Preparation method of nickel-based catalyst with high metal content and small particle size and application of nickel-based catalyst in polymer hydrogenation catalysis

Abstract

The invention discloses a preparation method of a nickel-based catalyst with high metal content and small particle size and application of the nickel-based catalyst in polymer hydrogenation catalysis. The catalyst comprises 40-60 wt% of nickel, 3-8 wt% of M metal, 3-8 wt% of metal oxide N and 10-30 wt% of silicon. And performing hydrogen reduction in a coprecipitation manner to form the nickel silicate loaded nickel-based catalyst. The preparation process is simple, and the product is stable, suitable for amplification and ideal in performance. The catalyst has good activity in polymer hydrogenation, and especially in petroleum resin catalytic hydrogenation, the hydrogenation degree is greater than or equal to 98% under mild conditions.

Description

Technical Field

[0001] The present invention belongs to the technical field of industrial catalysis, and relates to a preparation method of a nickel-based catalyst with a high metal content and small particle size and its application in polymer hydrogenation catalysis. Background Art

[0002] A hydrogenation catalyst is a substance that can lower the activation energy of a hydrogenation reaction, thereby accelerating the chemical reaction rate between hydrogen and reactant molecules. In a hydrogenation reaction, hydrogen molecules are activated under the action of a catalyst, and then undergo an addition reaction with unsaturated bonds (such as C=C double bonds, C≡N triple bonds, C=O double bonds, C=N double bonds, etc.) in the reactant molecules, converting unsaturated compounds into saturated compounds. Nickel-based catalysts are a commonly used type of hydrogenation catalyst and are widely used in various hydrogenation catalyses. CN119504661A prepared a nickel-based catalyst with a porous carbon / molybdenum disulfide material carrier to hydrogenate succinic acid to obtain tetrahydrofuran. CN119386878A prepared a nickel-based catalyst supported on an Al2O3-Ga2O3 carrier for selective hydrogenation of the first stage of pyrolysis gasoline.

[0003] In hydrogenation reactions, polymer hydrogenation is an important way to improve the stability and antioxidant properties of polymers and enhance the added value of products. However, due to the large number of unsaturated bonds and large steric hindrance in polymers, a large number of active sites are required on the catalyst surface to increase the contact probability with hydrogen and unsaturated bonds. In addition, the strong acidity of the catalyst will cause chain scission of the polymer during hydrogenation, reducing the molecular weight of the polymer and affecting the subsequent application of the product. In small molecule hydrogenation, high dispersion and high activity of Ni can usually be achieved by the impregnation method. However, in polymer hydrogenation, due to the high content of unsaturated bonds, in order to achieve ideal hydrogenation activity, a high content of Ni metal needs to be loaded, which easily causes problems such as particle agglomeration and metal loss during the reduction of the catalyst, reducing the catalytic activity. The nickel - diatomaceous earth supported catalyst prepared by the impregnation method reported in Patent US 3040009 was used for the hydrogenation reaction of C5 petroleum resin, and the bromine value of the obtained hydrogenated petroleum resin was 1 - 3 gBr2 / 100 g, with low hydrogenation activity, easy metal agglomeration, and easy sintering at high temperatures. Finally, in order to avoid C-C bond scission in polymer hydrogenation, the acidity of the catalyst should be reduced as much as possible, and choosing a neutral or basic catalyst carrier is an ideal way, but it may affect the hydrogenation activity. Summary of the Invention

[0004] The present invention adopts a coprecipitation method to prepare a nickel silicate precursor, so as to achieve uniform loading of a high-loaded amount of Ni in the catalyst. In addition, the layered structure of nickel silicate has a strong metal-carrier interaction, which can effectively avoid the problem of Ni particle agglomeration and loss under reduction or high-temperature reaction. By using part of the unreduced nickel silicate as a carrier and adding metal oxides to improve the alkalinity of the carrier, the chain breaking in the hydrogenation of macromolecules can be reduced, and the adsorption and activation ability of the catalyst for unsaturated bonds can be improved. In addition, by adding a metal promoter, a Ni-M alloy is formed, so that Ni 0 The electronic structure is shifted and electron-rich, which promotes the adsorption and dissociation activation of hydrogen. Finally, the catalyst is used in polymer hydrogenation reaction, providing a cheap, easy to prepare, high hydrogenation activity, high stability and wide application range hydrogenation catalyst for industry.

