Catalyst, preparation method of catalyst and hydrogenation reaction method of dicyclopentadiene

Abstract

The invention relates to the technical field of catalysts, and discloses a catalyst, a preparation method of the catalyst and a hydrogenation reaction method of dicyclopentadiene, the preparation method comprises 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) carrying out aging treatment on the mixed solution to obtain a catalyst precursor; and (3) roasting the catalyst precursor. The catalyst prepared by the method has high hydrogenation activity, high dicyclopentadiene conversion rate, high selectivity and good stability of a saturated hydrogenation product tetrahydrodicyclopentadiene, and can realize continuous preparation of tetrahydrodicyclopentadiene.

Description

Technical Field

[0001] The invention relates to the technical field of catalysts, and in particular to a catalyst and a method for preparing the catalyst, and a method for hydrogenating dicyclopentadiene. Background Art

[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 byproduct of petroleum cracking, requires two steps: hydrogenation and isomerization. The hydrogenation step is a very important step. Supported nickel-based catalysts have simple preparation methods and good catalytic activity. A large number of application studies have been conducted in the reaction of hydrogenating DCPD to prepare THDCPD (tetrahydrodicyclopentadiene). However, the current supported catalysts have high nickel loading, low metal dispersion, poor low-temperature activity, and easy agglomeration of nickel, which limits their further application. Summary of the invention

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

[0004] In order to achieve the above object, the present invention provides a first aspect of a method for preparing a catalyst, comprising the following steps:

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

[0006] Wherein, the organic ligand is selected from terephthalic acid and / or trimesic acid;

[0007] (2) subjecting the mixed solution to an aging treatment to obtain a catalyst precursor;

[0008] (3) calcining the catalyst precursor.

[0009] Preferably, the calcination temperature is 350-750° C., and the calcination time is 3-15 h.

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

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

[0012] The preparation method of the catalyst provided by the present invention utilizes an organic ligand and a nickel source to assemble a catalyst precursor containing a MOFs structure, and utilizes the advantages of MOFs to improve the dispersion of the metal, while reducing the catalyst cost, which is more conducive to industrial application. The catalyst prepared by the method has a high hydrogenation activity, a dicyclopentadiene conversion rate of 100%, a saturated hydrogenation product tetrahydrodicyclopentadiene selectivity of not less than 80%, preferably not less than 99%, and exhibits high stability, and can achieve continuous preparation of tetrahydrodicyclopentadiene. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 is the XRD spectra of the catalyst precursor and the catalyst prepared in Example 1 of the present invention;

[0014] Figure 2 This is a Fourier infrared spectrum of the catalyst precursor prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0015] The endpoints and any values ​​of the ranges disclosed in this article 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 each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

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

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

[0018] Wherein, the organic ligand is selected from terephthalic acid and / or trimesic acid;

[0019] (2) subjecting the mixed solution to an aging treatment to obtain a catalyst precursor;

[0020] (3) calcining the catalyst precursor.

[0021] In the prior art, commercial Raney nickel catalysts and reported supported nickel-based catalysts all have problems such as high nickel loading and low metal dispersion, resulting in poor low-temperature activity of the catalyst and easy agglomeration of nickel metal. In order to solve this problem, the inventors of the present invention creatively proposed that a catalyst precursor containing a MOFs structure is formed by self-assembly of an organic ligand and nickel metal, and then the organic ligand is removed by roasting to obtain a catalyst with high metal dispersion. The inventors of the present invention found in the study that in the process of self-assembly of terephthalic acid and / or trimesic acid and nickel metal to form a MOFs structure, the high porosity and porous structural characteristics of MOFs can be used to greatly improve the dispersion of metallic nickel, and at the same time, the dispersion of precious metal components can also be improved, so as to further play the synergistic effect of nickel and precious metals, improve the utilization rate of active metals, and reduce the amount of metals. In addition, terephthalic acid and trimesic acid, especially terephthalic acid, are cheap and easy to obtain, which is conducive to further reducing the preparation cost of the catalyst and is more conducive to industrial application.

