Nickel-based catalyst for catalytic hydrogenation of unsaturated hydrocarbon polymer as well as preparation method and application of nickel-based catalyst

Abstract

The invention provides a nickel-based catalyst for catalytic hydrogenation of unsaturated hydrocarbon polymers as well as a preparation method and application of the nickel-based catalyst. The nickel-based catalyst contains a first component, a second component and a third component, wherein the first component is Ni; the second component is selected from one or more of Al and Si; and an optional third component, wherein the third component is one or more metal additives selected from Mo, Fe, Cr, Co, Ti, Mn, La and Ce. According to the preparation method of the porous nickel-based catalyst, all the components of the catalyst are mixed and then smelted at a high temperature to form an alloy, and then the alloy is activated by alkali liquor to remove Al or Si, so that the porous nickel-based catalyst is prepared. The catalyst is especially suitable for partial hydrogenation and deep hydrogenation of butadiene and styrene block copolymerized polymers.

Description

Technical Field

[0001] The present invention belongs to the field of catalytic hydrogenation, and in particular relates to a nickel-based catalyst for catalytic hydrogenation of unsaturated hydrocarbon polymers, a preparation method thereof, and application thereof in partial hydrogenation and deep hydrogenation of unsaturated hydrocarbon polymers. Background Art

[0002] In the field of polymer materials, unsaturated hydrocarbon polymers containing carbon-carbon double bonds are widely used in various industrial fields due to their unique physical and chemical properties. Among them, styrene-butadiene-styrene block copolymer (SBS), a common thermoplastic elastomer (TPE), has attracted much attention due to its excellent processing properties and its ability to avoid vulcanization. However, the presence of unsaturated double bonds in the SBS molecular structure results in deficiencies in thermal stability, UV resistance, and mechanical properties, which to some extent limits its application in high-performance materials. In recent years, researchers have focused on improving the properties of SBS through hydrogenation. Currently, the hydrogenation of the carbon-carbon double bonds of the butadiene units in SBS is widely studied, but the deep hydrogenation of the benzene ring and the unsaturated carbon-carbon bonds of butadiene units is less studied. The product of full hydrogenation (i.e., deep hydrogenation) of the benzene ring and the unsaturated carbon-carbon bonds of butadiene units in SBS is a polycyclic block copolymer (CBC), in which the unsaturated phenyl groups are converted to saturated cyclohexanes. CBC not only retains the original processing properties of SBS but also significantly improves its thermodynamic stability, antioxidant capacity, and mechanical properties. Therefore, CBC has broad application prospects in optical materials and medical materials.

[0003] In the catalytic hydrogenation application of SBS, although homogeneous catalysts have good hydrogenation activity, there is a problem that they are difficult to separate from the product and will remain in the product. For example, patent CN 104226365A discloses a method for synthesizing SEBS (hydrogenated styrene-butadiene-styrene block copolymer) using a bis-titanocenes catalyst from SBS, but this method is limited to the selective hydrogenation of C=C double bonds, the reaction selectivity is limited, it is difficult to effectively hydrogenate the benzene ring, and the preparation process is relatively complex, difficult to apply on a large scale, and the removal of the catalyst after the reaction is difficult. Patent CN 114192188A discloses a method for synthesizing CBC (hydrogenated styrene-butadiene-styrene block copolymer) from SBS using a titanocene catalyst system, but this method has a low catalytic hydrogenation degree and is difficult to separate from the product. At the same time, catalyst residues may affect the performance of the final product (especially in the presence of multiple organic compounds). In addition, U.S. Patent US 00565 4253A discloses a noble metal catalyst supported by silica for the hydrogenation treatment of aromatic polymers. This method significantly improves the hydrogenation efficiency by optimizing the pore structure and specific surface area of ​​the carrier. However, the high cost of precious metal catalysts and the easy loss of precious metals on silicon-based carriers limit their widespread application in industrial production.

[0004] In contrast, heterogeneous nickel-based catalysts have advantages over precious metal catalysts, such as low cost, easy separation and recovery, good stability, and a wide range of applications, making them more advantageous in industrial production. Nickel-based catalysts prepared by the melting method have higher catalytic activity and mechanical strength than nickel-based catalysts prepared by precipitation and impregnation methods, which makes the catalyst have a longer service life in complex industrial applications. However, when heterogeneous nickel-based catalysts are used for hydrogenation of unsaturated hydrocarbon polymers (especially for hydrogenation of SBS to CBC), there is a problem of low deep catalytic hydrogenation activity.

[0005] Therefore, the present invention aims to provide a high-activity nickel-based catalyst with excellent hydrogenation effect on unsaturated hydrocarbon polymers and a method for preparing the catalyst, and elaborates in detail the application of the catalyst in the hydrogenation of SBS to produce CBC. Summary of the Invention

[0006] An object of the present invention is to provide a hydrogenation catalyst for hydrogenating SBS to CBC which has high catalytic hydrogenation activity and is easily separable.

[0007] Another object of the present invention is to provide a method for preparing the hydrogenation catalyst for hydrogenating SBS to CBC.

[0008] The third object of the present invention is to provide an application of the hydrogenation catalyst for preparing CBC by hydrogenating SBS.

[0009] Specifically, the above-mentioned object of the present invention is achieved through the following aspects:

[0010] In a first aspect, the present invention provides a nickel-based catalyst for catalytic hydrogenation of unsaturated hydrocarbon polymers, wherein the nickel-based catalyst comprises:

[0011] A first component, wherein the first component is Ni;

[0012] A second component, the second component being selected from one or more of Al and Si;

[0013] and an optional third component, wherein the third component is one or more metal additives selected from the group consisting of Mo, Fe, Cr, Co, Ti, Mn, La and Ce.

[0014] In a second aspect, the present invention provides a method for preparing the nickel-based catalyst according to the first aspect, wherein the method comprises the following steps:

[0015] (1) melting a first component, a second component, and an optional third component to form an alloy, wherein the first component is Ni, the second component is selected from one or more of Al and Si, and the third component is one or more metal additives selected from Mo, Fe, Cr, Co, Ti, Mn, La, and Ce;

[0016] (2) mechanically crushing and grinding the alloy into particles to obtain a precursor alloy;

[0017] (3) mixing the precursor alloy with a NaOH aqueous solution to perform a leaching reaction to obtain a porous nickel-based catalyst;

[0018] (4) The porous nickel-based catalyst is repeatedly washed with deionized water until it becomes neutral, and then washed with anhydrous ethanol to obtain the nickel-based catalyst.

[0019] In a third aspect, the present invention provides use of the nickel-based catalyst for catalytic hydrogenation of unsaturated hydrocarbon polymers.

[0020] In a fourth aspect, the present invention provides a method for catalytic hydrogenation of unsaturated hydrocarbon polymers using the above nickel-based catalyst.