[0005] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a method for preparing a nickel-based catalyst with high metal content and small particle size and its application in polymer hydrogenation catalysis. The nickel-based catalyst is prepared by a coprecipitation method, which has a simple preparation process, high catalytic hydrogenation activity and good stability. By adding a metal promoter M, a Ni-M alloy is formed to improve the hydrogen dissociation activity. By adding a metal oxide N and doping it in a nickel silicate carrier, the adsorption catalytic activity of the catalyst for unsaturated bonds is improved. The synergistic effect of multiple components can obtain an ideal catalytic hydrogenation performance.

[0006] To achieve the above object, the technical solution adopted by the present invention is: A method for preparing a nickel-based catalyst with high metal content and small particle size, wherein the preparation method adopts a coprecipitation method, and the raw materials are calculated by weight. The coprecipitation method specifically comprises the following steps: Step 1: Add 1-6 parts of weak alkaline salt to the reactor, dissolve it in 120-200 parts of deionized water as the base liquid, heat it to 70-110°C, and stir it at a speed of 300-650 rad / min. Further optimization: add 2-4 parts of weak alkaline salt to the reactor, dissolve it in 140-180 parts of deionized water as the base liquid, heat it to 80-100°C, and stir it at a speed of 400-550 rad / min.

[0007] Step 2: Weigh 3-15 parts of silicon source, 5-20 parts of weak alkaline salt, 100-300 parts of deionized water to make solution A; weigh 20-50 parts of nickel source, 1-10 parts of M metal source, 1-10 parts of N metal source, 100-300 parts of deionized water to make solution B. Further optimization: weigh 3-10 parts of silicon source, 8-15 parts of weak alkaline salt, 150-250 parts of deionized water to make solution A; weigh 20-40 mol of nickel source, 1-5 parts of M metal source, 1-5 parts of N metal source, 150-250 parts of deionized water to make solution B.

[0008] Step 3: Simultaneously add Solution A and Solution B to the reactor in Step 1, control the dropping rate to complete the addition within 10 - 40 minutes, and after completion, control the pH value between 7.0 - 9.0. After the dropping is completed, continue the reaction for 1.5 - 4 hours until the reaction ends, obtaining Material X.

[0009] Step 4: Wash the reacted Material X with deionized water to remove soluble salts in the solvent until the conductivity of the filtrate is lower than 0.1 S / m. Then, it can be replaced with one solvent among deionized water, absolute ethanol, propanol, and acetone, and filtered to obtain Filter Cake Y.

[0010] Preparation of powder catalyst: Step 5: Dry Filter Cake Y in an oven, spray dryer, flash dryer, or fluidized bed dryer at 50 - 90 °C until the water content is <5 wt% to complete the drying, obtaining the catalyst precursor.

[0011] Or preparation of shaped particle catalyst: Step 5: Add one or two mixtures of kaolin, diatomite, montmorillonite, illite, allophane, etc. to Filter Cake Y, with a mass ratio of 1:1 - 20, and further optimize the mass ratio to 1:1 - 10.

[0012] After mixing, fill the material into a granulator to obtain a catalyst precursor in the form of cylindrical, spherical, or irregularly shaped particles (1 - 10 mm).

[0013] Step 6: Place the catalyst precursor in a tubular furnace or fixed bed, under an atmosphere of H2 or 2% - 20% H2 / Ar, with a heating rate of 1 - 5 °C / min and a reduction temperature of 300 - 700 °C, and reduce for 1 - 8 hours to obtain the nickel-based catalyst. Further optimize, with a reduction temperature of 300 - 500 °C and a reduction time of 1 - 4 hours.

