Catalyst and method for preparing the same, and method for hydrogenation of dicyclopentadiene

Abstract

The application relates to the technical field of catalysts, and discloses a catalyst, a preparation method of the catalyst, and a dicyclopentadiene hydrogenation reaction method, the preparation method comprising the following steps: (1) providing a mixed solution containing a nickel source, a noble metal source, an alumina precursor and an organic ligand; wherein the organic ligand is selected from terephthalic acid and / or trimesic acid; (2) performing aging treatment on the mixed solution to obtain a catalyst precursor; and (3) performing calcination on the catalyst precursor. The catalyst prepared by the method has high hydrogenation activity, high dicyclopentadiene conversion rate, high selectivity of saturated hydrogenation product tetrahydrodicyclopentadiene, good stability, and can realize continuous preparation of tetrahydrodicyclopentadiene.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, specifically to a catalyst and a method for preparing the catalyst, and a method for hydrogenation of dicyclopentadiene. Background Technology

[0002] JP-10 is currently the most widely used and best-performing high-density liquid hydrocarbon fuel. The preparation of JP-10 from dicyclopentadiene (DCPD), a petroleum cracking byproduct, involves two steps: hydrogenation and isomerization. The hydrogenation step is crucial. Supported nickel-based catalysts are simple to prepare and exhibit good catalytic activity, and have been extensively studied in the hydrogenation of DCPD to THDCPD (tetrahydrodicyclopentadiene). However, current supported catalysts suffer from high nickel loading, low metal dispersion, poor low-temperature activity, and a tendency for nickel agglomeration, limiting their further application. Summary of the Invention

[0003] The purpose of this invention is to overcome the problems of insufficient activity and poor stability of existing dicyclopentadiene hydrogenation catalysts, and to provide a catalyst, a method for preparing the catalyst, and a method for dicyclopentadiene hydrogenation reaction. This catalyst has excellent dicyclopentadiene hydrogenation activity and good stability.

[0004] To achieve the above objectives, the first aspect of the present invention provides a method for preparing a catalyst, comprising the following steps:

[0005] (1) Provide a mixture containing a nickel source, a noble metal source, an alumina precursor and an organic ligand;

[0006] The organic ligand is selected from terephthalic acid and / or trimesic acid;

[0007] (2) The above mixture is subjected to aging treatment to obtain a catalyst precursor;

[0008] (3) The catalyst precursor is calcined.

[0009] Preferably, the roasting temperature is 350-750℃ and the roasting time is 3-15h.

[0010] A second aspect of the present invention provides a catalyst prepared by the above-described preparation method.

[0011] A third aspect of the present invention provides a method for hydrogenation of dicyclopentadiene, comprising: contacting dicyclopentadiene and hydrogen with a hydrogenation catalyst under hydrogenation reaction conditions; wherein the hydrogenation catalyst is the catalyst described in the second aspect.

[0012] The catalyst preparation method provided by this invention utilizes organic ligands and nickel to assemble a catalyst precursor containing MOFs (Metal-Oxide-Fractions). Leveraging the advantages of MOFs, the metal dispersion can be improved while reducing catalyst cost, making it more suitable for industrial applications. The catalyst prepared by this method exhibits high hydrogenation activity, with a 100% conversion rate of dicyclopentadiene and a selectivity of at least 80% for the saturated hydrogenation product tetrahydrodicyclopentadiene, preferably at least 99%. It also demonstrates high stability and enables the continuous preparation of tetrahydrodicyclopentadiene. Attached Figure Description

[0013] Figure 1 These are the XRD patterns of the catalyst precursor and the catalyst prepared in Example 1 of this invention;

[0014] Figure 2 This is the Fourier transform infrared spectrum of the catalyst precursor prepared in Example 1 of this invention. Detailed Implementation

[0015] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0016] The first aspect of this invention provides a method for preparing a catalyst, comprising the following steps:

[0017] (1) Provide a mixture containing a nickel source, a noble metal source, an alumina precursor and an organic ligand;

[0018] The organic ligand is selected from terephthalic acid and / or trimesic acid;

[0019] (2) The above mixture is subjected to aging treatment to obtain a catalyst precursor;

[0020] (3) The catalyst precursor is calcined.

