CN117753453A

CN117753453A - Nickel-based transition metal carbide catalyst and preparation method and application thereof

Info

Publication number: CN117753453A
Application number: CN202311376757.6A
Authority: CN
Inventors: 蒋剑春; 王奎; 黄茹露; 王善勇
Original assignee: Institute of Chemical Industry of Forest Products of CAF
Current assignee: Institute of Chemical Industry of Forest Products of CAF
Priority date: 2023-10-23
Filing date: 2023-10-23
Publication date: 2024-03-26

Abstract

The invention discloses a nickel-based transition metal carbide catalyst and a preparation method and application thereof, belonging to the fields of supported catalyst preparation technology and biomass-based catalytic application. The nickel-based transition metal carbide catalyst containing Lewis acid sites and electron-rich metal sites is obtained based on a liquid-solid process, carburizing treatment and wet reduction strategy, has catalytic activity higher than that of a homogeneous liquid acid catalyst, is convenient to recycle, has excellent stability, can be well applied to hydrogenation reaction of 5-HMF, can selectively regulate and control the generation of various hydrogenation products with high added value, can realize high-value utilization of bio-based oxygen-containing chemicals, and has extremely high economic benefit.

Description

Nickel-based transition metal carbide catalyst and preparation method and application thereof

Technical Field

The invention relates to the field of preparation technology of supported catalysts and biomass-based catalysis application, in particular to a nickel-based transition metal carbide catalyst, and a preparation method and application thereof.

Background

Renewable and abundant lignocellulosic biomass can be converted into high value-added fuels and chemicals, with 5-hydroxymethylfurfural (5-HMF) possessing tremendous market potential, considered as a "sleeping giant" in the sustainable chemistry field. The prominent advantages of 5-HMF are represented by the fact that it has a variety of oxygen-containing functionalities, including carbonyl, hydroxymethyl and furan rings, on its own, which retain sufficient reactivity, and thus selective hydroconversion of 5-HMF is difficult. When the active component acts on aldehyde group to be hydrogenated and reduced into hydroxymethyl, 2, 5-furan dimethanol (BHMF), which is a high added value diol, has a special chemical structure, is an important polymer monomer and a drug synthesis intermediate, can be used for synthesizing polymeric materials such as polyester, polyurethane and the like, has the same aromaticity with petroleum-based chemicals such as terephthalyl alcohol, and therefore, the BHMF has great potential for substituting terephthalyl alcohol to synthesize polymeric materials; when the active component acts on hydroxymethyl to reduce, 5-Methylfurfural (MF) is obtained, which is an important food additive and synthetic intermediate; when the active components continuously act on aldehyde groups and hydroxymethyl groups (avoiding excessive hydrogenation of furan rings), 5-methyl-2-furanmethanol (MFA) and 2, 5-dimethyl furan (DMF) can be obtained successively, and the DMF has the advantages of high energy density (30 MJ/L) and high octane number (119), is soluble in gasoline, is a second-generation liquid biofuel, has the advantages of easy transportation management, high combustion efficiency, difficult water absorption and moisture absorption, low energy consumption for separation and purification and the like, and is the most widely studied fuel substitute. Based on this, selective hydrogenation of 5-HMF is critical for conversion to high value added biomass-based oxygen-containing chemicals and liquid fuels.

Currently, the hydrogenation reduction of 5-HMF mainly utilizes noble metal catalysts with high performance, mainly comprising ruthenium (Ru), platinum (Pt), palladium (Pd) and the like, such as Pt/MCM-41 and Ru/MnCo ₂ O ₄ High selectivity to BHMF and high selectivity to DMF of Pd/MOF-808, but because noble metal catalyst is expensive and scarce in reserves, it limits its large-scale industrial application, so it is considered to replace it with inexpensive and readily available non-noble metal nickel (Ni) with hydrogenation advantage. On the basis of the existing research, the carrier structure of the catalyst has great influence on the catalytic performance, and the common catalyst carriers are metal oxides, molecular sieves, carbon materials and the likeThe carbon material has the characteristics of good porosity, various structures and excellent stability, can well attach the active components to the surface or in the pore canal of the carrier, and the transition metal carbide is a very attractive carbon material, is an intermetallic filling compound, has similar surface electronic properties to Pt and has good catalytic activity in catalytic hydrogenation reaction. Thus, nickel-based transition metal carbides with dual-effect hydrogenation properties offer new possibilities for selective hydrogenation of 5-HMF.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention provides a nickel-based transition metal carbide catalyst, a preparation method and application thereof, and the preparation method is used for preparing a high-efficiency and stable catalyst, so that 5-HMF selective hydrogenation can be realized, and a biomass-based high-added-value chemical product can be obtained.