[0014] Step 7: After reduction, add one or more mixtures of light oil, paraffin oil, methylcyclohexane, cyclohexane, cyclopentane, acetone, absolute ethanol, etc. to the catalyst for liquid sealing, and encapsulate and store the catalyst.

[0015] The finished catalyst, through elemental analysis, contains 40 - 60 wt% nickel, 3 - 8 wt% M metal, 3 - 8 wt% N metal, 10 - 30 wt% silicon, and the remaining are O and H elements.

[0016] The M metal is one or a mixture of two or more of Co, Cu, Fe, Pd, Pt, and Ag, which forms a Ni-M alloy with nickel in the catalyst, making nickel in an electron-rich state.

[0017] The N metal mentioned above is one or a mixture of two or more of Mg, Mn, Al, Ti, Ca, Ba, Ce, La, Sr, and Zn. It exists in the form of an oxide state in the catalyst and is doped in the nickel silicate support to adjust the acidity and basicity of the catalyst and promote the adsorption and activation of the catalyst on unsaturated bonds.

[0018] The nickel-based catalyst mentioned above is a nickel-based catalyst with nickel silicate as the support. It can be in powder form (particle size is 5 - 60 μm) or in granular form (1 - 10 nm), and both need to be stored sealed.

[0019] The silicon source can be one or a mixture of two or more of liquid water glass, sodium metasilicate pentahydrate, and sodium silicate nonahydrate.

[0020] The nickel source can be one or a mixture of two or more of nickel chloride hexahydrate, nickel chloride, nickel nitrate, nickel acetylacetonate, nickel acetate, etc.

[0021] The weak basic salt can be one or a mixture of two or more of sodium carbonate, sodium bicarbonate, ammonium chloride, sodium chloride, sodium hydroxide, potassium carbonate, potassium bicarbonate, etc.

[0022] The M metal source and N metal source can be one or a mixture of two or more of chlorides, nitrates, acetates, acetylacetonates, acetates, nitrites, phosphates, sulfates, and sulfites.

[0023] The application in polymer hydrogenation catalysis mentioned above: The powder catalyst is used in a high-pressure reactor. The reaction temperature is 130 - 300 °C, the hydrogen pressure is 0.5 - 10 MPa, and for the powder catalyst, the ratio of catalyst to reactant is 0.01 - 0.25:1.

[0024] The shaped particle catalyst is used in a fixed-bed reactor. The reaction temperature is 130 - 300 °C, the hydrogen pressure is 0.5 - 10 MPa, for the particle catalyst, the hydrogen-oil volume ratio is 100 - 1000, and the reaction space velocity is 0.1 - 5 h -1 。

[0025] The application in polymer hydrogenation catalysis mentioned above can be used in the hydrogenation of petroleum resins (C5 petroleum resin, C9 petroleum resin, C5 / C9 mixed petroleum resin, DCPD resin), the hydrogenation of polystyrene, the hydrogenation of polypropylene, the hydrogenation of polycarbonate, the hydrogenation of turpentine, the hydrogenation of DCPD, the hydrogenation of ethylene, and the hydrogenation of propylene. After further optimization, it can be used in the hydrogenation of petroleum resins (C5 petroleum resin, C9 petroleum resin, C5 / C9 mixed petroleum resin, DCPD resin), the hydrogenation of DCPD, the hydrogenation of ethylene, and the hydrogenation of propylene, and all show ideal hydrogenation effects.

[0026] The present invention has the following advantages: 1) The synthesis method is simple, suitable for batch production. The active components are in a highly dispersed state at the nanoscale. The nickel-based catalyst supported on nickel silicate has high activity and high stability, and can catalyze various unsaturated organic molecules, especially unsaturated macromolecular polymers, and further especially in petroleum resins, to achieve efficient hydrogenation under suitable conditions.

[0027] 2) The promoters in the catalyst have multiple functions. The M metal forms a Ni-M alloy with nickel. Through electronic regulation, Ni 0 shows a rich electron state, promoting the dissociation of hydrogen molecules; the metal oxide N is doped into the nickel silicate support to adjust the acidity and basicity of the support, improve the adsorption and activation ability of the catalyst for unsaturated bonds, reduce the hydrogenation activation energy, and promote the efficient and deep hydrogenation of macromolecular polymers. Description of the Drawings

[0028] Figure 1 is the XRD pattern of the unreduced precursors of P2, P4-P7 catalysts; Figure 2 is the XRD pattern of P2, P4-P7 catalysts; Figure 3 is the C2H4-TPD pattern of P2, P4-P7 catalysts; Figure 4 is the XRD pattern and XPS pattern of P2, PD1, PD2 catalysts; Figure 5 is the SEM pattern of P2 catalyst. Detailed Embodiments

[0029] The present invention will be described in detail below through specific examples, but these examples do not limit the content of the present invention. The parts of raw materials used in the examples are parts by weight.

[0030] Example 1 Step 1: Add 2 parts of sodium bicarbonate to the reaction kettle, dissolve it in 160 parts of deionized water as the bottom liquid, heat it to 90 °C, and the stirring speed is 450 rad / min.

[0031] Step 2: Weigh 7.6 parts of sodium silicate pentahydrate, 10 parts of sodium bicarbonate, and 200 parts of deionized water to prepare solution A; weigh 23.7 parts of nickel chloride hexahydrate, 2.9 parts of cobalt nitrate, 2.8 parts of magnesium nitrate, and 200 parts of deionized water to prepare solution B.

[0032] Step 3: Add solution A and solution B to the reaction kettle in step 1 simultaneously, control the dropping speed to be added within 20 minutes, and control the pH value to be about 8.0 after completion. After the dropping is completed, continue to react for 2 hours and then the reaction ends to obtain material X.

[0033] Step 4: Wash the reacted material X with deionized water to remove the soluble salts in the solvent until the conductivity of the filtrate is lower than 0.1 S / m. After that, anhydrous ethanol can be used for replacement and filtration to obtain the filter cake Y.

[0034] Preparation of powder catalyst: Step 5: Dry the filter cake Y in an oven at 60 °C until the water content is < 5 wt% to complete the drying and obtain the catalyst precursor.

[0035] Or preparation of shaped particle catalyst: Step 5: Add kaolin to the filter cake Y with a mass ratio of 1:10.

[0036] After mixing, fill the material into a granulator to obtain columnar particles of 2 - 3 mm.

[0037] Step 6: Place the catalyst precursor in a tubular furnace, under a H2 atmosphere, with a heating rate of 2 °C / min, a reduction temperature of 300 / 400 / 500 °C, and reduce for 2 hours.

[0038] Step 7: After reduction, add light oil to the catalyst for liquid sealing, and encapsulate and store the catalyst. Among them, according to different reduction temperatures, the powder catalysts are marked as P-Ni1Co 0.1 / PS-1Mg-300 (P1), P-Ni1Co 0.1 / PS-1Mg-400 (P2), P-Ni1Co 0.1 / PS-1Mg-500 (P3). The particulate catalysts are marked as L-Ni1Co 0.1 / PS-1Mg-300 (L1), L-Ni1Co 0.1 / PS-1Mg-400 (L2), L-Ni1Co 0.1 / PS-1Mg-500 (L3).

[0039] Example 2 Most of the operation steps are the same as those in Example 1, except that the M metal source is replaced with copper nitrate or iron chloride or palladium acetate or cobalt acetylacetonate. The reduction temperature is controlled at 400 °C to obtain powder catalysts marked as P-Ni1Cu 0.1 / PS-1Mg-400 (P4), P-Ni1Fe 0.1 / PS-1Mg-400 (P5), P-Ni1Pd 0.1 / PS-1Mg-400 (P6), P-Ni1Co 0.1 / PS-1Mg-400 (P7).

