Supported Ni-based heterogeneous catalyst, its preparation method and application

Abstract

The present invention discloses a supported Ni-based heterogeneous catalyst, wherein the support of the catalyst is SiO2, and the active component is a nickel element wrapped by a nitrogen-doped carbon material, and the nickel element wrapped by the nitrogen-doped carbon material is uniformly dispersed on the support SiO2. The present invention also discloses a preparation method and application of the supported Ni-based heterogeneous catalyst. The present invention adopts a Ni-MOF mesoporous nanostructure catalyst prepared by a simple process, which is low in cost. It can achieve high catalytic activity and high selectivity under mild conditions to achieve selective hydrogenation of quinoline compounds to synthesize py-THQs, overcoming the problems of the heterogeneous catalyst required for the selective hydrogenation reaction of quinoline compounds: high cost, complex preparation method, harsh reaction conditions, poor stability and selectivity. The catalyst supported by the nitrogen-doped carbon material makes the catalytic structure stable, the active components of the catalyst are not easy to be leached and poisoned, and it is convenient for long-term use.

Description

Technical Field

[0001] The present invention belongs to the technical field of chemical engineering, and particularly relates to a supported Ni-based heterogeneous catalyst for selective hydrogenation of quinoline compounds, a preparation method thereof, and an application thereof. Background Art

[0002] The 1,2,3,4-tetrahydroquinoline (py-THQ) system is a very common structural motif. The py-THQ unit is used as a bioactive structural unit and a key intermediate in the production of pharmaceuticals, alkaloids, pesticides, and other fine chemicals, and its synthesis has received increasing attention. Direct hydrogenation of readily available quinoline is a simple and promising method to obtain py-THQ and its derivatives in a simple and highly atom-efficient manner. The selective hydrogenation of quinoline compounds has the following disadvantages and challenges: (1) The reaction process is slow and the conditions are harsh; (2) There are many intermediates and by-products; (3) The selectivity is poor; (4) It is prone to leaching or poisoning, and the stability and reusability are poor. Therefore, it is urgent to develop a new type of high-performance heterogeneous catalyst with mild reaction conditions, good selectivity, strong stability, and low cost, and it is still a huge challenge.

[0003] People have long been committed to developing high-performance catalysts for the selective hydrogenation of quinoline compounds to prepare py-THQs. Among them, there are many achievements in the field of noble metals (Pd, Pt, Ru, Rh, Ir, and Au), but the high price and limited substrate range also hinder their industrial application. In the field of non-noble metals (Fe, Co, Ni, and Cu), there are many reports on Fe, Co, Cu-based or their alloys. Although they have excellent catalytic activity and selectivity, the reaction conditions are relatively harsh, usually requiring high temperature, high H2 pressure, and long reaction time. In addition, their stability as catalysts also needs to be improved urgently. The research on high-performance Ni-based heterogeneous catalysts for the selective hydrogenation of quinoline compounds to prepare py-THQs is relatively less.

[0004] Literature 1 (J. Mater. Chem. 2012, 19(16): 2295-2297). In the early work of Czaplik and his colleagues, Raney-Ni was used as an efficient reusable catalyst for the selective hydrogenation of 8-hydroxyquinoline, and the yield of the corresponding py-THQ derivative was 88%. The catalyst was easily recovered using an external magnetic stir bar, providing a useful approach for laboratory-scale hydrogenation reactions. However, its yield is not ideal.

[0005] Literature 2 (RSC Adv. 2013, 3(46), 23984−23988). Liu et al. found that compared with Raney-Ni, skeletal Ni (QSNi) prepared by quenching technology showed higher catalytic performance in the selective hydrogenation of quinolone due to its abundant low-coordination sites and defects. However, the stability of this catalyst was poor.

[0006] Literature 3 (Mol. Catal. 2021, 514, 111855). Niu et al. prepared nano-nickel hollow mesoporous silica (Ni@hw-mSiO2) with highly dispersed inner surface by four consecutive steps of depositing nickel, coating silica, calcining, and reducing using carbon spheres as templates. This catalyst had excellent catalytic activity and stability in the process of selective hydrogenation of quinoline to py-THQ. However, there was a sudden drop in conversion after the fifth cycle test.