[0022] According to some preferred embodiments of the present invention, the organic ligand is terephthalic acid. Terephthalic acid and nickel self-assemble to form a MOF-69 structure, and the catalyst further prepared can have 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 noble metal source calculated as noble metal elements is 5-20:1, preferably 7-18:1.

[0024] The present invention has a wide range of choices for the nickel source, and can be selected from any soluble nickel compound, which 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 the present 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 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 has no particular limitation on the specific type of the noble metal source, and it can be a soluble compound of the noble metal, such as noble metal chloride, nitrate, and coordination compound, etc. For example, the Pd source can be at least one of dichlorotetraamminepalladium, palladium nitrate, palladium chloride, and potassium chloropalladate.

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

[0028] According to the present invention, preferably, the mass ratio of the total amount of the nickel source and the noble metal source to the alumina precursor is 0.01-0.2:1, 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, preferably 0.03-0.07: 1. The above preferred implementation is conducive to reducing costs while ensuring high activity.

[0030] The present invention has a wide range of choices for the alumina precursor, which can be any crystalline alumina or any substance that can be formed into alumina by calcination, and those skilled in the art can select according to actual needs. In order to further improve the metal dispersibility and improve the catalyst dicyclopentadiene hydrogenation activity and stability, preferably, the alumina precursor is γ-Al2O3.

[0031] The present invention has no particular limitation on the specific operation mode and feeding sequence of providing the mixed solution in step (1), as long as the components can form a uniform mixed solution.

[0032] According to some preferred embodiments of the present invention, the method of providing the mixed solution 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 for a second time. The above preferred embodiments are used to further improve the dispersion of the nickel and noble metal components in the prepared catalyst, and to improve the hydrogenation activity and stability of the catalyst.

[0033] Preferably, the first mixing and the second mixing are each independently performed under stirring conditions. The present invention has no particular limitation on the stirring conditions, as long as the mixing uniformity can be improved.

[0034] In the present invention, the nickel source, the noble metal source, the alumina precursor and the organic ligand can be dispersed together in a solvent to form the mixed solution; the nickel source, the noble metal source, the alumina precursor and the organic ligand can also be dispersed in a solvent separately to form a metal source dispersion, an alumina precursor dispersion and an organic ligand dispersion, and then the dispersions are mixed to form the mixed solution. The present invention has a wide range of choices for the solvent, and conventional organic or inorganic solvents in the field can be applied to the present invention, based on the uniform dispersion of each component. 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, the alumina precursor dispersion and the organic ligand dispersion can be the same or different, and can all meet the above 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, and the solvent in the metal source solution is preferably water.

[0036] According to some preferred embodiments of the present invention, the aluminum oxide precursor is provided by a dispersion of the aluminum oxide precursor, and the solvent in the dispersion can be selected from at least one of ethanol, methanol, acetone and N,N-dimethylformamide, preferably methanol and / or ethanol. The present invention has no particular requirements for the amount of the above solvent, which is based on the ability to fully disperse the aluminum oxide precursor.

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

[0038] The present invention has no particular limitation on the conditions of the aging treatment, as long as the nickel source and the organic ligands can self-assemble to form a nickel-organic framework compound, and the conditions for preparing conventional MOFs materials can be used.

[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. The above preferred embodiments are beneficial to the growth of MOF materials.

[0040] Preferably, the aging treatment is performed under stirring conditions. The present invention has no particular limitation on the stirring conditions, and the stirring treatment can be performed using conventional operation methods in the art.

[0041] According to the present invention, the preparation method further comprises: cooling, solid-liquid separation and drying the product obtained by the aging treatment to obtain the catalyst precursor. The solid-liquid separation and drying can be carried out in a conventional manner in the art, and the present invention has no particular limitation thereto.

[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 has a wide range of selection of calcination conditions, which is based on the ability to remove the organic ligands.