In order to solve the problems, the technical scheme adopted by the invention is as follows:

the preparation method of the nickel-based transition metal carbide catalyst comprises the following steps: dissolving dopamine hydrochloride and metal composite salt serving as raw materials in deionized water to form a metal-dopamine hydrochloride complex, adding ethanol and ammonia water into the complex, stirring, and collecting precipitate to obtain a metal-dopamine hydrochloride precursor; and then carburizing the metal-dopamine hydrochloride precursor to obtain transition metal carbide, adding the transition metal carbide into a compound solution of metallic nickel, performing ultrasonic treatment, finally adding a sodium borohydride solution under a low-temperature nitrogen atmosphere, standing at room temperature, filtering, washing and drying to obtain the nickel-based transition metal carbide.

Further, the metal complex salt is one of ammonium metatungstate, ammonium metavanadate and ammonium molybdate.

Further, the mass ratio of the dopamine hydrochloride to the metal composite salt is 1:0.5-2.

Further, the carburizing treatment is to heat up to 900-1100 ℃ at a heating rate of 1-5 ℃/min under the nitrogen atmosphere, and keep the temperature for 1-8 hours.

Further, the compound of the metallic nickel is one of nickel nitrate, nickel chloride and nickel sulfate, and the concentration is 0.15-0.30mol/L.

Further, the concentration of the added sodium borohydride solution is 0.30-0.50mol/L.

Further, the preparation method of the nickel-based transition metal carbide catalyst comprises the following steps:

(1) Sequentially dissolving dopamine hydrochloride and metal composite salt in a mass ratio of 1:0.5-2 in deionized water, stirring to form a metal-dopamine hydrochloride complex, adding ethanol into the solution, adding ammonia water rapidly with stirring, continuously stirring at room temperature, centrifugally collecting precipitate, filtering, washing and drying to obtain a metal-dopamine hydrochloride precursor;

(2) Placing a metal-dopamine hydrochloride precursor into a tube furnace, heating to 900-1100 ℃ at a heating rate of 1-5 ℃/min under nitrogen atmosphere, preserving heat for 1-8h, and performing carburizing treatment to obtain transition metal carbide;

(3) Adding transition metal carbide into any one of nickel nitrate, nickel chloride and nickel sulfate with the concentration of 0.15-0.30mol/L, fully mixing, carrying out ultrasonic treatment on the obtained mixture, placing the mixture in a low-temperature reactor, slowly adding sodium borohydride solution with the concentration of 0.30-0.50mol/L under the atmosphere of continuously introducing nitrogen, standing at room temperature, and finally, washing three times by using deionized water and ethanol respectively, and drying for 12 hours at 60 ℃ in a vacuum drying oven to obtain the nickel-based transition metal carbide.

Further, the nickel-based transition metal carbide catalyst is prepared by the preparation method of the nickel-based transition metal carbide catalyst.

Further, the nickel-based transition metal carbide catalyst is applied to the selective hydrogenation reaction of 5-HMF.

Further, the application is as follows: mixing 5-HMF, nickel-based transition metal carbide catalyst and reaction solvent, placing in a sealed high-pressure reaction kettle, replacing air with hydrogen, and carrying out hydrogenation reaction by taking hydrogen as a hydrogen donor, wherein the reaction temperature is 160-190 ℃ and the reaction time is 0.5-3h.

Compared with the prior art, the invention has the advantages that:

1) The nickel-based transition metal carbide catalyst containing Lewis acid sites and electron-rich metal sites is obtained based on a liquid-solid process, carburizing treatment and wet reduction strategy, has catalytic activity higher than that of a homogeneous liquid acid catalyst, is convenient for recycling, and has excellent stability.

2) The catalyst disclosed by the invention can be well applied to hydrogenation reaction of 5-HMF, and meanwhile, the generation of various hydrogenation products with high added value can be selectively regulated and controlled.

3) The invention adopts non-noble metal nickel (Ni) based transition metal carbide with hydrogenation advantage to catalyze 5-HMF selective hydrogenation, thereby reducing the operation cost while ensuring high selectivity and being beneficial to large-scale industrialized application.

4) The transition metal carbide of the present invention is a very attractive carbon material, which is an intermetallic packing compound in which tungsten carbide has surface electronic properties similar to Pt and has good catalytic activity in catalytic hydrogenation reactions. Thus, nickel-based transition metal carbides with dual-effect hydrogenation properties offer new possibilities for selective hydrogenation of 5-HMF.

Drawings

FIG. 1 is a gas chromatogram of the analysis of the product of a nickel-based transition metal carbide catalyst catalyzed selective hydrogenation of 5-HMF at various times;

FIG. 2 is a 5-HMF selective hydrogenation path diagram;

FIG. 3 shows tungsten carbide and Ni obtained in example 4 _0.30 An NH3-TPD characterization of WC-1;

FIG. 4 shows tungsten carbide and Ni obtained in example 4 _0.30 Py-FTIR characterization of WC-1;

FIG. 5 shows tungsten carbide and Ni obtained in example 4 _0.30 XPS Ni 2p of @ WC-1 _3/2 A figure;

FIG. 6 shows tungsten carbide and Ni obtained in example 4 _0.30 XPS W4 f plot of @ WC-1.

Detailed Description

In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof.

Example 1

A method for catalyzing 5-HMF selective hydrogenation by nickel-based transition metal carbide comprises the following specific steps:

(1) Sequentially dissolving dopamine hydrochloride and ammonium metatungstate in a mass ratio of 1:0.5 in deionized water, stirring to form a tungsten-dopamine hydrochloride complex, adding ethanol into the solution, adding ammonia water rapidly with stirring, continuously stirring at room temperature, centrifugally collecting precipitate, filtering, washing and drying to obtain a tungsten-dopamine hydrochloride precursor;

(2) The tungsten-dopamine hydrochloride precursor is placed in a tube furnace for carburizing treatment, the temperature is raised to 900 ℃ at the heating rate of 1 ℃/min under the nitrogen atmosphere, and the temperature is kept for 1h to obtain tungsten carbide;

(3) Adding tungsten carbide into 0.15mol/L nickel nitrate solution, performing ultrasonic treatment on the mixture, placing the mixture in a low-temperature reactor, slowly adding 0.30mol/L sodium borohydride solution under the atmosphere of continuously introducing nitrogen, standing at room temperature, filtering, washing and drying to obtain nickel-base tungsten carbide, and recording as Ni _0.15 @WC-0.5；

(4) 5-HMF and Ni obtained in the step (3) _0.15 Mixing WC-0.5 and solvent, placing in a sealed high-pressure reaction kettle, replacing air with hydrogen, and carrying out hydrogenation reaction under the pressure of 2MPa hydrogen by taking hydrogen as a hydrogen donor.

The Ni obtained in this example _0.15 Analysis of the product of catalytic 5-HMF hydrogenation at different reaction conditions @ WC-0.5, as shown in table 1:

table 1: the Ni obtained in example 1 _0.15 Product analysis Table for catalyzing hydrogenation of 5-HMF under different reaction conditions @ WC-0.5

Example 2

(1) Sequentially dissolving dopamine hydrochloride and ammonium metatungstate in a mass ratio of 1:1 in deionized water, stirring to form a tungsten-dopamine hydrochloride complex, adding ethanol into the solution, adding ammonia water along with stirring, continuously stirring at room temperature, centrifugally collecting precipitate, filtering, washing and drying to obtain a tungsten-dopamine hydrochloride precursor;

(2) The tungsten-dopamine hydrochloride precursor is placed in a tube furnace for carburizing treatment, the temperature is raised to 900 ℃ at the heating rate of 2 ℃/min under the nitrogen atmosphere, and the temperature is kept for 2 hours to obtain tungsten carbide;