[0021] Beneficial effects

[0022] The present invention modifies the performance of a nickel-based catalyst by adding different metal additives. After smelting at high temperature to form an alloy, the alloy is activated with alkaline solution to remove Al or Si to produce a porous nickel-based catalyst. The resulting catalyst exhibits high hydrogenation activity for unsaturated hydrocarbons in polymers and is particularly suitable for partial and deep hydrogenation of butadiene and styrene block copolymers. Specifically, the nickel-based catalyst provided by the present invention has many beneficial properties:

[0023] (1) The nickel-based catalyst of the present invention has high mechanical strength and excellent catalytic hydrogenation activity;

[0024] (2) The nickel-based catalyst of the present invention can fully hydrogenate the benzene ring and C=C double bond on SBS, and the obtained CBC has high light transmittance and certain tensile strength;

[0025] (3) The nickel-based catalyst of the present invention is a heterogeneous catalyst, which has the advantages of low cost, easy separation and recovery, good stability, and a wide range of applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The 1H-NMR spectra of the unhydrogenated SBS raw material and the SBS product after hydrogenation using the catalysts prepared by Examples 3 and 6 of the present invention are shown. When the hydrogenated SBS product was subjected to 1H-NMR analysis, the double bond protons (C=C) in butadiene showed characteristic peaks at 4.8-5.7ppm, and the benzene ring protons in the styrene segment showed characteristic peaks at 6.25-7.2ppm, corresponding to the unsaturated carbon-hydrogen bonds of butadiene and the hydrogen atoms on the benzene ring, respectively. Compared with the unhydrogenated SBS raw material, the olefin proton peaks at 4.8-5.7ppm and the aromatic proton peaks at 6.25-7.2ppm in the 1H-NMR spectrum of the hydrogenated SBS gradually weakened or even completely disappeared, indicating that the hydrogenation reaction caused the double bonds of butadiene and the hydrogen atoms of the benzene ring in the styrene segment to change to varying degrees. Figure 1 As shown, the catalyst prepared by Example 3 achieves a high degree of hydrogenation of olefins under experimental conditions, but partially hydrogenates the benzene ring of the styrene segment; the catalyst prepared by Example 6 can completely hydrogenate the unsaturated bonds of olefins and aromatics under certain experimental conditions. DETAILED DESCRIPTION

[0027] The specific embodiments of the present invention are described in detail below. The specific embodiments described herein are only used to illustrate and explain the present invention, but are not used to limit the present invention.

[0028] In this document, unless otherwise specified, the term "specific surface area" means the specific surface area measured by the BET method (Brunauer-Emmet-Teller), as described in standard NFX 11-621; the term "particle size distribution" means the particle size distribution, which is measured by light scattering.

[0029] In the present invention, the term "heterogeneous" means that the catalyst and other components in the reaction system (such as reactants or solvents) are in different physical states, usually manifested as a system in which the catalyst is solid and the reactants are liquid or gaseous.

[0030] In the present invention, the term "modification" refers to the process of changing the metallographic structure, specific surface area, electronic properties and other properties of the nickel-based catalyst by adding different metal additives.

[0031] In the present invention, unless otherwise specified, the term "nickel-based catalyst", also known as "Ni-based catalyst", refers to a multi-metal solid material with metallic nickel as the main active component, compounded with other metal elements and formed after alloying, treatment and structural regulation, and has a heterogeneous morphology and hydrogenation catalytic function.

[0032] In the present invention, the term "pore volume" refers to the total pore volume of the catalyst in the porous structure, which is measured by nitrogen adsorption-desorption method or corresponding standards.

[0033] In the present invention, the term "pore size" refers to an average pore size calculated by a nitrogen adsorption-desorption method.

[0034] In the present invention, the term "melting" refers to a process of heating a metal material under high temperature conditions until it is completely melted and the components are fully mixed to form an alloy with uniform composition.

[0035] In the present invention, the term "leaching" refers to the process of placing a solid material in a specific solution under certain temperature and reaction conditions so that some components therein are selectively dissolved and removed from the solid.

[0036] In the present invention, the terms "optional" and "optionally" mean that the objects they modify occur or do not occur, appear or do not appear. For example, "the catalyst contains a first component, a second component and an optional third component" covers: the catalyst contains a first component and a second component, or the catalyst contains a first component, a second component and a third component; for another example, "the first component, the second component and the optional third component are melted to form an alloy" covers: the first component and the second component are melted to form an alloy, or the first component, the second component and the third component are melted to form an alloy.

[0037] In the present invention, the term "partial hydrogenation" refers to a process in which unsaturated hydrocarbons in a polymer (such as double bonds or triple bonds in butadiene and styrene block copolymers) are only partially converted into saturated hydrocarbons under the action of a catalyst. That is, by controlling the reaction conditions, some of the unsaturated bonds in the polymer undergo hydrogenation reaction while retaining the chemical structure of the remaining unsaturated bonds, thereby achieving the regulation of polymer properties.

[0038] In the present invention, the term "deep hydrogenation" (also called "full hydrogenation") refers to the process in which all unsaturated hydrocarbons in a polymer (such as double bonds or triple bonds in butadiene and styrene block copolymers) are completely converted into saturated hydrocarbons under the action of a catalyst, that is, by optimizing the reaction conditions, all unsaturated bonds in the polymer undergo hydrogenation reaction, thereby achieving the transformation of the polymer from an unsaturated state to a fully saturated state.

[0039] For the purposes of this invention, the term "olefin hydrogenation degree" refers to the extent to which olefin double bonds in a polymer are saturated by hydrogenation during the hydrogenation reaction. It is typically expressed as the olefin double bond conversion rate or the content of saturated hydrocarbons in the hydrogenated product. This indicator reflects the catalytic efficiency and selectivity of a catalyst for olefin hydrogenation and can be used to evaluate catalyst performance during partial or deep hydrogenation processes.

[0040] In this application, the term "degree of aromatic hydrogenation" refers to the extent to which aromatic structures (such as benzene rings) in a polymer are saturated during hydrogenation. It is typically expressed as the conversion of aromatic structures or the content of saturated hydrocarbons in the hydrogenated product. This indicator reflects the catalytic efficiency and selectivity of a catalyst for aromatic hydrogenation and can be used to evaluate catalyst performance during partial or deep hydrogenation processes.

[0041] In some embodiments, the present invention provides a nickel-based catalyst for catalytic hydrogenation of unsaturated hydrocarbon polymers, wherein the nickel-based catalyst comprises:

[0042] A first component, wherein the first component is Ni;

[0043] A second component, the second component being selected from one or more of Al and Si;

[0044] and an optional third component, wherein the third component is one or more metal additives selected from the group consisting of Mo, Fe, Cr, Co, Ti, Mn, La and Ce.

[0045] In a preferred embodiment of the catalyst active component, the mass content of the first component Ni is 80-97wt%, such as 81-97wt%, 85-97wt%, 81-94wt%, 81-95wt%, 85-95wt%, 86-95wt%, 87-95wt%, 88-95wt%, or 89-94wt%, relative to the total mass of the nickel-based catalyst.

[0046] In a preferred embodiment, the second component is Al; preferably, the mass content of Al is 3-20 wt%, such as 3-15 wt%, 5-10 wt%, 5-9 wt%, 5-8 wt%, 5.5-9 wt%, 5.5-8 wt%, or 5.5-7.5 wt%, relative to the total mass of the nickel-based catalyst.

