Preparation method and application of an organic liquid hydrogenation catalyst

Abstract

The present invention discloses a preparation method of an organic liquid hydrogenation catalyst, which relates to the technical field of hydrogen energy storage and transportation. The preparation method is as follows: soak alumina spheres in an aqueous nickel salt solution, add an alkali solution to form nickel hydroxide on the surface of the alumina spheres, precipitate, filter, wash, and dry and cool; drop a mixed solution of hydrochloric acid dopamine and palladium chloride onto the alumina spheres loaded with nickel hydroxide precipitate, put it into a tubular furnace, introduce air, perform programmed temperature roasting, cool down, introduce a H2 / N2 mixed gas for reduction, and the obtained alumina spheres supported core-shell palladium-nickel catalyst can be obtained after cooling. By preparing the alumina spheres supported core-shell palladium-nickel catalyst and applying it to the organic liquid hydrogenation process, using the alumina spheres as the catalyst carrier, and utilizing the synergistic enhancement effect generated by the formation of the core-shell structure of palladium and nickel, while improving the activity of the non-noble metal catalyst, the dosage and cost of the noble metal catalyst are reduced, and the problem of catalyst separation can be solved.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogen energy storage and transportation, and specifically to a preparation method and application of an organic liquid hydrogenation catalyst. Background Art

[0002] Hydrogen energy is a green energy source with wide sources, high energy density, clean combustion, renewability, and storability. Its application can not only solve the carbon emission problem faced by the current use of fossil energy, but also, as an efficient energy storage medium, combined with wind energy, solar energy, nuclear energy, etc., can play a role in peak shaving and valley filling and balancing the power grid. The hydrogen energy industry chain includes links such as hydrogen production, storage, transportation, and application. Among them, hydrogen energy storage is the technical bottleneck problem in the current development of hydrogen energy. Hydrogen storage technologies mainly include physical hydrogen storage and chemical hydrogen storage. The organic liquid hydrogen storage technology based on the chemical reaction method has attracted great attention due to its advantages such as large hydrogen storage capacity, high energy density, safe and convenient liquid storage and transportation, etc. The organic liquid hydrogen storage technology uses the catalytic hydrogenation and dehydrogenation reversible reaction of unsaturated aromatic hydrocarbons and corresponding hydrides (saturated aromatic hydrocarbons) to realize the storage and release of hydrogen energy. Since the reaction process is highly reversible, the reactants and products can be recycled. At the same time, since the properties of organic liquids are similar to those of oil products, the existing oil product storage and transportation infrastructure can be fully utilized for storage and transportation, which can greatly reduce the hydrogen storage and transportation cost. Moreover, long-distance transportation in the form of organic liquids can also solve the problem of uneven regional distribution of energy. Therefore, this technology is considered to be an effective means to solve large-scale hydrogen energy storage, long-distance hydrogen energy transportation, and replace traditional fossil fuels, and will play a crucial role in the future "hydrogen economy era".

[0003] However, on the one hand, the hydrogen storage process of organic liquids needs to be realized through high-pressure hydrogenation reactions. At present, most of the research on hydrogenation catalysts used is based on noble metal catalysts. Although noble metals have good catalytic activity, the large amount of use of noble metals also brings the problem of high cost, causing certain difficulties for the large-scale promotion of organic liquid hydrogen storage technology. And the existing conventional supported non-noble metal catalysts also have the disadvantage of low activity, resulting in difficulty in fully hydrogenating organic liquids. Therefore, there is an urgent need to provide high-activity and low-cost hydrogenation catalysts; on the other hand, the hydrogenation reaction is generally carried out in a high-pressure reaction kettle in the form of gas-liquid-solid three phases. In order to make the organic liquid fully contact with the catalyst, the catalyst is generally in a powder state, but this brings the problem of difficult separation from the liquid after the reaction, increasing the operation cost. Therefore, there is an urgent need to change the operation mode of the organic liquid catalytic hydrogenation reaction process, and on the premise of not reducing the reaction efficiency, reduce or even avoid the separation operation difficulty of the catalyst in the later stage of the reaction. Summary of the Invention

[0004] The purpose of the present invention is to provide a preparation method and application of an organic liquid hydrogenation catalyst to solve the problem of catalyst separation.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] A preparation method of an organic liquid hydrogenation catalyst, wherein the hydrogenation catalyst is a core-shell palladium-nickel catalyst supported on alumina spheres, and the preparation method is as follows:

[0007] Step S1: Select alumina spheres with particle diameters of 150 - 300 μm, 400 - 600 μm, 1 - 2 mm, 2 - 3 mm, and 3 - 5 mm;

[0008] Step S2: Immerse the five specifications of alumina spheres in a nickel salt aqueous solution with a certain concentration, add an alkali solution with a certain concentration to form nickel hydroxide on the surface of the alumina spheres, and then perform precipitation, filtration, washing, and drying and cooling;

[0009] Step S3: Drop a mixed solution of dopamine hydrochloride and palladium chloride onto the alumina spheres loaded with nickel hydroxide precipitate, place it in a tube furnace, introduce air with a certain flow rate, raise the temperature to 350 - 550 °C for calcination, lower the temperature to 250 - 350 °C, introduce a H2 / N2 mixed gas for reduction, and after cooling, obtain the alumina sphere-supported core-shell palladium-nickel catalyst.