(3) Adding tungsten carbide into 0.15mol/L nickel chloride solution, performing ultrasonic treatment on the mixture, placing the mixture in a low-temperature reactor, slowly adding 0.40mol/L sodium borohydride solution under the atmosphere of continuously introducing nitrogen, standing at room temperature, filtering, washing and drying to obtain nickel-base tungsten carbide, and recording as Ni _0.15 @WC-1；

(4) 5-HMF and Ni obtained in the step (3) _0.15 Mixing WC-1 and a solvent, placing in a sealed high-pressure reaction kettle, replacing air with hydrogen, and carrying out hydrogenation reaction under the pressure of 2MPa hydrogen by taking the hydrogen as a hydrogen donor.

The Ni obtained in this example _0.15 Analysis of the product of catalytic 5-HMF hydrogenation at different reaction conditions @ WC-1 is shown in table 2:

table 2: ni obtained in example 2 _0.15 Product analysis Table for catalyzing hydrogenation of 5-HMF under different reaction conditions for WC-1

Example 3

(1) Sequentially dissolving dopamine hydrochloride and ammonium metatungstate in a mass ratio of 1:2 in deionized water, stirring to form a tungsten-dopamine hydrochloride complex, adding ethanol into the solution, adding ammonia water rapidly with stirring, continuously stirring at room temperature, centrifugally collecting precipitate, filtering, washing and drying to obtain a tungsten-dopamine hydrochloride precursor;

(2) The tungsten-dopamine hydrochloride precursor is placed in a tube furnace for carburizing treatment, the temperature is raised to 900 ℃ at the temperature rising rate of 5 ℃/min under the nitrogen atmosphere, and the temperature is kept for 2 hours, so that tungsten carbide is obtained;

(3) Adding tungsten carbide into 0.15mol/L nickel sulfate solution, performing ultrasonic treatment on the mixture, placing the mixture in a low-temperature reactor, slowly adding 0.50mol/L sodium borohydride solution under the atmosphere of continuously introducing nitrogen, standing at room temperature, filtering, washing and drying to obtain nickel-base tungsten carbide, and recording as Ni _0.15 @WC-2；

(4) 5-HMF and Ni obtained in the step (3) _0.15 Mixing WC-2 and a solvent, placing in a sealed high-pressure reaction kettle, replacing air with hydrogen, and carrying out hydrogenation reaction under the pressure of 2MPa hydrogen by taking the hydrogen as a hydrogen donor.

The Ni obtained in this example _0.15 Analysis of the product of catalytic 5-HMF hydrogenation at different reaction conditions @ WC-2 is shown in table 3:

table 3: the Ni obtained in example 3 _0.15 Product analysis Table for catalyzing hydrogenation of 5-HMF under different reaction conditions for WC-2

Example 4

(2) The tungsten-dopamine hydrochloride precursor is placed in a tube furnace for carburizing treatment, the temperature is raised to 900 ℃ at the heating rate of 1 ℃/min under the nitrogen atmosphere, and the temperature is kept for 8 hours to obtain tungsten carbide;

(3) Adding tungsten carbide into 0.30mol/L nickel nitrate solution, performing ultrasonic treatment on the mixture, placing the mixture in a low-temperature reactor, slowly adding 0.50mol/L sodium borohydride solution under the atmosphere of continuously introducing nitrogen, standing at room temperature, filtering, washing and drying to obtain nickel-base tungsten carbide, and recording as Ni _0.30 @WC-1；

(4) 5-HMF and Ni obtained in the step (3) _0.30 Mixing WC-1 and a solvent, placing in a sealed high-pressure reaction kettle, replacing air with hydrogen, and carrying out hydrogenation reaction under the pressure of 2MPa hydrogen by taking the hydrogen as a hydrogen donor.