[0021] In existing technologies, commercially available Raney nickel catalysts and reported supported nickel-based catalysts suffer from problems such as high nickel loading and low metal dispersion, resulting in poor low-temperature activity and easy agglomeration of nickel metal. To address this issue, the inventors of this invention have creatively proposed a method to obtain a catalyst precursor with high metal dispersion by self-assembling an organic ligand with nickel metal to form a MOF-containing structure, followed by calcination to remove the organic ligand. The inventors discovered that during the self-assembly of terephthalic acid and / or trimellitic acid with nickel metal to form a MOF-containing structure, the high porosity and porous structure of MOFs can significantly improve the dispersion of both nickel and noble metal components. This facilitates the synergistic effect of nickel and noble metals, increases the utilization rate of active metals, and reduces the amount of metal used. Furthermore, terephthalic acid and trimellitic acid, especially terephthalic acid, are inexpensive and readily available, further reducing the catalyst preparation cost and making it more suitable for industrial applications.

[0022] According to some preferred embodiments of the present invention, the organic ligand is terephthalic acid. Terephthalic acid self-assembles with nickel to form a MOF-69 structure, and the catalyst prepared further can achieve both high catalytic activity and stability.

[0023] According to some preferred embodiments of the present invention, the mass ratio of the nickel source (calculated as nickel) to the precious metal source (calculated as a precious metal element) is 5-20:1, preferably 7-18:1.

[0024] The present invention allows for a wide range of selections for the nickel source, which can be selected from any nickel-soluble compound, as is well known to those skilled in the art. Preferably, the nickel source is selected from at least one of nickel chloride, nickel sulfate, nickel nitrate, and nickel acetate.

[0025] In this invention, preferably, the noble metal in the noble metal source is selected from at least one of Pd, Pt, and Ru, more preferably Pd. In the above-mentioned preferred case, the dicyclopentadiene hydrogenation activity of the prepared catalyst can be further improved through the synergistic effect of nickel and palladium.

[0026] The present invention does not particularly limit the specific type of the noble metal source, which can be a soluble compound of a noble metal, such as a noble metal chloride, nitrate, or coordination compound. For example, the Pd source can be at least one of dichlorotetraamminepalladium, palladium nitrate, palladium chloride, and potassium chloride palladiumate.

[0027] The nickel source or precious metal source may also contain water of crystallization, as is well known to those skilled in the art.

[0028] According to the present invention, preferably, the total amount of the nickel source and the noble metal source, calculated as metals, to the mass ratio of the alumina precursor is 0.01-0.2:1, more preferably 0.04-0.1:1.

[0029] Preferably, the mass ratio of the organic ligand to the alumina precursor is 0.03-0.1:1, more preferably 0.03-0.07:1. Adopting the above-mentioned preferred embodiments helps to reduce costs while ensuring high activity.

[0030] This invention offers a wide range of choices for the alumina precursor, allowing for the use of alumina of any crystal form or any substance that can be calcined to form alumina. Those skilled in the art can select the appropriate precursor based on actual needs. To further improve metal dispersibility and enhance the hydrogenation activity and stability of the dicyclopentadiene catalyst, preferably, the alumina precursor is γ-Al₂O₃.

[0031] The present invention does not have any particular limitation on the specific operation method and feeding sequence of the mixture provided in step (1), as long as the components can be formed into a uniform mixture.

[0032] According to some preferred embodiments of the present invention, the method of providing the mixture in step (1) includes: first mixing the nickel source, the noble metal source, and the alumina precursor, and then mixing them with the organic ligand. Using the above preferred embodiments is beneficial to further improve the dispersion of nickel and noble metal components in the obtained catalyst, and to improve the hydrogenation activity and stability of the catalyst.