[0047] In another preferred embodiment, the second component is Si; preferably, the mass content of Si is 3-25wt%, such as 10-25wt%, 3-15wt%, 5-12wt%, 5-11wt%, 6-11wt%, 7-11wt%, or 6.5-7.5wt%, relative to the total mass of the nickel-based catalyst.

[0048] In another preferred embodiment, the second component is Al and Si; preferably, relative to the total mass of the nickel-based catalyst, the mass content of Al is 3-15wt% (e.g., 5-10wt%, 5-9wt%, 5-8wt%, 5.5-9wt%, 5.5-8wt%, or 7-8wt%) and the mass content of Si is 10-25wt% (e.g., 10-15wt%, 11-15wt%, 11-14wt%, or 11-12wt%).

[0049] In a preferred embodiment, the mass content of the third component, i.e., the metal additive, is 0-9wt%, preferably 0.8-5wt%, 0.8-9wt%, 0.9-9wt%, 1-9wt%, 1-8wt%, 2-8wt%, 2-9wt%, 2.5-7.5wt%, 5-7.5wt% or 2-8.5wt%, relative to the total mass of the nickel-based catalyst.

[0050] In a preferred embodiment, the nickel-based catalyst contains the first component, the second component and the third component.

[0051] In a preferred embodiment, the specific surface area of ​​the nickel-based catalyst is greater than 40 m 2 / g (preferably greater than 50m 2 / g), the pore volume is 0.4mL / g or more (preferably 0.5mL / g or more), and the pore diameter is 2-50nm (preferably 5-10nm).

[0052] In a preferred embodiment, the specific surface area of ​​the nickel-based catalyst is 50-100 m 2 / g, for example 50-90m 2 / g, or 50-80m 2 / g, the pore volume is 0.4-1.0 mL / g, for example, 0.4-0.8 mL / g, or 0.5-0.8 mL / g, and the pore diameter is 2-40 nm, for example, 5-40 nm, 5-20 nm, or 5-10 nm.

[0053] In a preferred embodiment, the nickel-based catalyst is in cyclohexane, and the concentration of the nickel-based catalyst in the cyclohexane is 5-10 wt %, such as 5-8 wt %, or 5-6 wt %. In a preferred exemplary embodiment, the element weight percentage composition of the nickel-based catalyst is selected from one of the following:

[0054] Ni:Al:Ti=89.6%:6.0%:4.4%;

[0055] Ni:Si:Cr=88.9%:6.7%:4.4%;

[0056] Ni:Al:Mn=89.6%:6.2%:4.2%;

[0057] Ni:Al:Fe=90.9%:6.7%:2.4%;

[0058] Ni:Al:Co=93.7%:5.5%:0.8%;

[0059] Ni:Al:Mo=88.5%:6.9%:4.6%;

[0060] Ni:Al:La=92.0%:6.2%:1.8%;

[0061] Ni:Al:Ce=89.2%:6.6%:4.2%;

[0062] Ni:Al=93.8%:6.2%;

[0063] Ni:Si=92.5%:7.5%;

[0064] Ni:Al:Si=81.7%:7.3%:11.0%;

[0065] Ni:Al:Mo:Ce=89.2%:6.1%:3.9%:0.8%.

[0066] In the present invention, the term "unsaturated hydrocarbon polymer" refers to a polymer compound formed by polymerization of unsaturated hydrocarbons (hydrocarbon compounds containing carbon-carbon double or triple bonds), wherein the polymer compound contains one or more carbon-carbon double bonds. In a preferred embodiment, the unsaturated hydrocarbon polymer is selected from one or more of the following groups: styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), polybutadiene (PBD), nitrile butadiene rubber (NBR), and isoprene rubber (IR).

[0067] In some embodiments, the present invention provides a method for preparing the above-mentioned nickel-based catalyst, wherein the method comprises the following steps:

[0068] (1) melting a first component, a second component, and an optional third component to form an alloy, wherein the first component is Ni, the second component is selected from one or more of Al and Si, and the third component is one or more metal additives selected from Mo, Fe, Cr, Co, Ti, Mn, La, and Ce;

[0069] (2) mechanically crushing and grinding the alloy into particles to obtain a precursor alloy;

[0070] (3) mixing the precursor alloy with a NaOH aqueous solution to perform a leaching reaction to obtain a porous nickel-based catalyst;

[0071] (4) The porous nickel-based catalyst is repeatedly washed with deionized water until it becomes neutral, and then washed with anhydrous ethanol to obtain the nickel-based catalyst.

[0072] In a preferred embodiment, in step (1), the smelting is carried out in a furnace at 1500-1800°C.

[0073] In a preferred embodiment, in step (1), the second component is Al; preferably, the mass ratio of Ni and Al is Ni:Al=(45-55):(45-55), for example, Ni:Al=45:55, Ni:Al=47:53, Ni:Al=48:52, Ni:Al=49:51, Ni:Al=50:50, Ni:Al=51:49, Ni:Al=52:48.

[0074] In a preferred embodiment, in step (1), the second component is Si; preferably, the mass ratio of Ni and Si is Ni:Si=(45-55):(45-55), for example, Ni:Si=45:55, Ni:Si=47:53, Ni:Si=48:52, Ni:Si=49:51, Ni:Si=50:50, Ni:Si=51:49, Ni:Si=52:48.

[0075] In a preferred embodiment, in step (1), the second component is Al and Si; preferably, the mass ratio of Ni, Al and Si is Ni:Al:Si=(40-60):(20-45):(10-30), for example, Ni:Al:Si=45:45:10.

[0076] In a preferred embodiment, in step (1), the weight percentage of the third component, i.e., the metal additive, relative to the Ni is 0-10wt%, such as 1-10wt%, 2-9wt%, 2-8wt%, 2-7.5wt%, or 2-6wt%.

[0077] In a preferred embodiment, in step (3), the particle size of the porous nickel-based catalyst is 60-300 mesh.

[0078] In a preferred embodiment, in step (3), the concentration of the NaOH aqueous solution is 15-35 wt%, such as 15-30 wt%, 15-25 wt%, or 15-20 wt%.

[0079] In a preferred embodiment, in step (3), the mass ratio of the precursor alloy to the NaOH in the NaOH aqueous solution is 1:(0.5-2), preferably 1:(1.0-1.5), and more preferably 1:(1.2-1.4).

[0080] In a preferred embodiment, in step (3), the precursor alloy is added to the NaOH aqueous solution in batches in small amounts and multiple times to perform the mixing; preferably, the addition time is 0.5-1.5 h, such as 0.5-1 h, or 1-1.5 h.

[0081] In a preferred embodiment, in step (3), the reaction temperature of the leaching reaction is 60-80°C, such as 60-70°C, or 70-80°C.

[0082] In a preferred embodiment, in step (3), the reaction time of the leaching reaction is 0.5-2 h, such as 0.5-1.5 h, 0.5-1 h, or 1-1.5 h.