[0010] Based on the above technical solutions, the present invention also provides the following optional technical solutions:

[0011] In an optional solution: In step S1, the specific surface area of the alumina spheres measured by the N2 low-temperature physical adsorption method is not less than 150 m 2 / g, and the pore volume is not less than 0.4 mL / g.

[0012] In an optional solution: The nickel salt is one of halogen salts, nitrates, or acetates, the nickel salt concentration is 1 - 10 mol / L, and the weight percentage of nickel hydroxide precipitate on the alumina spheres is 20 - 80%.

[0013] In an optional solution: In the mixed solution of dopamine hydrochloride and palladium chloride, the concentration of palladium chloride is 0.001 - 0.1 mol / L, the molar ratio of dopamine hydrochloride to palladium chloride is 50:1, and the molar ratio of palladium chloride to nickel hydroxide is 1:500 - 1:2000.

[0014] Application of the alumina sphere-supported core-shell palladium-nickel catalyst prepared according to the above-mentioned preparation method of the organic liquid hydrogenation catalyst in the hydrogenation reaction process of organic liquids.

[0015] In an optional solution: The organic liquid is naphthalene, biphenyl, terphenyl, benzyltoluene, or dibenzyltoluene.

[0016] In an alternative solution: The reactor used in the hydrogenation reaction process of the organic liquid is an autoclave reactor, a slurry bed reactor, a fixed bed reactor or a trickle bed reactor.

[0017] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0018] 1. For different properties of organic liquid hydrogen storage agent raw materials, different reactor forms are selectively used for operation. For example, unsaturated aromatic hydrocarbons such as naphthalene, biphenyl, and terphenyl are solids at room temperature and are more suitable for reactors in the form of reaction kettles or slurry beds, while benzyltoluene, dibenzyltoluene, etc. are liquids at room temperature and can use reactors in the form of fixed beds or trickle beds;

[0019] 2. Different carrier particle sizes are selected to prepare the catalyst according to the reactor form, which not only facilitates the full mixing of the catalyst and the material during the reaction, but also facilitates the separation of the catalyst and the material in the later stage of the reaction; the determination of the molar ratio of palladium to nickel is adapted to the hydrogenation difficulty of different organic liquid raw material molecules;

[0020] 3. The selection of the total metal loading takes into account both the need for catalyst activity and the adaptation to the reactor form. High-loading catalysts are suitable for application in reaction kettles or slurry beds to avoid thermal runaway during the reaction process. Specific Embodiments

[0021] In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to embodiments. The embodiments listed in the present invention are only used to illustrate the present invention and are not used to limit the scope of the present invention. Any obvious modification or change made to the present invention does not depart from the spirit and scope of the present invention.

[0022] The present invention provides a method for preparing a core-shell palladium-nickel catalyst supported on alumina spheres, and the specific steps of the method include:

[0023] Select commercial alumina spheres with particle diameters of 150 - 300 μm, 400 - 600 μm, 1 - 2 mm, 2 - 3 mm, and 3 - 5 mm respectively, and place them in a vacuum oven at 80 °C for drying for 12 h;

[0024] Soak the cooled alumina spheres of each size in an aqueous nickel salt solution with a certain concentration. After 6 h, add an aqueous NaOH solution with a certain concentration to the solution to form nickel hydroxide precipitation on the surface of the alumina spheres. After standing for aging for 6 h, filter and wash until the salt ion concentration in the filtrate is lower than 100 mg / L. Then, place the alumina spheres loaded with nickel hydroxide precipitation in a vacuum oven at 60 °C for drying for 6 h;

[0025] Prepare a mixed solution of dopamine hydrochloride and palladium chloride, and drop it onto the alumina spheres loaded with nickel hydroxide precipitate after cooling. After standing for 6 h, put it into a tubular furnace, introduce air with a flow rate of 500 mL / min, and calcine at 350 - 550 °C at a heating rate of 2 °C / min for 6 h;

[0026] Cool down to 250 - 350 °C, introduce 10% H2 / N2 mixed gas to reduce for 6 h, and the obtained alumina sphere-supported core-shell palladium-nickel catalyst can be obtained after cooling.