[0007] Literature 4 (Mol. Catal. 2020, 493, 111094). Yang et al. found that adding DMBS would promote the increase of nickel dispersion and enhance the interaction between metal and support. The prepared Ni / mSiO2-DMBS0.005 had good dispersion and stronger metal-support interaction, so it showed good catalytic activity and stability. However, it did not show an advantage in the selectivity for py-THQ.

[0008] Literature 5 (J. Alloy Compd. 2022, 925, 166703). Zhu et al. first used aqueous solutions of polyacrylamide (PAM) and nickel acetate (NiAc) as precursors and prepared nickel nanoparticles embedded in highly nitrogen-doped carbon nanofibers (Ni@NCNFs) by electrospinning and carbonization. The prepared catalyst could be successfully applied to the selective hydrogenation of quinoline to py-THQ and showed excellent catalytic performance and extremely high selectivity at full conversion. However, the reaction temperature required for its catalysis was relatively high and there was room for improvement.

[0009] Literature 6 (Mol. Catal. 2022, 520, 112166). Wang et al. well-dispersed Fe-Ni and Ni-Cu alloys on MCM-41 zeolite. For the Fe4Ni6Cu5 / MCM-41 catalyst, efficient selective hydrogenation of quinoline was achieved under the synergistic effect of Fe-Ni and Ni-Cu alloys. However, the reaction time required for its catalysis was too long, affecting production.

[0010] The relevant parameters of the catalysts reported in domestic and foreign literature during the catalytic hydrogenation reaction are shown in the following table.

[0011] Summary of the Invention

[0012] The first technical problem to be solved by the present invention is to provide a supported Ni-based heterogeneous catalyst, which has high activity, selectivity and stability under mild conditions when applied to the selective hydrogenation of quinoline compounds.

[0013] The second technical problem to be solved by the present invention is to provide a method for preparing the above catalyst.

[0014] To solve the first technical problem mentioned above, the carrier of the supported Ni-based multiphase catalyst provided by the present invention is SiO2, and the active component is a nickel element wrapped by a nitrogen-doped carbon material, and the nickel element wrapped by the nitrogen-doped carbon material is uniformly dispersed on the carrier SiO2.

[0015] In order to solve the above second technical problem, the preparation scheme designed by the present invention comprises the following steps:

[0016] 1) mixing nickel salt and polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) with a solvent to prepare a solution;

[0017] 2) mixing 2-methylimidazole (2-MelM) (as a curing accelerator), triethylamine (TEA) (for promoting the interaction between Ni2+ and deprotonated 2-MelM) and water to prepare an aqueous solution;

[0018] 3) under heating and stirring conditions, the solutions prepared in step 1) and step 2) are mixed evenly, and then tetraethyl orthosilicate is added dropwise, and stirred for reaction to obtain a green suspension;

[0019] 4) filtering, washing, drying and fully grinding to obtain green powder, which is Ni-MOF / SiO2, i.e., catalyst precursor;

[0020] 5) High temperature calcination and reduction to obtain a black Ni-NC / SiO2-T catalyst.

[0021] Furthermore, the molar ratio of the nickel salt, the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, 2-methylimidazole and triethylamine is 1:0.27-0.405:8-12:8-12.

[0022] Furthermore, in the catalyst, the mass percentage of SiO2 is 7-8%.

[0023] Furthermore, the nickel salt is nickel nitrate hexahydrate.

[0024] Furthermore, the solvent in step 1) includes but is not limited to water and anhydrous ethanol, preferably anhydrous ethanol.

[0025] Furthermore, in the step 3), the heating temperature is 50°C.

[0026] Further, in step 5), the heating program for high-temperature calcination is a heating rate of 5 °C / min, a calcination temperature of 700 - 900 °C, and a calcination time of 2 - 3 h.

[0027] The present invention also provides the application of the above catalyst in the selective hydrogenation of quinoline compounds. This application includes the following steps:

[0028] 1) Mix the catalyst, quinoline compound, and organic solvent;

[0029] 2) Introduce hydrogen at a certain temperature and pressure for selective hydrogenation reaction to produce hydrogenated quinoline compounds.

[0030] Further, the reaction temperature of the selective hydrogenation reaction is 80 - 90 °C, the reaction pressure is 0.1 - 4.0 MPa, and the reaction time is 5 - 7 h.

[0031] Further, the quinoline compound is quinoline, isoquinoline, or functionalized quinoline.

[0032] Still further, the functionalized quinoline refers to one or several of halogen, vinyl, aldehyde group, hydroxyl group, alkyl group, and phenyl group being connected to the benzene ring or pyridine ring of quinoline.

[0033] Further, the organic solvent is one or several of methanol, ethanol, toluene, and tetrahydrofuran.

[0034] Further, the mass ratio of the quinoline compound to the supported catalyst is (3.225 - 5.175):1.

[0035] The Ni-MOF mesoporous nanostructure catalyst prepared by the simple process of the present invention uses a non-noble metal Ni as the raw material and is a heterogeneous catalyst with low cost. Nickel has a small atomic radius, good electronic structure, low surface energy, and moderate chemical inertness. Therefore, nickel has relatively good hydrogen adsorption, catalytic activity, and thermal stability, and can achieve high catalytic activity and high selectivity for the selective hydrogenation of quinoline compounds to synthesize py-THQs under mild conditions, overcoming the problems existing in the heterogeneous catalysts required for the selective hydrogenation reaction of quinoline compounds, such as high cost, complex preparation method, harsh reaction conditions, poor stability and selectivity, etc. The catalyst supported by the nitrogen-doped carbon material makes the catalytic structure stable, and the active components of the catalyst are not easily leached and poisoned, facilitating long-term use. Description of the Drawings

[0036] Figure 1 It is the influence of the calcination temperature on the THQ performance of the Ni-NC / SiO2-T catalyst.

[0037] Figure 2To study the influence of reaction solvents on the THQ performance of the Ni-NC / SiO2-T catalyst.

[0038] Figure 3 To study the influence of reaction temperature on the THQ performance of the Ni-NC / SiO2-T catalyst.

[0039] Figure 4 To study the influence of hydrogen pressure on the THQ performance of the Ni-NC / SiO2-T catalyst.

[0040] Figure 5 To study the influence of reaction time on the THQ performance of the Ni-NC / SiO2-T catalyst.

[0041] Figure 6 To study the influence of the number of uses on the THQ performance of the Ni-NC / SiO2-T catalyst.

[0042] Figure 7 XRD pattern of the Ni-NC / SiO2-T catalyst.

[0043] Figure 8 TEM image (50nm) of the Ni-NC / SiO2-T catalyst.

[0044] Figure 9 TEM image (10nm) of the Ni-NC / SiO2-T2 catalyst. Detailed implementation mode

[0045] The technical solutions of the present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, and are only used to illustrate the present invention and should not be construed as a limitation of the present invention.

[0046] Example 1

[0047] This example illustrates the preparation, catalytic experiment and gas phase detection of the Ni-NC / SiO2-T catalyst.

[0048] (1): Preparation of the catalyst Ni-NC / SiO2-T:

[0049] (a): Take 0.74g Ni(NO3)2·6H2O and 3.92g P123 in beaker A, add 50mL anhydrous ethanol, and stir in an ultrasonic machine until completely dissolved, which is solution A. Take 1.62g 2-MelM and 2.00g triethylamine in beaker B, add 50mL deionized water, and ultrasonicate until dissolved, which is solution B. Quickly mix solutions A and B and stir at 40°C for 30min to fully mix, add 2.912g tetraethyl orthosilicate dropwise, and continue stirring for 24h to form a green suspension. Filter, wash alternately with anhydrous ethanol and deionized water 3 times, dry in an oven at 50°C for 12h, and grind thoroughly to obtain a green powder, which is Ni-MOF / SiO2, i.e., a catalyst precursor.

[0050] (b): Weigh a certain amount of catalyst precursor Ni-MOF / SiO2 and put it into a crucible, place it in a tube furnace for calcination and reduction, the calcination conditions are: heating rate 5℃ / min, calcination temperature 600-1000℃, calcination time 3h, and naturally cool to room temperature to obtain black catalysts Ni-NC / SiO2-600, Ni-NC / SiO2-700, Ni-NC / SiO2-800, Ni-NC / SiO2-900 and Ni-NC / SiO2-1000.