[0083] In a preferred embodiment, in step (3), after the leaching reaction, the upper layer of alkali solution is removed to obtain the porous nickel-based catalyst.

[0084] In the present invention, in step (4), "repeatedly washing the porous nickel-based catalyst with deionized water until it becomes neutral" means performing multiple washing operations until the washing liquid obtained after the last washing of the catalyst is neutral.

[0085] In a preferred embodiment, in step (4), the obtained nickel-based catalyst is stored in anhydrous ethanol for future use; preferably, the nickel-based catalyst is dried before use.

[0086] In some embodiments, in step (4), the specific surface area of ​​the nickel-based catalyst modified with the metal promoter is greater than 40 m 2 / g (preferably greater than 50m 2 / g), the pore volume is 0.4mL / g or more (preferably 0.5mL / g), and the pore diameter is 2-50nm (preferably 5-10nm).

[0087] In a preferred embodiment, the specific surface area of ​​the nickel-based catalyst is 50-100 m 2 / g, for example 50-90m 2 / g, or 50-80m 2 / g, the pore volume is 0.4-1.0 mL / g, for example, 0.4-0.8 mL / g, or 0.5-0.8 mL / g, and the pore diameter is 2-40 nm, for example, 5-40 nm, 5-20 nm, or 5-10 nm.

[0088] In some embodiments, the present invention provides the use of the above-mentioned nickel-based catalyst for catalytic hydrogenation of unsaturated hydrocarbon polymers. Preferably, the use is for catalytic hydrogenation of unsaturated hydrocarbon polymers with a degree of olefin hydrogenation of more than 98% and a degree of aromatic hydrogenation of more than 60%.

[0089] In a preferred embodiment, the unsaturated hydrocarbon polymer is selected from one or more of the group consisting of styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), polybutadiene (PBD), nitrile rubber (NBR), and isoprene rubber (IR); more preferably, the unsaturated hydrocarbon polymer is styrene-butadiene-styrene (SBS).

[0090] In a preferred embodiment, the use is for catalytic hydrogenation of SBS to prepare CBC.

[0091] In a preferred embodiment, the degree of olefin hydrogenation is above 99%.

[0092] In a preferred embodiment, the degree of hydrogenation of the aromatic hydrocarbons is 70% or higher, preferably 80% or higher, more preferably 90% or higher, further preferably 95% or higher, and even more preferably 99% or higher.

[0093] In some embodiments, the present invention provides a method for catalytically hydrogenating unsaturated hydrocarbon polymers using the above nickel-based catalyst. Preferably, the method is a method for catalytically hydrogenating SBS using the above nickel-based catalyst.

[0094] In a preferred embodiment, the method comprises: placing the above-mentioned nickel-based catalyst in a reactor, introducing an unsaturated hydrocarbon polymer (preferably an SBS raw material) and hydrogen into the reactor to contact the catalyst, so as to catalytically hydrogenate the unsaturated hydrocarbon polymer (preferably SBS) by the catalyst.

[0095] In a preferred embodiment, the method is a method of catalytically hydrogenating SBS to convert it into a polycyclic block copolymer CBC.

[0096] In a preferred embodiment, the unsaturated hydrocarbon polymer (preferably SBS) is in cyclohexane, and the concentration of the unsaturated hydrocarbon polymer (preferably SBS) in the cyclohexane is 5-15 wt%, such as 5-10 wt%, or 10-15 wt%.

[0097] In a preferred embodiment, the nickel-based catalyst is in cyclohexane, and the concentration of the nickel-based catalyst in the cyclohexane is 5-10 wt%, such as 5-8 wt%, or 5-6 wt%.

[0098] In a preferred embodiment, the reaction conditions of the hydrogenation are: reaction pressure 4-6 MPa, reaction temperature 150-170°C, hydrogen flow rate 1900-2100 mL / min, and reaction time 45-50 h, for example, reaction pressure 5-6 MPa, reaction temperature 160-170°C, hydrogen flow rate 2000-2100 mL / min, and reaction time 48-50 h.

[0099] In a preferred embodiment, the hydrogenated product is a polycyclic block copolymer (CBC).

[0100] The present invention is not limited to the preferred embodiments and applications described above, and those skilled in the art may modify these embodiments and applications without departing from the purpose of the present invention.

[0101] Example

[0102] The following examples are used to illustrate the present invention in more detail, but the present invention is not limited thereto. Unless otherwise stated, the reagents, materials, and apparatus used in the following examples are all commercially available and conventional in the art. The SBS (styrene-butadiene-styrene block copolymer) used in the examples has a butadiene weight percentage of approximately 53% and a styrene weight percentage of approximately 47%.

[0103] In the following examples, the atomic ratio of the catalyst was measured by ICP (Inductively Coupled Plasma, ICP).

[0104] Example 1

[0105] Preparation of catalyst:

[0106] 104g nickel, 96g aluminum, and 5.2g titanium were weighed and smelted in a furnace at 1700°C to form an alloy. After the alloy was fully cooled naturally, it was mechanically crushed and ground into particles to obtain a precursor alloy.

[0107] 70g of sodium hydroxide and 130g of deionized water were placed in a beaker and prepared into a 35wt% sodium hydroxide solution under constant stirring. 50g of the above-mentioned precursor alloy was weighed and added to the above-mentioned sodium hydroxide solution in small amounts and multiple times. The feeding time was about 0.5h. After leaching (i.e., alkali solution activation treatment) at a constant temperature of 80°C for 2h, the upper layer of alkali solution was removed to obtain a porous nickel-based catalyst with a particle size of 60-300 mesh.

[0108] After alkali activation treatment, the porous nickel-based catalyst was washed several times with deionized water until the washing liquid was neutral, then washed with ethanol, and dried to obtain a sample catalyst. The mass composition ratio of the sample catalyst was determined by ICP test to be: Ni:Al:Ti=89.6%:6.0%:4.4%, which was designated as catalyst C-1. The specific surface area of ​​the catalyst was 55 m 2 / g, pore volume is 0.5mL / g, and pore diameter is 9.3nm.

[0109] Reaction test:

[0110] The catalyst hydrogenation activity was evaluated. 60 g of Catalyst C-1 was weighed and mixed evenly with 1200 g of a 5 wt% SBS cyclohexane solution. The mixture was then placed in a stainless steel reactor. The air in the reactor was first replaced with an inert gas (N2), and then hydrogen was introduced into the reactor for reaction. The reaction pressure was 5 MPa, the reaction temperature was 160°C, the hydrogen flow rate was 2000 mL / min, and the reaction time was 48 h. The reaction results are listed in Table 1.

[0111] Example 2

[0112] Preparation of catalyst:

[0113] 102g of nickel, 98g of silicon, and 5.1g of chromium were weighed and smelted in a furnace at a high temperature of 1600°C to form an alloy. After the alloy was fully cooled naturally, it was mechanically crushed and ground into particles to obtain a precursor alloy.