[0027] In the preparation method of the alumina sphere-supported core-shell palladium-nickel catalyst of the present invention, the specific surface area of the alumina spheres determined by the N2 low-temperature physical adsorption method is not less than 150 m 2 / g, and the pore volume is not less than 0.4 mL / g. It is a commercial product, such as, but not limited to, activated alumina produced by Zibo Baida Chemical Co., Ltd.

[0028] The nickel salt is selected from one of halide salts, nitrates or acetates, the concentration of the nickel salt is 1 - 10 mol / L, preferably 2 - 8 mol / L. The molar ratio of sodium hydroxide to nickel salt in the solution is 2:1, and the weight percentage of nickel hydroxide precipitate on the alumina spheres is 20 - 80%.

[0029] In the mixed solution of dopamine hydrochloride and palladium chloride, the concentration of palladium chloride is 0.001 - 0.1 mol / L, preferably 0.005 - 0.05 mol / L. Among them, the molar ratio of dopamine hydrochloride to palladium chloride is 50:1, and the molar ratio of palladium chloride to nickel hydroxide is 1:500 - 1:2000, preferably 1:800 - 1:1600.

[0030] Example 1 (Catalyst Preparation):

[0031] Select 300 g of alumina spheres with a particle diameter of 150 - 300 μm. After drying and cooling, soak them in 500 mL of nickel chloride aqueous solution with a concentration of 8 mol / L. After 6 h, add 500 mL of NaOH solution with a concentration of 16 mol / L to the solution to form nickel hydroxide precipitate on the surface of the alumina spheres. After standing for aging for 6 h, filter and wash until the salt ion concentration in the filtrate is lower than 100 mg / L. Then put the alumina spheres loaded with nickel hydroxide precipitate into a vacuum oven and dry at 60 °C for 6 h. Then prepare 100 mL of a mixed solution of dopamine hydrochloride and palladium chloride, where the concentration of palladium chloride is 0.1 mol / L and the concentration of dopamine hydrochloride is 5 mol / L. Drop it on the cooled alumina spheres loaded with nickel hydroxide precipitate. After standing for 6 h, put it into a tubular furnace, and introduce air with a flow rate of 500 mL / min. Heat it up to 450 °C at a rate of 2 °C / min and calcine for 6 h. Finally, cool down to 300 °C, introduce 10% H2 / N2 mixed gas and reduce for 6 h. After cooling, the alumina sphere-supported core-shell palladium-nickel catalyst is obtained, where the molar ratio of palladium to nickel is 1:800 and the loading amount based on the total amount of metal is 40%.

[0032] Example 2 (Catalyst Preparation):

[0033] Select 500 g of alumina spheres with a particle diameter of 2 - 3 mm. After drying and cooling, soak them in 1000 mL of nickel nitrate aqueous solution with a concentration of 1 mol / L. After 6 h, add 500 mL of NaOH solution with a concentration of 8 mol / L to the solution to form nickel hydroxide precipitate on the surface of the alumina spheres. After standing for aging for 6 h, filter and wash until the salt ion concentration in the filtrate is lower than 100 mg / L. Then put the alumina spheres loaded with nickel hydroxide precipitate into a vacuum oven and dry at 60 °C for 6 h. Then prepare 400 mL of a mixed solution of dopamine hydrochloride and palladium chloride, where the concentration of palladium chloride is 0.005 mol / L and the concentration of dopamine hydrochloride is 0.25 mol / L. Drop it on the cooled alumina spheres loaded with nickel hydroxide precipitate. After standing for 6 h, put it into a tubular furnace, and introduce air with a flow rate of 500 mL / min. Heat it up to 550 °C at a rate of 2 °C / min and calcine for 6 h. Finally, cool down to 350 °C, introduce 10% H2 / N2 mixed gas and reduce for 6 h. After cooling, the alumina sphere-supported core-shell palladium-nickel catalyst is obtained, where the molar ratio of palladium to nickel is 1:1000 and the loading amount based on the total amount of metal is 15%.

[0034] Example 3 (Catalyst Preparation):

[0035] Select 100 g of alumina spheres with a particle diameter of 400 - 600 μm. After drying and cooling, soak them in 200 mL of nickel acetate aqueous solution with a concentration of 10 mol / L. After 6 h, add 400 mL of NaOH solution with a concentration of 10 mol / L to the solution to form nickel hydroxide precipitate on the surface of the alumina spheres. After standing for aging for 6 h, filter and wash until the salt ion concentration in the filtrate is lower than 100 mg / L. