-cobalt bimetallic oxide support on the catalytic activity of the catalyst was evaluated. When the calcination temperature was increased from 300°C to 500°C (Table 3, Examples 7, 11-12), the obtained catalyst was used for the hydrogenation experiment of HMF, and the HMF conversion rate increased from 61.3% to 99.9%, and the BHMTHF yield increased from 45.2% to 80.1%. When the calcination temperature was further increased to 600°C, the obtained catalyst was used for the hydrogenation experiment of HMF, and the HMF conversion rate remained basically unchanged, while the BHMTHF yield was slightly reduced to 70.2% (Table 3, Example 13). It can be seen that the optimal calcination temperature of the support is 500°C.

[0161] Table 4 Test results of Examples 7, 14-16

[0162]

[0163] The effect of the molar ratio of nickel and cobalt in the nickel-cobalt bimetallic oxide on the catalytic activity of the catalyst was evaluated. When the molar ratio of nickel and cobalt was 1:1, the obtained catalyst was used for the hydrogenation experiment of HMF, and the HMF conversion rate was 99.2% and the BHMTHF yield was 44.8% (Table 4, Example 14). When the molar ratio of nickel and cobalt was 1:2, the yield of BHMTHF was increased to 80.1% (Table 4, Example 7). In addition, when the molar ratio of nickel and cobalt was 1:4 and 1:6, the two obtained catalysts were used for the hydrogenation experiment of HMF, and both obtained HMF conversion rates of up to 99% could be obtained, while only a medium yield of BHMTHF (50%-60%, Table 4, Examples 15-16) could be obtained; it can be seen that the optimal molar ratio of nickel and cobalt is 1:2.

[0164] Table 5 Test results of Examples 7, 17-22

[0165]

[0166] In addition, the effect of metal palladium loading on the catalytic activity of the catalyst was further evaluated. 1 Co 2 O x -0.2VC-500 was used as a catalyst to catalyze HMF, the HMF conversion rate was 99.8% and the BHMTHF yield was 40.8% (Table 5, Example 17). When the metal palladium loading was further increased to 1.0wt%, HMF was basically completely converted, the intermediate products (2,5-furan dimethanol and 5-hydroxymethyltetrahydrofuran formaldehyde) decreased, and the BHMTHF yield increased significantly to 80.1% (Table 5, Example 7). It is worth noting that when the metal palladium loading was further increased to 2wt%, the HMF conversion rate and BHMTHF yield remained basically unchanged (Table 5, Example 18). In addition, the catalytic activity of the catalyst when other metals were loaded on the nickel cobalt oxide support was further investigated. When ruthenium or platinum was loaded on the nickel cobalt oxide support, the intermediate product (2,5-furan dimethanol) was mainly generated, and only a small amount of BHMTHF was generated (Table 5, Examples 19-20). Under room temperature conditions (30°C), the reaction time was extended to 4 hours, and the reaction time was 2 hours with Pd(1) / Ni 1 Co 2 O x -0.2VC-500 was used as catalyst for HMF hydrogenation reaction, HMF was almost completely converted, and the BHMTHF yield was as high as 95.1% (Table 5, Example 21). The reaction temperature was appropriately increased to 60°C, Pd(1) / Ni 1 Co 2 O x-0.2VC-500 only takes 1.5 hours to completely convert HMF and obtain a BHMTHF yield of up to 91.1% (Table 5, Example 22). 1 Co 2 O x -0.2VC-500 catalyst catalyzes the hydrogenation of HMF to synthesize BHMTHF at a rate of up to 395.3 mol BHMTHF mol Pd -1 h -1 (1MPa H 2 , 60°C, 1.5h, Table 5, Example 22), which exceeds most of the catalysts reported so far.