[0033] Preferably, the first and second mixing are carried out independently under stirring conditions. The present invention does not impose any particular limitation on the stirring conditions, as long as they improve the uniformity of mixing.

[0034] In this invention, the nickel source, noble metal source, alumina precursor, and organic ligand can be dispersed together in a solvent to form the mixture; alternatively, the nickel source, noble metal source, alumina precursor, and organic ligand can be dispersed separately in a solvent to form a metal source dispersion, an alumina precursor dispersion, and an organic ligand dispersion, and then these dispersions are mixed to form the mixture. This invention allows for a wide range of solvent choices; conventional organic or inorganic solvents in the art can be used to ensure uniform dispersion of the components. Preferably, the solvent is at least one of water, ethanol, methanol, acetone, and N,N-dimethylformamide. In this case, the solvents in the metal source dispersion, alumina precursor dispersion, and organic ligand dispersion can be the same or different, all satisfying the aforementioned solvent range.

[0035] According to some preferred embodiments of the present invention, the nickel source and the noble metal source are provided by a metal source solution, wherein the solvent in the metal source solution is preferably water.

[0036] According to some preferred embodiments of the present invention, the alumina precursor is provided by a dispersion of the alumina precursor, wherein the solvent in the dispersion may be selected from at least one of ethanol, methanol, acetone and N,N-dimethylformamide, preferably methanol and / or ethanol. The present invention does not have particular requirements on the amount of the above solvents, as long as they are sufficient to adequately disperse the alumina precursor.

[0037] According to some preferred embodiments of the present invention, the organic ligand is provided by an organic ligand solution, wherein the solvent in the organic ligand solution is preferably DMF.

[0038] The present invention does not particularly limit the conditions for the aging treatment, as long as the nickel source and organic ligand can self-assemble to form a nickel-organic framework compound, and can be carried out under conventional conditions for preparing MOF materials.

[0039] According to some preferred embodiments of the present invention, the aging treatment conditions include: a temperature of 90-220°C, preferably 120-210°C, and a time of 5-25 hours, preferably 7-10 hours. Adopting the above preferred embodiments is beneficial to the growth of MOF materials.

[0040] Preferably, the aging treatment is carried out under stirring conditions. The present invention does not particularly limit the stirring conditions, and conventional operating methods in the art can be used.

[0041] According to the present invention, the preparation method further includes: cooling, separating solids and liquids, and drying the product obtained from the aging treatment to obtain the catalyst precursor. The solid-liquid separation and drying can be performed using methods conventional in the art, and the present invention does not particularly limit them.

[0042] According to the present invention, the organic ligands in the catalyst precursor are removed by calcination in step (3), thereby obtaining a catalyst with high metal dispersion. The present invention allows for a wide range of calcination conditions, as long as the organic ligands can be removed.

[0043] According to some preferred embodiments of the present invention, the calcination temperature is 350-750℃, preferably 450-600℃, and the calcination time is 3-15h, preferably 3-8h. Adopting the above preferred embodiments not only facilitates the thorough removal of organic ligands in the catalyst precursor but also ensures high metal dispersion, preventing metal aggregation during calcination, thereby further improving the low-temperature activity and stability of the catalyst.

[0044] According to some preferred embodiments of the present invention, the calcination is carried out in the presence of a reducing gas and / or an inert gas, wherein the reducing gas is preferably hydrogen; and the inert gas is selected from at least one of nitrogen, argon and helium.

[0045] When the calcination is carried out under a mixture of reducing and inert gases, preferably, the volume ratio of the reducing and inert gases is 1:1-0.5. Using the above-mentioned preferred calcination conditions is beneficial for the reduction of nickel and noble metal components.

[0046] A second aspect of the present invention provides a catalyst prepared by the above-described preparation method.

[0047] The catalyst includes a support and a first metal component and a second metal component supported on the support. The first metal component is Ni, and the second metal component is at least one of noble metals. The support is alumina.

[0048] A third aspect of the present invention provides a method for hydrogenation of dicyclopentadiene, comprising: contacting dicyclopentadiene and hydrogen with a hydrogenation catalyst under hydrogenation reaction conditions; wherein the hydrogenation catalyst is the catalyst described in the second aspect.

[0049] The hydrogenation method for dicyclopentadiene provided by this invention can be adapted to both continuous and batch reactions. The continuous reaction can be carried out, for example, in a fixed-bed reactor, while the batch reaction can be carried out, for example, in a high-pressure reactor. Most industrial Raney nickel catalysts and reported supported nickel-based catalysts can only be used in high-pressure reactors because fixed-bed reactors have short reaction times and no backmixing. However, fixed-bed reactors place higher demands on catalyst activity and stability, especially since olefins are prone to polymerization leading to coking, which affects the stability of continuous reactions. The catalyst of this invention combines high catalytic activity and high stability, making it suitable for both batch and continuous reactions.

[0050] According to some preferred embodiments of the present invention, the contact is carried out in a high-pressure reactor, and the hydrogenation reaction conditions include: a reaction temperature of 40-150°C, preferably 60-100°C, a pressure of 2-6 MPa, preferably 3-5 MPa, and a reaction time of 1-25 h, preferably 1-3 h.

[0051] Preferably, the contact is carried out under stirring conditions, and the stirring rate is 300-1000 r / min.

[0052] According to some preferred embodiments of the present invention, the contact is carried out in a fixed-bed reactor, and the hydrogenation reaction conditions include: a reaction temperature of 50-100°C, preferably 60-100°C; a pressure of 3-6 MPa, preferably 3-5 MPa; a hydrogen / hydrocarbon volume ratio of 200-600:1, preferably 300-500:1; and a reaction mass hourly space velocity of 1-3 h⁻¹. -1 Preferably 1-2 hours -1 .

[0053] According to the present invention, preferably, the contact is carried out in the presence of an organic solvent, preferably, the solvent is selected from methylcyclohexane and / or cyclohexane. The present invention provides a wide range of options for the amount of solvent used, and those skilled in the art can select the appropriate amount based on actual needs.

[0054] According to some preferred embodiments of the present invention, the contact is carried out in a high-pressure reactor, and the mass ratio of the organic solvent to dicyclopentadiene is 15-25:1.

[0055] According to some other preferred embodiments of the invention, the contact is carried out in a fixed-bed reactor, and the mass ratio of the organic solvent to dicyclopentadiene is 2-5:1.

[0056] Existing nickel-based catalysts, such as commercially available Raney nickel catalysts, typically operate at temperatures around 100°C during the hydrogenation of dicyclopentadiene. The hydrogenation method for dicyclopentadiene provided by this invention can be carried out at low-temperature reaction conditions below 100°C, preferably below 80°C, and exhibits high DCPD conversion and selectivity for the saturated hydrogenation product THDCPD, along with good reaction stability.

[0057] The present invention will be described in detail below through embodiments.

[0058] Unless otherwise specified, all raw materials used in the following embodiments are commercially available.

[0059] The X-ray diffraction pattern was obtained using an X-ray diffractometer. The test conditions included: Cu target, Kα radiation (λ = 0.154 nm), scan rate of 5° / min, and scan range of 5°-80°.

[0060] Fourier transform infrared (FTIR) spectra were obtained using a Nicolet 560 Fourier transform infrared spectrometer under the following conditions: resolution approximately 4 cm⁻¹. -1 Measurement range: 400-4000cm -1 .

[0061] Example 1

[0062] 0.59 g of nickel nitrate hexahydrate and 37.3 mg of dichlorotetraamminepalladium were completely dissolved in 34 mL of water. Then, 3 g of γ-Al₂O₃ was dispersed in 34 mL of ethanol, and the above aqueous solution was added under stirring. 0.13 g of terephthalic acid was dissolved in 34 mL of DMF and added to the above stirred solution. The reaction was carried out at 120 °C for 7 h. After cooling to room temperature, the mixture was separated and dried to obtain the catalyst precursor Pd-MOF-69 / Al₂O₃.

[0063] The XRD pattern of the catalyst precursor prepared above is shown in the figure. Figure 1 As shown, the diffraction peaks of the catalyst precursor are almost identical to those of the alumina support. The two peaks at 46.1° and 66.9° are attributed to γ-Al₂O₃, and the peak at 8.8° coincides with that of MOF-69, confirming the successful loading of MOF-69. The FTIR characterization of the catalyst precursor is as follows: Figure 2 As shown in the figure, 1579cm -1 and 1376cm -1 The peaks represent both asymmetric and symmetric stretching of the MOF-69 framework structure -(OCO)-; however, the catalyst precursor exhibits vibrational peaks identical to those of MOF-69. Combined with XRD and FTIR results, this indicates the formation of MOF-69 in the catalyst precursor.

[0064] The above-mentioned catalyst precursor was placed in a tube furnace and pyrolyzed at 500℃ for 200 min with a hydrogen to nitrogen volume ratio of 1:1 to obtain Al2O3-supported NiPd catalyst S1. The XRD pattern of catalyst S1 is shown below. Figure 1 As shown, it can be seen that the characteristic peak of MOF-69 disappears in catalyst S1 compared to the catalyst precursor.

[0065] Example 2

[0066] 0.75 g of nickel acetate and 37.3 mg of dichlorotetraamminepalladium were completely dissolved in 34 mL of water. Then, 3 g of γ-Al₂O₃ was dispersed in 34 mL of ethanol, and the above aqueous solution was added under stirring. 0.13 g of terephthalic acid was dissolved in 34 mL of DMF and added to the above stirred solution. The reaction was carried out at 120 °C for 7 h. After cooling to room temperature, the mixture was separated and dried to obtain the catalyst precursor Pd-MOF-69 / Al₂O₃. The above catalyst precursor was placed in a tube furnace and pyrolyzed at 500 °C for 200 min with a hydrogen to nitrogen volume ratio of 1:1 to obtain the Al₂O₃-supported NiPd catalyst S2.

[0067] Example 3

[0068] 0.59 g of nickel nitrate hexahydrate and 25 mg of dichlorotetraamminepalladium were completely dissolved in 34 mL of water. Then, 3 g of γ-Al₂O₃ was dispersed in 34 mL of ethanol, and the above aqueous solution was added under stirring. 0.21 g of terephthalic acid was dissolved in 34 mL of DMF and added to the above stirred solution. The reaction was carried out at 120 °C for 7 h. After cooling to room temperature, the mixture was separated and dried to obtain the catalyst precursor Pd-MOF-69 / Al₂O₃. The catalyst precursor was placed in a tube furnace and pyrolyzed at 500 °C for 200 min with a hydrogen to nitrogen volume ratio of 1:1 to obtain the Al₂O₃-supported NiPd catalyst S3.

[0069] Example 4

[0070] 0.59 g of nickel nitrate hexahydrate and 37.3 mg of dichlorotetraamminepalladium were completely dissolved in 34 mL of water. Then, 3 g of γ-Al₂O₃ was dispersed in 34 mL of ethanol, and the above aqueous solution was added under stirring. 0.13 g of terephthalic acid was dissolved in 34 mL of DMF and added to the above stirred solution. The reaction was carried out at 140 °C for 10 h. After cooling to room temperature, the mixture was separated and dried to obtain the catalyst precursor Pd-MOF-69 / Al₂O₃. The catalyst precursor was placed in a tube furnace and pyrolyzed at 600 °C for 180 min with a hydrogen to nitrogen volume ratio of 1:1 to obtain the Al₂O₃-supported NiPd catalyst S4.