The Ni obtained in this example _0.30 Analysis of the product of catalytic 5-HMF hydrogenation at different reaction conditions @ WC-1 is shown in table 4:

table 4: the Ni obtained in example 4 _0.30 Product analysis Table for catalyzing hydrogenation of 5-HMF under different reaction conditions for WC-1

Example 5

(1) Sequentially dissolving dopamine hydrochloride and ammonium metavanadate in a mass ratio of 1:1 in deionized water, stirring to form a vanadium-dopamine hydrochloride complex, adding ethanol into the solution, adding ammonia water rapidly with stirring, continuously stirring at room temperature, centrifugally collecting precipitate, filtering, washing and drying to obtain a vanadium-dopamine hydrochloride precursor;

(2) The vanadium-dopamine hydrochloride precursor is placed in a tube furnace for carburizing treatment, the temperature is raised to 1000 ℃ at the heating rate of 1 ℃/min under the nitrogen atmosphere, and the temperature is kept for 8 hours, so that vanadium carbide is obtained;

(3) Adding vanadium carbide into 0.30mol/L nickel nitrate solution, performing ultrasonic treatment on the mixture, placing the mixture in a low-temperature reactor, slowly adding 0.50mol/L sodium borohydride solution under the atmosphere of continuously introducing nitrogen, standing at room temperature, and finally obtaining nickel-based vanadium carbide, namely Ni by filtering, washing and drying _0.30 @VC-1；

(4) 5-HMF and Ni obtained in the step (3) _0.30 Mixing the @ VC-1 and a solvent, placing the mixture in a sealed high-pressure reaction kettle, replacing air with hydrogen, and carrying out hydrogenation reaction under the pressure of 2MPa hydrogen by taking the hydrogen as a hydrogen donor.

The Ni obtained in this example _0.30 Analysis of the product of catalytic hydrogenation of 5-HMF at different reaction conditions @ VC-1, as shown in table 5:

table 5: the Ni obtained in example 5 _0.30 Product analysis Table for catalyzing hydrogenation of 5-HMF under different reaction conditions for @ VC-1

Example 6

(1) Sequentially dissolving dopamine hydrochloride and ammonium molybdate in a mass ratio of 1:1 in deionized water, stirring to form molybdenum-dopamine hydrochloride complex, adding ethanol into the solution, adding ammonia water rapidly with stirring, continuously stirring at room temperature, centrifugally collecting precipitate, filtering, washing and drying to obtain molybdenum-dopamine hydrochloride precursor;

(2) The molybdenum-dopamine hydrochloride precursor is placed in a tube furnace for carburizing treatment, and is heated to 1100 ℃ at a heating rate of 1 ℃/min under nitrogen atmosphere, and is kept for 8 hours to obtain molybdenum carbide;

(3) Adding molybdenum carbide into 0.30mol/L nickel nitrate solution, performing ultrasonic treatment on the mixture, placing the mixture in a low-temperature reactor, slowly adding 0.50mol/L sodium borohydride solution under the atmosphere of continuously introducing nitrogen, standing at room temperature, and finally obtaining nickel-base molybdenum carbide, namely Ni by filtering, washing and drying _0.30 @MoC-1；

(4) 5-HMF and Ni obtained in the step (3) _0.30 Mixing MoC-1 and solvent, placing in a sealed high-pressure reaction kettle, replacing air with hydrogen, and carrying out hydrogenation reaction under the pressure of 2MPa hydrogen by taking hydrogen as a hydrogen donor.

The Ni obtained in this example _0.30 Analysis of the product of catalytic 5-HMF hydrogenation at different reaction conditions for MoC-1 is shown in table 6:

table 6: the Ni obtained in example 6 _0.30 Product analysis Table for catalyzing hydrogenation of 5-HMF under different reaction conditions by @ MoC-1

Example 7

A method for catalyzing 5-HMF selective hydrogenation by copper-based transition metal carbide comprises the following specific steps:

(3) Adding tungsten carbide into 0.30mol/L copper nitrate solution, and performing ultrasonic treatment on the mixtureSlowly adding 0.50mol/L sodium borohydride solution in a low-temperature reactor under the atmosphere of continuously introducing nitrogen, standing at room temperature, filtering, washing, and drying to obtain copper-based tungsten carbide, which is denoted as Cu _0.30 @WC-1；

(4) 5-HMF and Cu obtained in the step (3) _0.30 Mixing WC-1 and a solvent, placing in a sealed high-pressure reaction kettle, replacing air with hydrogen, and carrying out hydrogenation reaction under the pressure of 2MPa hydrogen by taking the hydrogen as a hydrogen donor.