[0043] According to some preferred embodiments of the present invention, the calcination temperature is 350-750°C, preferably 450-600°C, and the calcination time is 3-15h, preferably 3-8h. The above preferred embodiments are not only conducive to fully removing the organic ligands in the catalyst precursor, but also can ensure the high dispersion of the metal, avoid the aggregation of the metal during the calcination process, 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 roasting is carried out under a mixed gas of reducing gas and inert gas, preferably, the volume ratio of the reducing gas to the inert gas is 1:1-0.5. The above preferred roasting conditions are beneficial to the reduction of nickel and precious metal components.

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

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

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

[0049] The hydrogenation reaction method of dicyclopentadiene provided by the present invention can be adapted to continuous reaction or intermittent reaction, and the continuous reaction can be carried out in a fixed bed reactor, for example, and the intermittent reaction can be carried out in an autoclave. Most of industrial Raney nickel catalysts and reported supported nickel-based catalysts can only be applied to autoclaves, because the fixed bed reactor has a short reaction time and no back mixing. However, the fixed bed reactor has higher requirements for catalyst activity and stability, especially olefins are easily polymerized to cause coking, thereby affecting the stability of the continuous reaction, and the catalyst of the present invention has both high catalytic activity and high stability, and can be adapted to both intermittent reaction and continuous reaction.

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

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

[0052] According to some other preferred embodiments of the present invention, the contact is carried out in a fixed bed reactor, and the hydrogenation reaction conditions include: reaction temperature of 50-100°C, preferably 60-100°C, pressure of 3-6MPa, preferably 3-5MPa, hydrogen / hydrocarbon volume ratio of 200-600:1, preferably 300-500:1; reaction mass space velocity of 1-3h -1 , preferably 1-2h -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 has a wide range of selection for the amount of the solvent, and those skilled in the art can select according to actual needs.

[0054] According to some preferred embodiments of the present invention, the contacting 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 other preferred embodiments of the present invention, the contacting is carried out in a fixed bed reactor, and the mass ratio of the amount of the organic solvent to dicyclopentadiene is 2-5:1.

[0056] When nickel-based catalysts in the prior art, such as commercial Raney nickel catalysts, are used for the hydrogenation reaction of dicyclopentadiene, the reaction temperature is usually around 100° C. The hydrogenation reaction method of dicyclopentadiene provided by the present invention can be carried out under low temperature reaction conditions below 100° C., preferably below 80° C., and the DCPD conversion rate and the selectivity of the saturated hydrogenation product THDCPD are high, and the reaction stability is good.

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

[0058] In the following examples, unless otherwise specified, the raw materials used were commercially available.

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

[0060] Fourier transform infrared (FTIR) spectra were measured using a Nicolet 560 Fourier transform infrared spectrometer. Test conditions: resolution of about 4 cm -1 , measuring range 400-4000cm -1 .

[0061] Example 1

[0062] Completely dissolve 0.59g nickel nitrate hexahydrate and 37.3mg palladium dichlorotetraammine in 34mL water. Then disperse 3g of γ-Al2O3 in 34mL ethanol and add the above aqueous solution under stirring. Dissolve 0.13g terephthalic acid in 34mL DMF and add it to the above stirring solution and react at 120℃ for 7h. Then cool to room temperature, separate and dry to obtain the catalyst precursor Pd-MOF-69 / Al2O3.

[0063] The XRD spectrum of the catalyst precursor prepared above is as follows: Figure 1 As shown in Figure 2, the diffraction peaks of the catalyst precursor are almost consistent with those of the carrier alumina. The two peaks at 46.1° and 66.9° are attributed to γ-Al2O3, and the peak position at 8.8° coincides with MOF-69, proving that MOF-69 is successfully loaded. Figure 2 As shown in the figure, 1579cm -1 and 1376cm -1 The asymmetric and symmetric stretching peaks of the MOF-69 skeleton structure -(OCO)-, and the catalyst precursor showed the same characteristic vibration peaks as MOF-69. Combined with the XRD and FTIR test results, it shows that MOF-69 is formed in the catalyst precursor.

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

[0065] Example 2

[0066] Completely dissolve 0.75g nickel acetate and 37.3mg dichlorotetraamminepalladium in 34mL water. Then disperse 3g of γ-Al2O3 in 34mL ethanol and add the above aqueous solution under stirring. Dissolve 0.13g terephthalic acid in 34mL DMF and add it to the above stirring solution and react at 120℃ for 7h. Then cool to room temperature, separate and dry to obtain the catalyst precursor Pd-MOF-69 / Al2O3. The above catalyst precursor is placed in a tubular furnace and pyrolyzed at 500℃ for 200min. The volume ratio of hydrogen to nitrogen is 1:1 to obtain Al2O3-loaded NiPd catalyst S2.

[0067] Example 3

[0068] Completely dissolve 0.59g nickel nitrate hexahydrate and 25mg palladium dichlorotetraammine in 34mL water. Then disperse 3g of γ-Al2O3 in 34mL ethanol and add the above aqueous solution under stirring. Dissolve 0.21g terephthalic acid in 34mL DMF and add it to the above stirring solution and react at 120℃ for 7h. Then cool to room temperature, separate and dry to obtain the catalyst precursor Pd-MOF-69 / Al2O3. The above catalyst precursor is placed in a tubular furnace and pyrolyzed at 500℃ for 200min. The volume ratio of hydrogen to nitrogen is 1:1 to obtain Al2O3-loaded NiPd catalyst S3.

[0069] Example 4

[0070] Completely dissolve 0.59g nickel nitrate hexahydrate and 37.3mg palladium dichlorotetraammine in 34mL water. Then disperse 3g γ-Al2O3 in 34mL ethanol and add the above aqueous solution under stirring. Dissolve 0.13g terephthalic acid in 34mL DMF and add it to the above stirring solution and react at 140°C for 10h. Then cool to room temperature, separate and dry to obtain the catalyst precursor Pd-MOF-69 / Al2O3. The above catalyst precursor is placed in a tubular furnace and pyrolyzed at 600°C for 180min. The volume ratio of hydrogen to nitrogen is 1:1 to obtain Al2O3-loaded NiPd catalyst S4.

[0071] Example 5

[0072] Completely dissolve 0.59g nickel nitrate hexahydrate and 37.3mg palladium dichlorotetraammine in 34mL water. Then disperse 3g of γ-Al2O3 in 34mL ethanol and add the above aqueous solution under stirring. Dissolve 0.13g terephthalic acid in 34mL DMF and add it to the above stirring solution and react at 120℃ for 10h. Then cool to room temperature, separate and dry to obtain the catalyst precursor Pd-MOF-69 / Al2O3. The above catalyst precursor was placed in a tubular furnace and pyrolyzed at 550℃ for 220min. The volume ratio of hydrogen to nitrogen was 0.8:1 to obtain Al2O3-loaded NiPd catalyst S5.

[0073] Example 6

[0074] The method of Example 1 was followed, except that the amount of terephthalic acid added was 0.06 g.

[0075] Al2O3-supported NiPd catalyst S6 was obtained.

[0076] Example 7

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

[0078] Example 8

[0079] The method of Example 1 was followed, except that an equal amount of trimesic acid was used to replace terephthalic acid, to obtain Al2O3-supported NiPd catalyst S8.

[0080] Comparative Example 1

[0081] Using the conventional impregnation method, 0.59g nickel nitrate hexahydrate, 37.3mg dichlorotetraamminepalladium and 3g Al2O3 were dispersed in water and stirred at room temperature for 8h. After the reaction was completed, the precursor material was separated and dried. The above catalyst precursor was placed in a tubular furnace and pyrolyzed at 500℃ for 200min, with a volume ratio of hydrogen to nitrogen of 1:1, to obtain 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 of the above-mentioned embodiment and comparative example was added to the inner lining of the reactor, and then 20 g of methylcyclohexane (solvent) and 1 g of dicyclopentadiene were added. After the reactor was loaded and sealed, the air in the reactor was replaced and the hydrogen pressure in the reactor was maintained at 3 MPa. The reaction was stirred at a reaction temperature of 70° C. for 1 hour, and then the product composition was analyzed by Agilent 7890 chromatograph, and the results are shown in Table 1.