[0051] The Ni-NC / SiO2-(600-1000) catalyst is used for the hydrogenation of quinoline to prepare py-THQ reaction:

[0052] Add 10 mL of methanol as solvent to the reactor, add 40 mg of the catalyst and 1 mmol (0.1174 g) of quinoline, and the mass ratio of catalyst to quinoline is 0.32:1. Assemble the reactor, vent and release hydrogen three times, introduce hydrogen to 2 MPa, stir and react at 70°C and 600 rpm for 3 hours, and stop the reaction. Wait for the reactor to cool to room temperature and discharge the hydrogen. Add ethylbenzene to the product as an internal standard, take a small amount of liquid after filtering the membrane for gas chromatography to analyze the product composition. The experimental results are shown in Figure 1 When the catalyst calcination time was 700°C, the quinoline conversion rate was 32.9% and the py-THQ selectivity was 31.9%; at 800°C, the quinoline conversion rate was 30.4% and the py-THQ selectivity was 29.5%; at 900°C, the quinoline conversion rate was 42.3% and the py-THQ selectivity was 41.7%.

[0053] Example 2

[0054] This example illustrates the effect of hydrogenation reaction organic solvent on the catalytic performance of Ni-NC / SiO2-900 catalyst and gas phase detection.

[0055] Add 10 mL of methanol, ethanol, toluene, n - hexane, tetrahydrofuran, and isopropanol into the autoclave as solvents, add 40 mg of the catalyst described above, and 1 mmol (0.1174 g) of quinoline. The mass ratio of the catalyst to quinoline is 0.32:1. Assemble the autoclave, purge with hydrogen three times, introduce hydrogen to 2 MPa, stir and react at 70 °C and 600 rpm for 3 h, and then stop the reaction. Wait for the autoclave to cool down to room temperature and discharge the hydrogen. Add ethylbenzene as an internal standard to the product, filter through a membrane, and take a small amount of the liquid for gas chromatography detection to analyze its product composition. The experimental results are shown in Figure 2 When the reaction solvent is toluene, the conversion rate of quinoline is 40.6%, and the selectivity of py - THQ is 40.0%; when it is ethanol, the conversion rate of quinoline is 38.0%, and the selectivity of py - THQ is 37.5%; when it is methanol, the conversion rate of quinoline is 42.3%, and the selectivity of py - THQ is 41.7%.

[0056] Example 3

[0057] This example illustrates the catalytic experiment of organic solvents for the Ni - NC / SiO₂ - 900 catalyst in the hydrogenation reaction and gas - phase detection.

[0058] The Ni - NC / SiO₂ - 900 catalyst is used for the reaction of hydrogenating quinoline to prepare py - THQ:

[0059] Add 10 mL of methanol into the autoclave as a solvent, add 40 mg of the catalyst described above, and 1 mmol (0.1174 g) of quinoline. The mass ratio of the catalyst to quinoline is 0.32:1. Assemble the autoclave, purge with hydrogen three times, introduce hydrogen to 3 MPa, stir and react at 60, 70, 80, and 90 °C respectively at 600 rpm for 3 h, and then stop the reaction. Wait for the autoclave to cool down to room temperature and discharge the hydrogen. Add ethylbenzene as an internal standard to the product, filter through a membrane, and take a small amount of the liquid for gas chromatography detection to analyze its product composition. The experimental results are shown in Figure 3 When the reaction temperature is 80 °C, the conversion rate of quinoline is 64.0%, and the selectivity of py - THQ is 63.5%; when it is 90 °C, the conversion rate of quinoline is 100.0%, and the selectivity of py - THQ is 99.1%.

[0060] Example 4

[0061] This example illustrates the influence of hydrogen pressure on the catalytic performance of the Ni - NC / SiO₂ - 900 catalyst in the hydrogenation reaction and gas - phase detection.

[0062] Add 10 mL of methanol as a solvent into the autoclave, add 40 mg of the catalyst described above and 1 mmol (0.1174 g) of quinoline. The mass ratio of the catalyst to quinoline is 0.32:1. Assemble the autoclave, purge and introduce hydrogen three times, and introduce hydrogen to 0.1 MPa, 1 MPa, 2 MPa, 3 MPa, and 4 MPa respectively. Stir and react at 80 °C and 600 rpm for 3 h, and then stop the reaction. Wait for the autoclave to cool down to room temperature and discharge the hydrogen. Add ethylbenzene as an internal standard to the product, filter through a membrane, and take a small amount of the liquid for gas chromatography detection to analyze its product composition. The experimental results are shown in Figure 4 , when the hydrogen pressure is 2 MPa, the conversion rate of quinoline is 43.2%, and the selectivity of py-THQ is 41.7%; when it is 3 MPa, the conversion rate of quinoline is 64.0%, and the selectivity of py-THQ is 63.5%; when it is 4 MPa, the conversion rate of quinoline is 61.1%, and the selectivity of py-THQ is 60.8%.