[0167] Table 6 Test results of Examples 21, 23-27

[0168]

[0169] The results of Examples 21, 23-27 show that when alcohols or aldehydes such as furfuryl alcohol, furfural, 5-methylfurfural and 5-methylfurfural, 2,5-furan dimethanol, and 5-hydroxymethylfurfural are used as reaction substrates, the products obtained are tetrahydrofurfuryl alcohol, tetrahydro-5-methyl-2-furanmethanol or BHMTHF. 1 Co 2 O x -0.2VC-500 catalytic reaction, the conversion rate of raw materials can be as high as 98% or more, and the product yield can be as high as 91.1%-96.1%. It can be seen that the catalyst has excellent catalytic performance in the selective conversion of furan aldehyde alcohol compounds to prepare tetrahydrofuran alcohol compounds under mild reaction conditions.

[0170] Table 7 Test results of Examples 28-32

[0171]

[0172] The results of Examples 28-32 show that at a pure HMF concentration of 5wt%-60wt%, the BHMTHF yield can also reach more than 90%. In addition, at a pure HMF concentration of 60wt%, in order to reduce the initial reaction pressure, a measure of discontinuously or indirectly supplementing hydrogen at least once during the reaction is taken. The experimental results of Example 32 show that this measure is effective. Even if 5-20wt% of unpurified and refined HMF crude raw material (HMF crude product purchased from Zhongke Guosheng (Hangzhou) Technology Co., Ltd., the HMF content in the crude product is 61wt%, the water content is 30wt%, the 2-hydroxyacetyl furan content is 3wt%, furfural is 2wt%, and levulinic acid is 1wt%, added to the reaction system as a raw material, Table 7, Examples 33-36), the BHMTHF yield can also reach 83.1-91.0%. It can be seen that the catalyst synthesized in the present invention has an important promoting significance for the large-scale production of BHMTHF, and solves the problem that the current catalytic system cannot catalyze more than 10wt% of high-concentration HMF in the aqueous phase to prepare BHMTHF by efficient selective hydrogenation. At the same time, high-yield products can also be obtained through crude raw materials, which can greatly improve the synthesis efficiency and production cost of BHMTHF.

[0173] The present catalytic system was compared with the prior art catalytic system, and the results are shown in Table 8.

[0174] Table 8 Comparison of this catalytic system with other catalytic systems

[0175]

[0176]

[0177] a The amount of catalyst indicates the weight ratio of catalyst to substrate; b It refers to the amount of catalyst used: the molar ratio of HMF to the precious metal. c HMF concentration; d The production rate refers to the amount of target product (mole) obtained per precious metal amount (mass) per hour under the listed reaction conditions, [mmol BHMTHF g catalyst -1 h -1 ]. e The production rate refers to the amount of target product (mol) obtained per mole of precious metal per hour under the listed reaction conditions, [mol BHMTHF mol metal -1 h -1 ].

[0178] The above other catalytic systems are from the following references:

[0179] [1]J.Am.Chem.Soc.1955,77,393-396.

[0180] [2]Organic Process Research&Development 2010,14,459-465.

[0181] [3]ACS Sustainable Chemistry&Engineering 2014,2,173-180.

[0182] [4]Green Chem.2015,17,2504-2514.

[0183] [5]Green Chem.2021,23,7996-8002.

[0184] [6]ChemSusChem 2016,9,521-531.

[0185] [7]Chemical Engineering Science 2024,298,120243.

[0186] [8]ACS Catal. 2015, 5, 722-733.

[0187] [9]Green Chem.2012,14,1413-1419.

[0188]

[10] Green Chem.2020,22,850-859.

[0189]

[11] )Catalysis Communications 2010,12,154-156.

[0190]

[12] ACS Catal.2014,4,2718-2726.

[0191]

[13] ACS Sustainable Chemistry&Engineering 2019,7,10670-10678.

[0192]

[14] Chem.Eng.J.2023,460,141779.

[0193] As can be seen from Table 8 above, the catalyst of the present invention can efficiently catalyze the hydrogenation of 5-hydroxymethylfurfural to synthesize 2,5-bis(hydroxymethyl)tetrahydrofuran, and the generation rate is as high as 395.3 mol BHMTHF mol Pd-1 h -1 , which exceeds that of most catalysts reported so far.

[0194] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention without departing from the principles and intent of the present invention.

Claims

1. A Pd / NiCoO x A catalyst characterized by: The NiCoO x Shown is a composite support of Ni oxide and Co oxide, on which Pd is supported.