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

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

[0087] Table 1

[0088] Catalyst No. Reaction temperature℃ Reaction pressure MPa DCPD conversion rate % THDCPD selectivity % 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] In order 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 the reaction was repeated three times, 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 on a fixed bed

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

[0094] Table 3

[0095]

[0096] It can be seen from the results of Tables 1 to 3 that the catalyst prepared in the embodiment of the present invention has a high hydrogenation activity, a conversion rate of dicyclopentadiene of 100%, a selectivity of saturated hydrogenation product tetrahydrodicyclopentadiene of more than 80%, preferably more than 99%, and exhibits high stability, and can achieve continuous preparation of tetrahydrodicyclopentadiene. The reason is that an organic ligand is introduced during the preparation process, and the organic ligand and the nickel source are assembled to form a catalyst precursor containing a MOFs structure. By utilizing the advantages of MOFs, the dispersion of the metal can be improved, and the low-temperature hydrogenation activity of the catalyst can be improved.

[0097] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for preparing a catalyst, characterized in that: The following steps are involved: (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) subjecting the mixed solution to an aging treatment to obtain a catalyst precursor; (3) calcining the catalyst precursor.

2. The preparation method according to claim 1, wherein The organic ligand is terephthalic acid; Preferably, the mass ratio of the nickel source calculated as nickel to the noble metal source calculated as the noble metal element is 5-20:1, preferably 7-18:1; Preferably, the nickel source is selected from at least one of nickel chloride, nickel sulfate, nickel nitrate and nickel acetate; Preferably, the noble metal in the noble metal source is selected from at least one of Pd, Pt and Ru, preferably Pd.

3. The preparation method according to claim 1 or 2, wherein The mass ratio of the total amount of the nickel source and the noble metal source to the alumina precursor is 0.01-0.2:1, preferably 0.04-0.1:1; Preferably, the mass ratio of the organic ligand to the alumina precursor is 0.01-0.1:1, preferably 0.03-0.07:1; Preferably, the alumina precursor is γ-Al2O3; Preferably, the aluminum oxide precursor is provided by a dispersion of the aluminum oxide precursor, and the solvent in the dispersion is selected from at least one of ethanol, methanol, acetone and N,N-dimethylformamide.

4. The preparation method according to any one of claims 1 to 3, wherein The method of providing the mixed solution in step (1) includes: firstly mixing the nickel source, the noble metal source and the aluminum oxide precursor, and then mixing them with the organic ligand for a second time.

5. The preparation method according to any one of claims 1 to 4, wherein: The aging treatment allows the nickel source and the organic ligand to self-assemble to form a nickel-organic framework compound; Preferably, the aging treatment conditions include: temperature of 90-220°C and time of 5-25h; Preferably, the aging treatment is carried out under stirring conditions.

6. The preparation method according to any one of claims 1 to 5, wherein: The calcination is carried out in the presence of a reducing gas and / or an inert gas, wherein the reducing gas is preferably hydrogen; the inert gas is selected from at least one of nitrogen, argon and helium; Preferably, the volume ratio of the reducing gas to the inert gas is 1:0.5-1; Preferably, the calcination temperature is 350-750° C., and the calcination time is 3-15 h.

7. A catalyst obtained by the preparation method according to any one of claims 1 to 6.

8. A method for hydrogenating dicyclopentadiene, comprising: Under hydrogenation reaction conditions, dicyclopentadiene and hydrogen are contacted with a hydrogenation catalyst; characterized in that the hydrogenation catalyst is the catalyst according to claim 7.

9. The method according to claim 8, wherein: The contact is carried out in a high-pressure reactor, and the hydrogenation reaction conditions include: reaction temperature of 40-150° C., pressure of 2-6 MPa, and reaction time of 1-25 h; Preferably, the contacting is carried out under stirring conditions, and the stirring rate is 300-1000 r / min.

10. The method according to claim 8, wherein: The contact is carried out in a fixed bed reactor. The hydrogenation reaction conditions include: reaction temperature of 50-100°C, pressure of 3-6MPa, hydrogen / hydrocarbon volume ratio of 200-600:1, reaction mass space velocity of 1-3h -1 .

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