[0114] 78g of sodium hydroxide and 182g of deionized water were placed in a beaker and prepared into a 30wt% sodium hydroxide solution under constant stirring. 60g of the above-mentioned precursor alloy was weighed and added to the above-mentioned sodium hydroxide solution in small amounts and multiple times. The feeding time was about 1.0h. After leaching (i.e., alkali solution activation treatment) at a constant temperature of 80°C for 1.5h, the upper layer of alkali solution was removed to obtain a porous nickel-based catalyst with a particle size of 60-300 mesh.

[0115] After alkali activation treatment, the porous nickel-based catalyst was washed several times with deionized water until the washing liquid was neutral, then washed with ethanol, and dried to obtain a sample catalyst. The mass composition ratio of the sample catalyst was as follows: Ni:Si:Cr=88.9%:6.7%:4.4% by ICP test, and was designated as catalyst C-2. The specific surface area of ​​the catalyst was 58m 2 / g, pore volume is 0.5mL / g, and pore diameter is 8.7nm.

[0116] Reaction test:

[0117] 60 g of catalyst C-2 was weighed and mixed evenly with 1200 g of a 10 wt% SBS cyclohexane solution. The mixture was then placed in a stainless steel reactor. The air in the reactor was first replaced with an inert gas (N2), and then hydrogen was introduced into the reactor for reaction. The reaction pressure was 5 MPa, the reaction temperature was 160°C, the hydrogen flow rate was 2000 mL / min, and the reaction time was 48 h. The reaction results are listed in Table 1.

[0118] Example 3

[0119] Preparation of catalyst:

[0120] 100g of nickel, 100g of aluminum, and 5g of manganese were weighed and smelted in a furnace at a high temperature of 1500°C to form an alloy. After the alloy was fully cooled naturally, it was mechanically crushed and ground into particles to obtain a precursor alloy.

[0121] 70g of sodium hydroxide and 210g of deionized water were placed in a beaker and prepared into a 25wt% sodium hydroxide solution under constant stirring. 50g of the above-mentioned precursor alloy was weighed and added to the above-mentioned sodium hydroxide solution in small amounts and multiple times. The feeding time was about 1.5h. After leaching (i.e., alkali solution activation treatment) at a constant temperature of 70°C for 1h, the upper layer of alkali solution was removed to obtain a porous nickel-based catalyst with a particle size of 60-300 mesh.

[0122] After alkali activation treatment, the porous nickel-based catalyst was washed several times with deionized water until the washing liquid was neutral, then washed with ethanol, and dried to obtain a sample catalyst. The mass composition ratio of the sample catalyst was as follows: Ni:Al:Mn=89.6%:6.2%:4.2% by ICP test, and was designated as catalyst C-3. The specific surface area of ​​the catalyst was 61m 2 / g, pore volume is 0.6mL / g, and pore diameter is 8.7nm.

[0123] Reaction test:

[0124] 60 g of catalyst C-3 was weighed and mixed evenly with 1200 g of a 15 wt% SBS cyclohexane solution. The mixture was then placed in a stainless steel reactor. The air in the reactor was first replaced with an inert gas (N2), and then hydrogen was introduced into the reactor for reaction. The reaction pressure was 5 MPa, the reaction temperature was 160°C, the hydrogen flow rate was 2000 mL / min, and the reaction time was 48 h. The reaction results are listed in Table 1.

[0125] Example 4

[0126] Preparation of catalyst:

[0127] 98g of nickel, 102g of aluminum, and 2.45g of iron were weighed and smelted in a furnace at a high temperature of 1500°C to form an alloy. After the alloy was fully cooled naturally, it was mechanically crushed and ground into particles to obtain a precursor alloy.

[0128] 70g of sodium hydroxide and 280g of deionized water were placed in a beaker and prepared into a 20wt% sodium hydroxide solution under constant stirring. 50g of the above-mentioned precursor alloy was weighed and added to the above-mentioned sodium hydroxide solution in small amounts and multiple times. The feeding time was about 1h. After leaching (i.e., alkali solution activation treatment) at a constant temperature of 60°C for 0.5h, the upper layer of alkali solution was removed to obtain a porous nickel-based catalyst with a particle size of 60-300 mesh.

[0129] After alkali activation treatment, the porous nickel-based catalyst was washed several times with deionized water until the washing liquid was neutral, then washed with ethanol, and dried to obtain a sample catalyst. The mass composition ratio of the sample catalyst was determined by ICP test to be: Ni:Al:Fe=90.9%:6.7%:2.4%, which was designated as catalyst C-4. The specific surface area of ​​the catalyst was 64m 2 / g, pore volume is 0.6mL / g, and pore diameter is 8.3nm.

[0130] Reaction test:

[0131] 60 g of catalyst C-4 was weighed and mixed evenly with 1200 g of a 5 wt% SBS cyclohexane solution. The mixture was then placed in a stainless steel reactor. The air in the reactor was first replaced with an inert gas (N2), and then hydrogen was introduced into the reactor for reaction. The reaction pressure was 5 MPa, the reaction temperature was 160°C, the hydrogen flow rate was 2000 mL / min, and the reaction time was 48 h. The reaction results are listed in Table 1.

[0132] Example 5

[0133] Preparation of catalyst:

[0134] 96g of nickel, 104g of aluminum, and 0.96g of cobalt were weighed and smelted in a furnace at a high temperature of 1600°C to form an alloy. After the alloy was fully quenched and cooled, it was mechanically crushed and ground into particles to obtain a precursor alloy.

[0135] 60g of sodium hydroxide and 340g of deionized water were placed in a beaker and prepared into a 15wt% sodium hydroxide solution under constant stirring. 50g of the above-mentioned precursor alloy was weighed and added to the above-mentioned sodium hydroxide solution in small amounts and multiple times. The feeding time was about 1h. After leaching (i.e., alkali solution activation treatment) at a constant temperature of 70°C for 1h, the upper layer of alkali solution was removed to obtain a porous nickel-based catalyst with a particle size of 60-300 mesh.

[0136] After alkali activation treatment, the porous nickel-based catalyst was washed several times with deionized water until the washing liquid was neutral, then washed with ethanol, and dried to obtain a sample catalyst. The mass composition ratio of the sample catalyst was determined by ICP test to be: Ni:Al:Co=93.7%:5.5%:0.8%, which was designated as catalyst C-5. The specific surface area of ​​the catalyst was 66 m 2 / g, pore volume is 0.7mL / g, and pore diameter is 8.4nm.

[0137] Reaction test:

[0138] 60 g of catalyst C-5 was weighed and mixed evenly with 1200 g of a 5 wt% SBS cyclohexane solution. The mixture was then placed in a stainless steel reactor. The air in the reactor was first replaced with an inert gas (N2), and then hydrogen was introduced into the reactor for reaction. The reaction pressure was 5 MPa, the reaction temperature was 160°C, the hydrogen flow rate was 2000 mL / min, and the reaction time was 48 h. The reaction results are listed in Table 1.