[0063] Example 5

[0064] This example illustrates the influence of the hydrogenation reaction time on the catalytic performance of the Ni-NC / SiO2-900 catalyst and gas phase detection.

[0065] Add 10 mL of methanol as a solvent into the autoclave, add 40 mg of the catalyst described above and 1 mmol (0.1174 g) of quinoline. The mass ratio of the catalyst to quinoline is 0.32:1. Assemble the autoclave, purge and introduce hydrogen three times, and introduce hydrogen to 3 MPa. Stir and react at 80 °C and 600 rpm for 1, 3, 5, and 7 h respectively, and then stop the reaction. Wait for the autoclave to cool down to room temperature and discharge the hydrogen. Add ethylbenzene as an internal standard to the product, filter through a membrane, and take a small amount of the liquid for gas chromatography detection to analyze its product composition. The experimental results are shown in Figure 5 , when the reaction time is 3 h, the conversion rate of quinoline is 64.0%, and the selectivity of py-THQ is 63.5%; when it is 5 h, the conversion rate of quinoline is 70.8%, and the selectivity of py-THQ is 69.7%; when it is 7 h, the conversion rate of quinoline is 100%, and the selectivity of py-THQ is 98.9%.

[0066] Example 6

[0067] This example illustrates the influence of the number of recycling times of the hydrogenation reaction on the catalytic performance of the Ni-NC / SiO2-900 catalyst and gas phase detection.

[0068] Add 10 mL of methanol as a solvent to the reaction kettle, add 40 mg of the catalyst described above, and 1 mmol (0.1174 g) of quinoline. The mass ratio of the catalyst to quinoline is 0.32:1. Assemble the reaction kettle, purge with hydrogen three times, introduce hydrogen to 3 Mpa, and stir and react at 80 °C and 600 rpm for 7 h respectively, then stop the reaction. Wait for the reaction kettle to cool to room temperature and discharge the hydrogen. Add ethylbenzene as an internal standard to the product, filter through a membrane, and take a small amount of the liquid for gas chromatography detection to analyze its product composition. Recover the catalyst used for the first time with a magnet, wash it, dry it under vacuum, and use it for the next reaction. React a total of 5 times under the above conditions, and measure the product composition each time. The experimental results are shown in Figure 6 , when the catalyst is used for the first time, the conversion rate of quinoline is 100.0%, and the selectivity of py-THQ is 98.9%; when it is used for the fifth time, the conversion rate of quinoline is 98.6%, and the selectivity of py-THQ is 97.2%.

[0069] Example 7

[0070] This example is the XRD characterization of the Ni-NC / SiO2-900 catalyst.

[0071] Perform XRD characterization on the Ni-NC / SiO2-900 catalyst obtained in Example 1. Mainly analyze its phase composition (see Figure 7 ). Through MDI Jade phase retrieval and analysis, an amorphous characteristic peak was found at 2θ = 21.9° for this catalyst, which belongs to the characteristic peak of SiO2 (PDF#71-0785). The characteristic peaks at 2θ = 44.5°, 51.8°, and 76.4° belong to Ni elemental species (PDF#70-1849), indicating that the active substance in the prepared Ni-NC / SiO2-900 catalyst exists in the form of Ni nanoparticles. At the same time, other diffraction peaks of the Ni phase appear at 2θ = 44.8°, namely Ni3Si (PDF#65-3243).

[0072] Example 8

[0073] This example is the TEM characterization of the Ni-NC / SiO2-900 catalyst.

[0074] Perform TEM characterization on the Ni-NC / SiO2-900 catalyst obtained in Example 1 (see Figure 8, 50nm), it can be found that the catalyst mainly presents a foamy morphology, the active species Ni single substance is uniformly loaded on the surface of the carrier SiO2 from all directions, and the distribution of Ni single substance is also relatively uniform, without obvious agglomeration and large particles, which makes the catalyst have sufficient active sites. At the same time, the foamy catalyst morphology makes its structure relatively loose, and the reactants can act on the catalyst surface more smoothly. These two main reasons improve its catalytic performance.

[0075] At the same time, from the TEM image of 10nm (see Figure 9 ) can be measured that its interplanar spacing d = 2.041nm, which is consistent with the Ni (110 crystal plane, d = 2.035nm) in PDF#70-1849, which once again proves that the active phase is Ni. At the same time, 40 Ni single-particles were randomly selected to measure their diameters. The average particle size is 12.7nm, concentrated in 10-16nm, and the maximum does not exceed 22nm.