[0040] The particulate catalyst is marked as L-Ni1Cu 0.1 / PS-1Mg-400 (L4), L-Ni1Fe 0.1 / PS-1Mg-400 (L5), L-Ni1Pd 0.1 / PS-1Mg-400 (L6), L-Ni1Co 0.1 / PS-1Mg-400 (L7).

[0041] Example 3 Most of the operation steps are the same as those in Example 1. The difference is that the N metal source is replaced with manganese nitrate or calcium chloride or aluminum nitrate or cerium nitrate or zinc acetate. The reduction temperature is controlled at 400 °C to obtain a powder catalyst, labeled as P-Ni1Co 0.1 / PS-1Mn-400 (P8), P-Ni1Co 0.1 / PS-1Ca-400 (P9), P-Ni1Co 0.1 / PS-1Al-400 (P10), P-Ni1Co 0.1 / PS-1Ce-400 (P11), P-Ni1Co 0.1 / PS-1Zn-400 (P12).

[0042] Comparative Sample 1: Most of the operation steps are the same as those in Example 1. The difference is that neither the N metal source nor the M metal source is added. The reduction temperature is controlled at 400 °C to obtain a powder catalyst, labeled as P-Ni / PS-400 (PD-1).

[0043] Comparative Sample 2: Most of the operation steps are the same as those in Example 1. The difference is that neither the N metal source nor the M metal source is added, and the nickel source is replaced with cobalt nitrate. The reduction temperature is controlled at 400 °C to obtain a powder catalyst, labeled as P-Co / PS-400 (PD-2).

[0044] Comparative Sample 3: Most of the operation steps are the same as those in Example 1. The difference is that the M metal source is not added. The reduction temperature is controlled at 400 °C to obtain a powder catalyst, labeled as P-Ni / PS-1Mg-400 (PD-3).

[0045] Comparative Sample 4: Most of the operation steps are the same as those in Example 1. The difference is that the N metal source is not added. The reduction temperature is controlled at 400 °C to obtain a powder catalyst, labeled as P-Ni1Co 0.1 / PS-400 (PD-4).

[0046] Hydrogenation reaction performance evaluation: Powder catalyst: The reaction was carried out in a high-pressure reactor at a reaction temperature of 260 °C, a hydrogen pressure of 8.0 MPa, and a mass ratio of powdered catalyst (P1 - P12) to DCPD resin of 0.02:1.

[0047] The reaction was carried out in a high-pressure reactor at a reaction temperature of 260 °C, a hydrogen pressure of 8.0 MPa, and a mass ratio of powdered catalyst (P2) to C9 petroleum resin of 0.02:1.

[0048] The reaction was carried out in a high-pressure reactor at a reaction temperature of 260 °C, a hydrogen pressure of 8.0 MPa, and a mass ratio of powdered catalyst (P2) to C5 petroleum resin of 0.02:1.

[0049] The reaction was carried out in a high-pressure reactor at a reaction temperature of 260 °C, a hydrogen pressure of 8.0 MPa, and a mass ratio of powdered catalyst (P2) to polystyrene of 0.02:1.

[0050] Granular catalyst: The reaction was carried out in a fixed-bed reactor at a reaction temperature of 150 °C, a hydrogen pressure of 4.0 MPa, with granular catalysts (L1 - L7), a hydrogen-oil volume ratio of 200:1, and a reaction space velocity of 0.5 h -1 The reactant was a 20 wt% DCPD solution and the solvent was cyclohexane.

[0051] Detection method: Color: Determined by the Gardner colorimetric method according to GB22295 - 2008.

[0052] Degree of hydrogenation: Determined according to the petrochemical industry standard SH / T0236 - 92.