[0139] Example 6

[0140] Preparation of catalyst:

[0141] 94g of nickel, 106g of aluminum, and 4.7g of molybdenum were weighed and smelted in a furnace at a high temperature of 1800°C to form an alloy. After the alloy was fully quenched and cooled, it was mechanically crushed and ground into particles to obtain a precursor alloy.

[0142] 70g of sodium hydroxide and 210g of deionized water were placed in a beaker and prepared into a 25wt% sodium hydroxide solution under constant stirring. 50g of the above-mentioned precursor alloy was weighed and added to the above-mentioned sodium hydroxide solution in small amounts and multiple times. The feeding time was about 1h. After leaching (i.e., alkali solution activation treatment) at a constant temperature of 80°C for 1h, the upper layer of alkali solution was removed to obtain a porous nickel-based catalyst with a particle size of 60-300 mesh.

[0143] After alkali activation treatment, the porous nickel-based catalyst was washed several times with deionized water until the washing liquid was neutral, then washed with ethanol, and dried to obtain a sample catalyst. The mass composition ratio of the sample catalyst was determined by ICP test to be: Ni:Al:Mo=88.5%:6.9%:4.6%, which was designated as catalyst C-6. The specific surface area of ​​the catalyst was 70 m 2 / g, the pore volume is 0.8mL / g, and the pore diameter is 8.6nm.

[0144] Reaction test:

[0145] 60 g of catalyst C-6 was weighed and mixed evenly with 1200 g of a 10 wt% SBS cyclohexane solution. The mixture was then placed in a stainless steel reactor. The air in the reactor was first replaced with an inert gas (N2), and then hydrogen was introduced into the reactor for reaction. The reaction pressure was 5 MPa, the reaction temperature was 160°C, the hydrogen flow rate was 2000 mL / min, and the reaction time was 48 h. The reaction results are listed in Table 1.

[0146] Example 7

[0147] Preparation of catalyst:

[0148] 92g of nickel, 108g of aluminum, and 1.84g of lanthanum were weighed and smelted in a furnace at a high temperature of 1500°C to form an alloy. After the alloy was fully quenched and cooled, it was mechanically crushed and ground into particles to obtain a precursor alloy.

[0149] 60g of sodium hydroxide and 180g of deionized water were placed in a beaker and prepared into a 25wt% sodium hydroxide solution under constant stirring. 50g of the above-mentioned precursor alloy was weighed and added to the above-mentioned sodium hydroxide solution in small amounts and multiple times. The feeding time was about 1.5h. After leaching (i.e., alkali solution activation treatment) at a constant temperature of 80°C for 1h, the upper layer of alkali solution was removed to obtain a porous nickel-based catalyst with a particle size of 60-300 mesh.

[0150] After alkali activation treatment, the porous nickel-based catalyst was washed several times with deionized water until the washing liquid was neutral, then washed with ethanol, and dried to obtain a sample catalyst. The mass composition ratio of the sample catalyst was determined by ICP test to be: Ni:Al:La=92.0%:6.2%:1.8%, which was designated as catalyst C-7. The specific surface area of ​​the catalyst was 74 m 2 / g, pore volume is 0.7mL / g, and pore diameter is 8.7nm.

[0151] Reaction test:

[0152] 60 g of catalyst C-7 was weighed and mixed evenly with 1200 g of a 5 wt% SBS cyclohexane solution. The mixture was then placed in a stainless steel reactor. The air in the reactor was first replaced with an inert gas (N2), and then hydrogen was introduced into the reactor for reaction. The reaction pressure was 5 MPa, the reaction temperature was 160°C, the hydrogen flow rate was 2000 mL / min, and the reaction time was 48 h. The reaction results are listed in Table 1.

[0153] Example 8

[0154] Preparation of catalyst:

[0155] 90g of nickel, 110g of aluminum, and 4.5g of cerium were weighed and smelted in a furnace at a high temperature of 1500°C to form an alloy. After the alloy was fully quenched and cooled, it was mechanically crushed and ground into particles to obtain a precursor alloy.

[0156] 70g of sodium hydroxide and 210g of deionized water were placed in a beaker and prepared into a 25wt% sodium hydroxide solution under constant stirring. 50g of the above-mentioned precursor alloy was weighed and added to the above-mentioned sodium hydroxide solution in small amounts and multiple times. The feeding time was about 1h. After leaching (i.e., alkali solution activation treatment) at a constant temperature of 80°C for 1h, the upper layer of alkali solution was removed to obtain a porous nickel-based catalyst with a particle size of 60-300 mesh.

[0157] After alkali activation treatment, the porous nickel-based catalyst was washed several times with deionized water until the washing liquid was neutral, then washed with ethanol, and dried to obtain a sample catalyst. The mass composition ratio of the sample catalyst was as follows: Ni:Al:Ce=89.2%:6.6%:4.2% by ICP test, and was designated as catalyst C-8. The specific surface area of ​​the catalyst was 78m 2 / g, pore volume is 0.8mL / g, and pore diameter is 6.7nm.

[0158] Reaction test:

[0159] 60 g of catalyst C-8 was weighed and mixed evenly with 1200 g of a 5 wt% SBS cyclohexane solution. The mixture was then placed in a stainless steel reactor. The air in the reactor was first replaced with an inert gas (N2), and then hydrogen was introduced into the reactor for reaction. The reaction pressure was 5 MPa, the reaction temperature was 160°C, the hydrogen flow rate was 2000 mL / min, and the reaction time was 48 h. The reaction results are listed in Table 1.

[0160] Example 9

[0161] Preparation of catalyst:

[0162] 104g of nickel and 96g of aluminum were weighed and smelted in a furnace at a high temperature of 1500°C to form an alloy. After the alloy was fully cooled naturally, it was mechanically crushed and ground into particles to obtain a precursor alloy.

[0163] 60g of sodium hydroxide and 240g of deionized water were placed in a beaker and prepared into a 20wt% sodium hydroxide solution under constant stirring. 50g of the above-mentioned precursor alloy was weighed and added to the above-mentioned sodium hydroxide solution in small amounts and multiple times. The feeding time was about 1h. After leaching (i.e., alkali solution activation treatment) at a constant temperature of 80°C for 1h, the upper layer of alkali solution was removed to obtain a porous nickel-based catalyst with a particle size of 60-300 mesh.

[0164] After the alkali activation treatment, the porous nickel-based catalyst was washed several times with deionized water until the washing liquid was neutral, then washed with ethanol, and dried to obtain a sample catalyst. The mass composition ratio of the sample catalyst was determined by ICP test to be Ni:Al=93.8%:6.2%, which was designated as catalyst C-9. The specific surface area of ​​the catalyst was 51m 2 / g, pore volume is 0.5mL / g, and pore diameter is 9.2nm.

[0165] Reaction test:

[0166] 60 g of catalyst C-9 was weighed and mixed evenly with 1200 g of a 5 wt% SBS cyclohexane solution. The mixture was then placed in a stainless steel reactor. The air in the reactor was first replaced with an inert gas (N2), and then hydrogen was introduced into the reactor for reaction. The reaction pressure was 5 MPa, the reaction temperature was 160°C, the hydrogen flow rate was 2000 mL / min, and the reaction time was 48 h. The reaction results are listed in Table 1.