[0071] Example 5

[0072] 0.59 g of nickel nitrate hexahydrate and 37.3 mg of dichlorotetraamminepalladium were completely dissolved in 34 mL of water. Then, 3 g of γ-Al₂O₃ was dispersed in 34 mL of ethanol, and the above aqueous solution was added under stirring. 0.13 g of terephthalic acid was dissolved in 34 mL of DMF and added to the above stirred solution. The reaction was carried out at 120 °C for 10 h. After cooling to room temperature, the mixture was separated and dried to obtain the catalyst precursor Pd-MOF-69 / Al₂O₃. The catalyst precursor was placed in a tube furnace and pyrolyzed at 550 °C for 220 min with a hydrogen to nitrogen volume ratio of 0.8:1 to obtain the Al₂O₃-supported NiPd catalyst S5.

[0073] Example 6

[0074] The method is the same as in Example 1, except that the amount of terephthalic acid added is 0.06g.

[0075] The NiPd catalyst S6 supported on Al2O3 was obtained.

[0076] Example 7

[0077] The method was followed in Example 1, except that the obtained catalyst precursor Pd-MOF-69 / Al2O3 was placed in a tube furnace and pyrolyzed at 790°C for 200 min with a hydrogen to nitrogen volume ratio of 1:1 to obtain Al2O3 supported NiPd catalyst S7.

[0078] Example 8

[0079] Following the method of Example 1, except that an equal mass of pyromellitic acid was used instead of terephthalic acid, an Al2O3-supported NiPd catalyst S8 was obtained.

[0080] Comparative Example 1

[0081] Using a conventional impregnation method, 0.59 g of nickel nitrate hexahydrate, 37.3 mg of dichlorotetraamminepalladium, and 3 g of Al₂O₃ were dispersed in water and stirred at room temperature for 8 h. After the reaction was complete, the precursor material was separated and dried to obtain the precursor material. The above catalyst precursor was placed in a tube furnace and pyrolyzed at 500 °C for 200 min with a hydrogen to nitrogen volume ratio of 1:1 to obtain the Al₂O₃-supported NiPd catalyst DS1.

[0082] Test characterization

[0083] (1) Testing the hydrogenation performance of the catalyst in a high-pressure reactor

[0084] 100 mg of the catalyst from the above examples and comparative examples was added to the lining of the reactor, followed by 20 g of methylcyclohexane (solvent) and 1 g of dicyclopentadiene. The reactor was then filled and sealed, the air inside was displaced, and the hydrogen pressure inside the reactor was maintained at 3 MPa. The reaction was stirred at 70 °C for 1 h, and the product composition was analyzed using an Agilent 7890 chromatography system. The results are shown in Table 1.

[0085] Wherein, the conversion rate (%) of dicyclopentadiene (DCPD) = (1 - DCPD peak area percentage) × 100%;

[0086] Tetrahydrodicyclopentadiene (THDCPD) selectivity (%) = (THDCPD peak area / total peak area of ​​reaction products) × 100%.

[0087] Table 1

[0088] S1 70 3 100 ＞99.9 S2 60 3 100 ＞99.9 S3 70 3 100 ＞99.9 S4 70 3 100 ＞99.9 S5 70 3 100 ＞99.9 S6 70 3 100 89 S7 70 3 100 82 S8 70 3 100 ＞99.9 DS1 70 3 100 30

[0089] To further investigate the stability of the catalyst, the catalyst S1 prepared in Example 1 was subjected to a repeatability test in a reactor. After three repeated reactions, the catalyst still maintained its initial activity. The reaction results are shown in Table 2.

[0090] Table 2

[0091]

[0092] (2) Testing the hydrogenation performance of the catalyst in a fixed bed

[0093] The catalyst powders obtained in Examples 1-4 and Example 8 were pressed into tablets and sieved. Catalysts with a particle size of 20-40 mesh were selected and loaded into the middle section of the reaction tube. The reaction conditions are shown in Table 3. The mass ratio of solvent methylcyclohexane to reactant DCPD was 2. After continuous operation for 50 hours, the reaction results are shown in Table 3.

[0094] Table 3

[0095]

[0096] As can be seen from the results in Tables 1-3, the catalyst prepared in the embodiments of the present invention exhibits high hydrogenation activity, with a dicyclopentadiene conversion rate of 100% and a selectivity of over 80% for the saturated hydrogenation product tetrahydrodicyclopentadiene, preferably over 99%. It also demonstrates high stability, enabling the continuous preparation of tetrahydrodicyclopentadiene. This is attributed to the introduction of organic ligands during the preparation process. These organic ligands and nickel source assemble to form a catalyst precursor containing MOFs (Metal-Oxide-Fractions). Utilizing the advantages of MOFs, the metal dispersion can be improved, thereby enhancing the low-temperature hydrogenation activity of the catalyst.

[0097] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for hydrogenating dicyclopentadiene, comprising: Under hydrogenation reaction conditions, dicyclopentadiene and hydrogen are contacted with a hydrogenation catalyst; The contact is carried out in a fixed-bed reactor, and the hydrogenation reaction conditions include: a reaction temperature of 50-100℃, a pressure of 3-6 MPa, a hydrogen / hydrocarbon volume ratio of 200-600:1, and a mass hourly space velocity of 1-2 h⁻¹. -1 ; The hydrogenation catalyst is prepared by the following method. (1) Provide a mixture containing a nickel source, a precious metal source, an alumina precursor and an organic ligand; The organic ligand is selected from terephthalic acid; the alumina precursor is γ-Al2O3. The mass ratio of the organic ligand to the alumina precursor is 0.03-0.07:1; (2) The above mixture is subjected to aging treatment to obtain the catalyst precursor; (3) The catalyst precursor is calcined. The roasting temperature is 450-600℃, and the roasting time is 3-8 hours.

2. The method according to claim 1, wherein, The mass ratio of the nickel source (calculated as nickel) to the precious metal source (calculated as a precious metal element) is 5-20:

1.

3. The method according to claim 2, wherein, The mass ratio of the nickel source (calculated as nickel) to the precious metal source (calculated as a precious metal element) is 7-18:

1.

4. The method according to claim 1, wherein, The nickel source is selected from at least one of nickel chloride, nickel sulfate, nickel nitrate, and nickel acetate.

5. The method according to claim 1, wherein, The precious metal in the precious metal source is selected from at least one of Pd, Pt and Ru.

6. The method according to claim 5, wherein, The precious metal in the precious metal source is Pd.

7. The method according to claim 1 or 2, wherein, The total amount of the nickel source and the noble metal source, calculated in metals, is in a mass ratio of 0.01-0.2:1 to the alumina precursor.

8. The method according to claim 7, wherein, The total amount of the nickel source and the noble metal source, calculated in metals, is in a mass ratio of 0.04-0.1:1 to the alumina precursor.

9. The method according to claim 1, wherein, The alumina precursor is provided by a dispersion of the alumina precursor, wherein the solvent in the dispersion is selected from at least one of ethanol, methanol, acetone and N,N-dimethylformamide.

10. The method according to any one of claims 1-3, wherein, The method of providing the mixture in step (1) includes: first mixing the nickel source, the noble metal source and the alumina precursor, and then mixing them with the organic ligand.

11. The method according to any one of claims 1-4, wherein, The aging process causes the nickel source and organic ligands to self-assemble into a nickel-organic framework compound.

12. The method according to any one of claims 1-4, wherein, The aging treatment conditions include: a temperature of 90-220℃ and a time of 5-25h.

13. The method according to any one of claims 1-4, wherein, The aging process is carried out under stirring conditions.

14. The method according to any one of claims 1-5, wherein, The calcination is carried out in the presence of a reducing gas and / or an inert gas selected from at least one of nitrogen, argon and helium.

15. The method according to claim 14, wherein, The reducing gas is hydrogen.

16. The method of claim 14, wherein, The volume ratio of the reducing gas to the inert gas is 1:0.5-1.

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