[0053] Table 1 Performance of various powdered catalysts on DCPD resin Table 2 Hydrogenation performance of catalyst P2 on different polymers Table 3 Hydrogenation performance of various granular catalysts on DCPD It can be easily seen from the above reaction results that the catalysts of various embodiments of the present invention have good hydrogenation catalytic performance on various reactant molecules. Due to the lack of addition of promoter metals, the hydrogenation performance of the comparative samples is weak. In particular, when the nickel-based catalyst in comparative sample 2 was replaced with a cobalt-based catalyst, its catalytic hydrogenation performance was even worse.

[0054] From Figure 1It can be seen that the prepared catalyst precursors all maintain the crystal structure of nickel silicate, which proves that layered nickel silicate is successfully synthesized by the co-precipitation method. From the SEM image of the P2 catalyst ( Figure 5 ), it is proved that the reduced catalyst maintains the morphology of layered nickel silicate. From Figure 2 it can be seen that the reduced catalyst forms a nickel-based catalyst supported on nickel silicate by in-situ precipitation of Ni 0 from nickel silicate. From Figure 3 it can be seen that by adding different metal oxides, the adsorption and activation ability of the catalyst for unsaturated double bonds can be effectively adjusted. Among them, the additive Mg added to P2 has the largest adsorption amount of C2H4, so the hydrogenation degree is the highest. From Figure 4 it can be seen that by adding the metal additive M, in XRD, the lattice of Ni 0 shifts, and the Ni-M alloy is successfully synthesized. In XPS, M provides electrons to Ni, making Ni 0 in a rich electron state and improving the hydrogen dissociation activity of Ni 0 . Since PD3 does not add the M metal source and does not form the Ni-Co alloy, the hydrogen dissociation activity decreases, which in turn affects the hydrogenation degree. And since PD4 does not add the N metal source, the basic strength of the catalyst support is lower than that of P2, and the adsorption amount of C2H4 is less than that of P2. Therefore, the adsorption and activation ability for double bonds is lower than that of P2, and the hydrogenation degree is lower.

[0055] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A preparation method of a nickel-based catalyst with high metal content and small particle size, characterized in that, The raw materials are calculated by weight, and the preparation method comprises the following steps: Step 1: Add 1-6 parts of weak alkaline salt to the reaction kettle, dissolve it in 120-200 parts of deionized water as the base liquid, heat it to 70-110°C, and stir it at a speed of 300-650 rad / min; Step 2: Weigh 3-15 parts of silicon source, 5-20 parts of weak alkaline salt, and 100-300 parts of deionized water to prepare solution A; weigh 20-50 parts of nickel source, 1-10 parts of M metal source, 1-10 parts of N metal source, and 100-300 parts of deionized water to prepare solution B; Step 3, simultaneously add solution A and solution B dropwise to the reactor in step 1, control the dropwise addition speed to complete the addition within 10-40 minutes, control the pH value to be between 7.0-9.0 after the addition is completed, continue the reaction for 1.5-4 hours, and then the reaction is terminated to obtain material X; Step 4: washing the reacted material X with deionized water until the conductivity of the filtrate is less than 0.1 S / m, then replacing it with a solvent selected from deionized water, anhydrous ethanol, propanol, and acetone, and filtering to obtain a filter cake Y; Powder catalyst preparation: Step 5: drying the filter cake Y in an oven, spray dryer, flash dryer or fluidized bed dryer at 50-90° C., and drying is completed when the water content is less than 5wt%, thereby obtaining a catalyst precursor; Or preparation of shaped particle catalyst: Step 5: adding one or a mixture of two of kaolin, diatomaceous earth, montmorillonite, illite, and bauxite to the filter cake Y in a mass ratio of 1:1-20, and after mixing, filling the materials into a granulator to obtain a columnar, spherical or irregularly shaped catalyst precursor with a particle size of 1-10 mm; Step 6: placing the catalyst precursor in a tube furnace or a fixed bed, in an atmosphere of H2 or 2%-20% H2 / Ar, with a heating rate of 1-5°C / min, a reduction temperature of 300-700°C, and reducing for 1-8 hours to obtain the nickel-based catalyst; Step 7: After reduction, one or a mixture of two or more of light oil, paraffin oil, methylcyclohexane, cyclohexane, cyclopentane, acetone, and anhydrous ethanol is added to the catalyst for liquid sealing, and the catalyst is packaged and stored.