The Cu obtained in this example _0.30 Analysis of the product of catalytic 5-HMF hydrogenation at different reaction conditions @ WC-1 is shown in table 7:

table 7: the Cu obtained in example 7 _0.30 Product analysis Table for catalyzing hydrogenation of 5-HMF under different reaction conditions for WC-1

Example 8

A method for catalyzing 5-HMF selective hydrogenation by iron-based transition metal carbide comprises the following specific steps:

(3) Adding tungsten carbide into 0.30mol/L ferric nitrate solution, performing ultrasonic treatment on the mixture, and placing the mixture at low temperatureSlowly adding 0.50mol/L sodium borohydride solution into a warm reactor under the atmosphere of continuously introducing nitrogen, standing at room temperature, filtering, washing, and drying to obtain iron-based tungsten carbide, which is denoted as Fe _0.30 @WC-1；

(4) 5-HMF, fe obtained in step (3) _0.30 Mixing WC-1 and a solvent, placing in a sealed high-pressure reaction kettle, replacing air with hydrogen, and carrying out hydrogenation reaction under the pressure of 2MPa hydrogen by taking the hydrogen as a hydrogen donor.

The Fe obtained in this example _0.30 Analysis of the product of catalytic 5-HMF hydrogenation at different reaction conditions @ WC-1 is shown in table 8:

table 8: the Fe obtained in example 8 _0.30 Product analysis Table for catalyzing hydrogenation of 5-HMF under different reaction conditions for WC-1

Example 9

A method for catalyzing 5-HMF selective hydrogenation by cobalt-based transition metal carbide comprises the following specific steps:

(3) Adding tungsten carbide into 0.30mol/L cobalt nitrate solution, performing ultrasonic treatment on the mixture, placing the mixture in a low-temperature reactor, slowly adding 0.50mol/L sodium borohydride solution under the atmosphere of continuously introducing nitrogen, standing at room temperature, and finally obtaining cobalt-based tungsten carbide, which is marked as Co, through filtering, washing and drying _0.30 @WC-1；

(4) 5-HMF, co obtained in step (3) _0.30 Mixing WC-1 and a solvent, placing in a sealed high-pressure reaction kettle, replacing air with hydrogen, and carrying out hydrogenation reaction under the pressure of 2MPa hydrogen by taking the hydrogen as a hydrogen donor.

The Co obtained in this example _0.30 Analysis of the product of catalytic 5-HMF hydrogenation at different reaction conditions @ WC-1 is shown in table 9:

table 9: co obtained in example 9 _0.30 Product analysis Table for catalyzing hydrogenation of 5-HMF under different reaction conditions for WC-1

From the above, it can be seen from the comparison of examples 1 to 9 that the selectivity of BHMF, MF, MFA and DMF in the 5-HMF selective hydrogenation control of the nickel-based transition metal carbide catalyst can be as high as 81.1%,48.6%,36.6% and 97.7%, respectively, which is far higher than that of other metal-based transition metal carbide catalysts.