[0076] The present invention also uses the Ni-NC / SiO2-900 catalyst obtained in Example 1 to catalyze isoquinoline and functionalized quinoline, and achieves good results. The catalytic reaction conditions are shown in the following table:

[0077]

[0078] Reaction conditions: 1 mmol substrate, 40 mg Ni-NC / SiO2, 5 mL methanol, 3 MPa H2, 80°C.

[0079] Among them, 1: isoquinoline; 2: 8-hydroxyquinoline; 3: 6-chloroquinoline; 4: 8-methylquinoline.

Claims

1. A supported Ni-based heterogeneous catalyst, characterized in that: The carrier of the catalyst is SiO2, and the active component is a nickel element wrapped by a nitrogen-doped carbon material, and the nickel element wrapped by the nitrogen-doped carbon material is uniformly dispersed on the carrier SiO2; the catalyst is prepared by the following method: 1) mixing nickel salt, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and a solvent to prepare a solution; 2) mixing 2-methylimidazole, triethylamine and water to prepare an aqueous solution; 3) under heating and stirring conditions, the solutions prepared in step 1) and step 2) are mixed evenly, and then tetraethyl orthosilicate is added dropwise, and stirred for reaction to obtain a green suspension; 4) filtering, washing, drying and fully grinding to obtain green powder, which is Ni-MOF / SiO2, i.e., catalyst precursor; 5) High temperature calcination and reduction to obtain a black Ni-NC / SiO2-T catalyst.

2. A preparation method of a supported Ni-based heterogeneous catalyst, characterized in that: The method comprises the following steps: 1) mixing nickel salt, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and a solvent to prepare a solution; 2) mixing 2-methylimidazole, triethylamine and water to prepare an aqueous solution; 3) under heating and stirring conditions, the solutions prepared in step 1) and step 2) are mixed evenly, and then tetraethyl orthosilicate is added dropwise, and stirred for reaction to obtain a green suspension; 4) filtering, washing, drying and fully grinding to obtain green powder, which is Ni-MOF / SiO2, i.e., catalyst precursor; 5) High temperature calcination and reduction to obtain a black Ni-NC / SiO2-T catalyst.

3. The preparation method of the supported Ni-based heterogeneous catalyst according to claim 2, characterized in that, The molar ratio of the nickel salt, the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, 2-methylimidazole and triethylamine is 1:0.27-0.405:8-12:8-12.

4. The preparation method of the supported Ni-based heterogeneous catalyst according to claim 2 or 3, characterized in that, In the catalyst, the mass percentage of SiO2 is 7-8%.

5. The preparation method of the supported Ni-based heterogeneous catalyst according to claim 2 or 3, characterized in that, The solvent in step 1) is anhydrous ethanol.

6. The preparation method of the supported Ni-based heterogeneous catalyst according to claim 2 or 3, characterized in that, In the step 3), the heating temperature is 50° C.; in the step 5), the temperature rising program of high temperature calcination is a heating rate of 5° C. / min, a calcination temperature of 700-900° C., and a calcination time of 2-3 hours.

7. Use of the supported Ni-based heterogeneous catalyst according to claim 1 in the selective hydrogenation of quinoline compounds, characterized in that, The application includes the following steps: 1) mixing a catalyst, a quinoline compound and an organic solvent; 2) Hydrogen is introduced at a certain temperature and pressure to carry out a selective hydrogenation reaction to generate hydrogenated quinoline compounds.

8. Use of the supported Ni-based heterogeneous catalyst according to claim 7 in the selective hydrogenation of quinoline compounds, characterized in that, The reaction temperature of the selective hydrogenation reaction is 80-90° C., the reaction pressure is 0.1-4.0 MPa, and the reaction time is 5-7 hours.

9. Use of the supported Ni-based heterogeneous catalyst according to claim 7 or 8 in the selective hydrogenation of quinoline compounds, characterized in that, The quinoline compound is quinoline, isoquinoline or functionalized quinoline.

10. Use of the supported Ni-based heterogeneous catalyst according to claim 7 or 8 in the selective hydrogenation of quinoline compounds, characterized in that, The organic solvent is one or more of methanol, ethanol, toluene and tetrahydrofuran.

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