2. The preparation method according to claim 1, characterized in that, The prepared nickel-based catalyst contains 40-60 wt % nickel, 3-8 wt % M metal, 3-8 wt % N metal, 10-30 wt % silicon, and the rest are O and H elements according to elemental analysis; The M metal is one or a mixture of two or more of Co, Cu, Fe, Pd, Pt, and Ag, which forms a Ni-M alloy with nickel in the catalyst, making nickel electron-rich. The N metal is one or a mixture of two or more of Mg, Mn, Al, Ti, Ca, Ba, Ce, La, Sr, and Zn, which exists in an oxidized form in the catalyst and is doped in the nickel silicate carrier to adjust the acidity and alkalinity of the catalyst and promote the adsorption and activation of the catalyst on unsaturated bonds.

3. The preparation method according to claim 1, wherein The nickel-based catalyst is a nickel-based catalyst using nickel silicate as a carrier, and is in powder or granular form, and needs to be sealed and stored.

4. The preparation method according to claim 1, characterized in that, The particle size of the powdered nickel-based catalyst is 5 - 60 μm; the particle size of the granular nickel-based catalyst is 1 - 10 nm.

5. The preparation method according to claim 1, characterized in that, The silicon source described in Step 2 is one or a mixture of two or more of liquid water glass, sodium silicate pentahydrate, and sodium silicate nonahydrate.

6. The preparation method according to claim 1, characterized in that, The nickel source described in Step 2 is one or a mixture of two or more of nickel chloride hexahydrate, nickel chloride, nickel nitrate, nickel acetylacetonate, and nickel acetate; the M metal source and the N metal source are one or a mixture of two or more of chlorides, nitrates, acetates, acetylacetonates, acetates, nitrites, phosphates, sulfates, and sulfites.

7. The preparation method according to claim 1, wherein The weak base salts described in Step 1 and Step 2 are one or a mixture of two or more of sodium carbonate, sodium bicarbonate, ammonium chloride, sodium chloride, sodium hydroxide, potassium carbonate, and potassium bicarbonate.

8. Use of a nickel-based catalyst with a high metal content and small particle size prepared by the preparation method according to any one of claims 1-7 in polymer hydrogenation catalysis, characterized in that, When the catalyst is in powder form, the hydrogenation reaction is carried out in a high-pressure reactor, the reaction temperature is 130 - 300 °C, the hydrogen pressure is 0.5 - 10 MPa, for the powdered catalyst, the mass ratio of the catalyst to the reactant is 0.01 - 0.25:

1.

9. Use of a nickel-based catalyst with high metal content and small particle size prepared by the preparation method according to any one of claims 1-7 in polymer hydrogenation catalysis, characterized in that, When the catalyst is in the form of shaped particles, the hydrogenation reaction is carried out in a fixed-bed reactor, with the reaction temperature being 130 - 300 °C, the hydrogen pressure being 0.5 - 10 MPa, the granular catalyst, the hydrogen-oil volume ratio being 100 - 1000, and the reaction space velocity being 0.1 - 5 h -1 .

10. The application according to claim 8 or 9, characterized in that The polymer hydrogenation catalysis reaction includes: hydrogenation of petroleum resin, hydrogenation of polystyrene, hydrogenation of polypropylene, hydrogenation of polycarbonate, hydrogenation of turpentine, hydrogenation of DCPD, hydrogenation of ethylene, and hydrogenation of propylene.

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