FIG. 1 is a graph showing the analysis of the products of example 4 at the same temperature for each reaction stage, at Ni _0.30 The reaction at WC-1 for 1h,5-HMF can be rapidly converted to BHMF, MF and MFA, while the reaction continues to show high selectivity to DMF. Based on the above experimental results, the reaction path of selective hydrogenation of 5-HMF is shown in FIG. 2, ni _0.30 The @ WC-1 shows good adsorption and catalytic performance on aldehyde groups and hydroxymethyl groups on 5-HMF, avoids excessive hydrogenation on furan rings, is developed by two routes of synthesizing BHMF and MF by preferential hydrogenation, and can generate DMF by continuous hydrogenation, so that the double-effect hydrogenation performance of nickel-based transition metal carbide can effectively regulate and control the generation of hydrogenation products. In addition, for the tungsten carbide and Ni obtained in example 4 _0.30 @ WC-1 was NH-doped ₃ TPD and XPS characterization, FIG. 3 shows that Ni-supported catalysts are shown to be in the low temperature zone respectively<Obvious diffraction peaks appear in the 250 ℃ and high-temperature region (500-800 ℃), which shows that weak acid sites and strong acid sites coexist, the acid content is obviously improved, and the acid strength, the acid content and the catalytic activity are further disclosedThere is a direct link to the nature and it is demonstrated from the Py-FTIR characterization results (FIG. 4) that the acidic sites appear as Lewis acid sites, effectively facilitating the hydrogenation reaction. As can be seen from FIGS. 5 to 6, ni 2p _{3/2 Spectrum} Three diffraction peaks presented in (a) are respectively attributed to metallic nickel-bonded Ni ⁰ Ni of nickel oxide/nickel hydroxide ²⁺ And satellite peaks, diffraction peaks in the W4 f spectrum representing metal tungsten bonded W, respectively ⁴⁺ 、W ⁶⁺ And W-C bond, and Ni _0.30 The @ WC-1 shows an offset of-0.2 eV, strongly indicating that it has a stronger electron-rich metal site, facilitating hydrogen activation and cleavage of the C-O bond and thus accelerating the hydrogenolysis process.

The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. The preparation method of the nickel-based transition metal carbide catalyst is characterized in that dopamine hydrochloride and metal composite salt are taken as raw materials and dissolved in deionized water to form a metal-dopamine hydrochloride complex, ethanol and ammonia water are added into the complex to be stirred, and sediment is collected to obtain a metal-dopamine hydrochloride precursor; and then carburizing the metal-dopamine hydrochloride precursor to obtain transition metal carbide, adding the transition metal carbide into a compound solution of metallic nickel, performing ultrasonic treatment, finally adding a sodium borohydride solution under a low-temperature nitrogen atmosphere, standing at room temperature, filtering, washing and drying to obtain the nickel-based transition metal carbide.

2. The method for preparing a nickel-based transition metal carbide catalyst according to claim 1, wherein the metal complex salt is one of ammonium metatungstate, ammonium metavanadate and ammonium molybdate.

3. The method for preparing a nickel-based transition metal carbide catalyst according to claim 1, wherein the mass ratio of the dopamine hydrochloride to the metal composite salt is 1:0.5-2.

4. The method for preparing a nickel-based transition metal carbide catalyst according to claim 1, wherein the carburizing treatment is to heat up to 900-1100 ℃ at a heating rate of 1-5 ℃/min under a nitrogen atmosphere, and heat-preserving for 1-8 hours.

5. The method for preparing a nickel-based transition metal carbide catalyst according to claim 1, wherein the compound of metallic nickel is one of nickel nitrate, nickel chloride and nickel sulfate, and the concentration is 0.15-0.30mol/L.

6. The method for preparing a nickel-based transition metal carbide catalyst according to claim 1, wherein the concentration of the added sodium borohydride solution is 0.30 to 0.50mol/L.

7. The method for preparing a nickel-based transition metal carbide catalyst according to any of claims 1 to 6, comprising the steps of:

(3) Adding transition metal carbide into any one of nickel nitrate, nickel chloride and nickel sulfate with the concentration of 0.15-0.30mol/L, fully mixing, performing ultrasonic treatment on the obtained mixture, placing the mixture in a low-temperature reactor, slowly adding sodium borohydride solution with the concentration of 0.30-0.50mol/L under the atmosphere of continuously introducing nitrogen, standing at room temperature, and finally filtering, washing and drying to obtain the nickel-based transition metal carbide.

8. A nickel-based transition metal carbide catalyst prepared by the method for preparing a nickel-based transition metal carbide catalyst according to any of claims 1-7.

9. Use of the nickel-based transition metal carbide catalyst according to claim 8 in a 5-HMF selective hydrogenation reaction.

10. Use according to claim 9, characterized in that 5-HMF, nickel-based transition metal carbide catalyst and reaction solvent are mixed in a sealed autoclave, air is replaced by hydrogen and hydrogenation is carried out with hydrogen as hydrogen donor at a temperature of 160-190 ℃ for a time of 0.5-3h.