2. A Pd / NiCoO according to claim 1 x A catalyst characterized by: The catalyst is composed of Pd and NiCoO x The total mass is calculated as 100%, and the mass percentage of Pd is 0.1-2wt%; in the composite carrier, the molar ratio of Ni element to Co element is 1:(1-6); Pd is a nanoparticle with an average particle size of 2-5nm, and the composite carrier corresponds to a mixed oxide with a spinel structure and is a black powder.

3. A Pd / NiCoO according to any one of claims 1 to 2 x The method for preparing a catalyst is characterized by: The steps include: (1) Co salt and Ni salt solid powders are mixed evenly and calcined in a high temperature oxygen-containing atmosphere to form NiCoO x Composite carrier; (2) Dispersing Pd salt and NiCoO in solvent x The composite support is uniform, and then the solvent is removed to obtain NiCoO x A solid mixture of a composite support and a Pd salt; (3) calcining the solid mixture in a high temperature oxygen-containing atmosphere to obtain a catalyst precursor; (4) subjecting the catalyst precursor to a reduction reaction in a high temperature hydrogen-containing atmosphere to obtain the catalyst.

4. The preparation method according to claim 3, characterized in that: The mixing process of step (1) also includes mixing ascorbic acid with solid powders of Co salt and Ni salt; the total molar ratio of ascorbic acid to nickel and cobalt elements in the metal salt is defined as a, a≤0.

4.

5. The preparation method according to claim 3, characterized in that: The nickel salt and cobalt salt in step (1) are nickel nitrate and cobalt nitrate respectively; the calcination temperature in step (1) is 400-600°C and the time is 4-6 hours, and the oxygen-containing atmosphere is air; the palladium salt in step (3) is palladium acetate or palladium chloride, the calcination temperature in step (3) is 400-600°C and the time is 4-6 hours, and the oxygen-containing atmosphere is air; the high temperature in step (4) is 150-250°C and the time is 1-2 hours, and the hydrogen-containing atmosphere is a combination of hydrogen / inert gas.

6. A method for catalytic hydrogenation of furan aldehyde alcohol compounds, characterized in that: The method comprises the following steps: adding furan aldehyde alcohol compound, water and Pd / NiCoOx catalyst into a reaction container, sealing the reaction container and filling it with pure hydrogen to react and obtain a hydrogenation product; the Pd / NiCoOx catalyst is x The catalyst is a Pd / NiCoO as described in claims 1 to 2 x The catalyst is a Pd / NiCoO prepared according to any one of claims 3 to 5. x catalyst.

7. The method for catalytic hydrogenation of furanic aldehyde-alcohol compounds according to claim 6, characterized in that: The hydrogenation reaction conditions are as follows: the hydrogen required for the reaction is added non-continuously, the hydrogen pressure in the reaction container is 0.5-6MPa, the temperature is room temperature-60°C, and the reaction time is 1-4 hours.

8. The method for catalytic hydrogenation of furanic aldehyde-alcohol compounds according to claim 7, characterized in that: The hydrogen required for the reaction is added once, or at least twice in a discontinuous manner.

9. The method for catalytic hydrogenation of furanic aldehyde-alcohol compounds according to claim 6, characterized in that: The furan aldehyde alcohol compound includes one of furfuryl alcohol, furfural, 5-methylfurfural, 5-methylfurfuryl alcohol, 2,5-furan dimethanol and 5-hydroxymethylfurfural, and the concentration of the furan aldehyde alcohol compound is 1-60wt%; the product is one of tetrahydrofurfuryl alcohol, tetrahydro-5-methyl-2-furanmethanol, and 2,5-bis(hydroxymethyl)tetrahydrofuran; more preferably, the concentration of the furan aldehyde alcohol compound is more than 10wt%.

10. The method for catalytic hydrogenation of furanic aldehyde-alcohol compounds according to claim 6, characterized in that: The Pd / NiCoO x The amount of catalyst used: the molar ratio of the furan aldehyde alcohol compound to the Pd element is: (100-1000):1.

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