[0167] Example 10

[0168] Preparation of catalyst:

[0169] 104 g of nickel and 96 g of silicon were weighed and smelted in a furnace at 1500° C. to form an alloy. After the alloy was fully cooled naturally, it was mechanically crushed and ground into particles to obtain a precursor alloy.

[0170] 60g of sodium hydroxide and 240g of deionized water were placed in a beaker and prepared into a 20wt% sodium hydroxide solution under constant stirring. 50g of the above-mentioned precursor alloy was weighed and added to the above-mentioned sodium hydroxide solution in small amounts and multiple times. The feeding time was about 1h. After leaching (i.e., alkali solution activation treatment) at a constant temperature of 80°C for 1h, the upper layer of alkali solution was removed to obtain a porous nickel-based catalyst with a particle size of 60-300 mesh.

[0171] After alkali activation treatment, the porous nickel-based catalyst was washed several times with deionized water until the washing liquid was neutral, then washed with ethanol, and dried to obtain a sample catalyst. The mass composition ratio of the sample catalyst was determined by ICP test to be Ni:Si=92.5%:7.5%, which was designated as catalyst C-10. The specific surface area of ​​the catalyst was 47m 2 / g, pore volume is 0.4mL / g, and pore diameter is 9nm.

[0172] Reaction test:

[0173] 60 g of catalyst C-10 was weighed and mixed evenly with 1200 g of a 5 wt% SBS cyclohexane solution. The mixture was then placed in a stainless steel reactor. The air in the reactor was first replaced with an inert gas (N2), and then hydrogen was introduced into the reactor for reaction. The reaction pressure was 5 MPa, the reaction temperature was 160°C, the hydrogen flow rate was 2000 mL / min, and the reaction time was 48 h. The reaction results are listed in Table 1.

[0174] Example 11

[0175] Preparation of catalyst:

[0176] 90g of nickel, 90g of aluminum, and 20g of silicon were weighed and smelted in a furnace at 1600°C to form an alloy. After the alloy was fully cooled naturally, it was mechanically crushed and ground into particles to obtain a precursor alloy.

[0177] 70g of sodium hydroxide and 210g of deionized water were placed in a beaker and prepared into a 25wt% sodium hydroxide solution under constant stirring. 50g of the above-mentioned precursor alloy was weighed and added to the above-mentioned sodium hydroxide solution in small amounts and multiple times. The feeding time was about 1h. After leaching (i.e., alkali solution activation treatment) at a constant temperature of 80°C for 1h, the upper layer of alkali solution was removed to obtain a porous nickel-based catalyst with a particle size of 60-300 mesh.

[0178] After alkali activation treatment, the porous nickel-based catalyst was washed several times with deionized water until the washing liquid was neutral, then washed with ethanol, and dried to obtain a sample catalyst. The mass composition ratio of the sample catalyst was determined by ICP test to be: Ni:Al:Si=81.7%:7.3%:11.0%, denoted as catalyst C-11. The specific surface area of ​​the catalyst was 56 m 2 / g, pore volume is 0.4mL / g, and pore diameter is 9.7nm.

[0179] Reaction test:

[0180] 60 g of catalyst C-11 was weighed and mixed evenly with 1200 g of a 5 wt% SBS cyclohexane solution. The mixture was then placed in a stainless steel reactor. The air in the reactor was first replaced with an inert gas (N2), and then hydrogen was introduced into the reactor for reaction. The reaction pressure was 5 MPa, the reaction temperature was 160°C, the hydrogen flow rate was 2000 mL / min, and the reaction time was 48 h. The reaction results are listed in Table 1.

[0181] Example 12

[0182] Preparation of catalyst:

[0183] 96g of nickel, 104g of aluminum, 4.8g of molybdenum, and 0.96g of cerium were weighed and smelted in a furnace at a high temperature of 1700°C to form an alloy. After the alloy was fully quenched and cooled, it was mechanically crushed and ground into particles to obtain a precursor alloy.

[0184] 70g of sodium hydroxide and 210g of deionized water were placed in a beaker and prepared into a 25wt% sodium hydroxide solution under constant stirring. 50g of the above-mentioned precursor alloy was weighed and added to the above-mentioned sodium hydroxide solution in small amounts and multiple times. The feeding time was about 1h. After leaching (i.e., alkali solution activation treatment) at a constant temperature of 80°C for 1h, the upper layer of alkali solution was removed to obtain a porous nickel-based catalyst with a particle size of 60-300 mesh.

[0185] After alkali activation treatment, the porous nickel-based catalyst was washed several times with deionized water until the washing liquid was neutral, then washed with ethanol, and dried to obtain a sample catalyst. The mass composition ratio of the sample catalyst was as follows: Ni:Al:Mo:Ce=89.2%:6.1%:3.9%:0.8% by ICP test, and was designated as catalyst C-12. The specific surface area of ​​the catalyst was 68m 2 / g, pore volume is 0.8mL / g, and pore diameter is 7.6nm.

[0186] Reaction test:

[0187] 60 g of catalyst C-12 was weighed and mixed evenly with 1200 g of a 5 wt% SBS cyclohexane solution. The mixture was then placed in a stainless steel reactor. The air in the reactor was first replaced with an inert gas (N2), and then hydrogen was introduced into the reactor for reaction. The reaction pressure was 5 MPa, the reaction temperature was 160°C, the hydrogen flow rate was 2000 mL / min, and the reaction time was 48 h. The reaction results are listed in Table 1.

[0188] Table 1 Hydrogenation performance of catalyst after 48h reaction

[0189] Example Olefin hydrogenation degree Aromatic hydrocarbon hydrogenation degree Example 1 98.3％ 68.4％ Example 2 98.7％ 73.1％ Example 3 99.0％ 76.5％ Example 4 99.2％ 79.7％ Example 5 99.3％ 93.8％ Example 6 99.8％ 99.5％ Example 7 99.5％ 99.2％ Example 8 99.7％ 99.6％ Example 9 98.6％ 65.3％ Example 10 98.4％ 62.6％ Example 11 98.6％ 60.1％ Example 12 99.6％ 99.4％

[0190] Table 1 shows the performance test results after 48 hours of hydrogenation reaction between the Ni-based catalysts prepared by Examples 1 to 12 and SBS. As shown in Table 1, the degree of olefin hydrogenation of the Ni-based catalysts of the present invention can reach 98% or more, and even 99% or more, indicating that the prepared Ni-based catalysts have excellent activity for the hydrogenation of olefins. At the same time, the degree of aromatic hydrocarbon hydrogenation of the Ni-based catalysts of the present invention can reach 60% or more, preferably 70% or more, more preferably 80% or more, further preferably 90% or more, even more preferably 95% or more, and even 99% or more, indicating that the prepared Ni-based catalysts have high activity for the hydrogenation of aromatic hydrocarbons.

[0191] It can be seen that in the study of hydrogenation reaction of butadiene and styrene block copolymers, the heterogeneous Ni-based catalyst of the present invention showed excellent hydrogenation activity. By adding nickel-based catalysts prepared by different metal additives, it is possible to carry out efficient partial hydrogenation and deep hydrogenation of unsaturated hydrocarbons in polymers. As shown in Table 1, these catalysts demonstrated excellent hydrogenation performance in the experiment. In summary, the catalyst of the present invention has broad application prospects in the field of polymer hydrogenation and provides strong technical support for the high performance and functionalization of polymers.

Claims

1. A nickel-based catalyst for the catalytic hydrogenation of unsaturated hydrocarbon polymers, wherein: The nickel-based catalyst contains: A first component, wherein the first component is Ni; A second component selected from one or more of Al and Si; and An optional third component, wherein the third component is one or more metal additives selected from the group consisting of Mo, Fe, Cr, Co, Ti, Mn, La and Ce; Preferably, relative to the total mass of the nickel-based catalyst, the mass content of the first component Ni is 80-97 wt%, and the mass content of the third component is 0-9 wt%.

2. The nickel-based catalyst according to claim 1, wherein The second component satisfies one of the following: The second component is Al, and the mass content of Al is preferably 3-20 wt% relative to the total mass of the nickel-based catalyst; or The second component is Si, and the mass content of Si is preferably 3-25 wt% relative to the total mass of the nickel-based catalyst; or The second component is Al and Si. Relative to the total mass of the nickel-based catalyst, the mass content of Al is preferably 3-15 wt%, and the mass content of Si is preferably 10-25 wt%.

3. The nickel-based catalyst according to claim 1 or 2, wherein The specific surface area of ​​the nickel-based catalyst is greater than 40m 2 / g; pore volume is above 0.4mL / g; pore diameter is 2-50nm.

4. The nickel-based catalyst according to any one of claims 1 to 3, wherein The nickel-based catalyst has an element weight percentage composition selected from the following: Ni:Al:Ti=89.6%:6.0%:4.4%; Ni:Si:Cr=88.9%:6.7%:4.4%; Ni:Al:Mn=89.6%:6.2%:4.2%; Ni:Al:Fe=90.9%:6.7%:2.4%; Ni:Al:Co=93.7%:5.5%:0.8%; Ni:Al:Mo=88.5%:6.9%:4.6%; Ni:Al:La=92.0%:6.2%:1.8%; Ni:Al:Ce=89.2%:6.6%:4.2%; Ni:Al=93.8%:6.2%; Ni:Si=92.5%:7.5%; Ni:Al:Si=81.7%:7.3%:11.0%; Ni:Al:Mo:Ce=89.2%:6.1%:3.9%:0.8%.

5. A method for preparing a nickel-based catalyst according to any one of claims 1 to 4, wherein: The preparation method comprises the following steps: (1) melting a first component, a second component, and an optional third component to form an alloy, wherein the first component is Ni, the second component is selected from one or more of Al and Si, and the third component is one or more metal additives selected from Mo, Fe, Cr, Co, Ti, Mn, La, and Ce; (2) mechanically crushing and grinding the alloy into particles to obtain a precursor alloy; (3) mixing the precursor alloy with a NaOH aqueous solution to perform a leaching reaction to obtain a porous nickel-based catalyst; (4) The porous nickel-based catalyst is repeatedly washed with deionized water until it becomes neutral, and then washed with anhydrous ethanol to obtain the nickel-based catalyst.

6. The preparation method according to claim 5, wherein in step (1), the smelting is carried out in a furnace at 1500-1800°C; Preferably, the weight percentage of the third component relative to the Ni is 0-10wt%; Preferably, the second component satisfies one of the following: The second component is Al, and the mass ratio of Ni to Al is preferably Ni:Al=(45-55):(45-55); or The second component is Si, and the mass ratio of Ni to Si is preferably Ni:Si=(45-55):(45-55); or The second component is Al and Si, and the mass ratio of Ni, Al and Si is preferably Ni:Al:Si=(40-60):(20-45):(10-30).

7. The preparation method according to claim 5 or 6, wherein in step (3), the particle size of the porous nickel-based catalyst is 60-300 mesh; Preferably, the concentration of the NaOH aqueous solution is 15-35 wt%; Preferably, the mass ratio of the precursor alloy to the NaOH in the NaOH aqueous solution is 1:(0.5-2); Preferably, the precursor alloy is added to the NaOH aqueous solution in batches to perform the mixing; Preferably, the reaction temperature of the leaching reaction is 60-80°C; Preferably, the reaction time of the leaching reaction is 0.5-2h; Preferably, after the leaching reaction, the upper layer of alkali solution is removed to obtain the porous nickel-based catalyst.

8. The preparation method according to any one of claims 5 to 7, wherein in step (4), the obtained nickel-based catalyst is stored in anhydrous ethanol for later use; Preferably, the nickel-based catalyst is dried before use; Preferably, the specific surface area of ​​the nickel-based catalyst is greater than 40 m 2 / g; pore volume is above 0.4mL / g; pore diameter is 2-50nm.

9. Use of the nickel-based catalyst according to any one of claims 1 to 4 or the nickel-based catalyst obtained by the preparation method according to any one of claims 5 to 8 for catalytic hydrogenation of unsaturated hydrocarbon polymers; Preferably, the use is for catalytic hydrogenation of unsaturated hydrocarbon polymers with a degree of olefin hydrogenation of more than 98% and a degree of aromatic hydrocarbon hydrogenation of more than 60%; Preferably, the unsaturated hydrocarbon polymer is selected from one or more of the group consisting of styrene-butadiene-styrene SBS, styrene-isoprene-styrene SIS, polybutadiene PBD, nitrile butadiene rubber NBR, and isoprene rubber IR.

10. A method for catalytic hydrogenation of an unsaturated hydrocarbon polymer using the nickel-based catalyst according to any one of claims 1 to 4 or the nickel-based catalyst obtained by the preparation method according to any one of claims 5 to 8; Preferably, the method comprises: placing the nickel-based catalyst in a reactor, and introducing the unsaturated hydrocarbon polymer and hydrogen into the reactor to contact the nickel-based catalyst, so as to catalytically hydrogenate the unsaturated hydrocarbon polymer by the nickel-based catalyst; Preferably, the unsaturated hydrocarbon polymer is selected from one or more of the group consisting of styrene-butadiene-styrene SBS, styrene-isoprene-styrene SIS, polybutadiene PBD, nitrile butadiene rubber NBR, isoprene rubber IR; Preferably, the unsaturated hydrocarbon polymer and the nickel-based catalyst are in cyclohexane, the concentration of the unsaturated hydrocarbon polymer in the cyclohexane is 5-15 wt %, and the concentration of the nickel-based catalyst in the cyclohexane is 5-10 wt %; Preferably, the reaction conditions of the hydrogenation are: reaction pressure 4-6 MPa, reaction temperature 150-170° C., hydrogen flow rate 1900-2100 mL / min, and reaction time 45-50 h; Preferably, the method is a method of catalytically hydrogenating styrene-butadiene-styrene (SBS) to convert it into a polycyclic block copolymer (CBC).

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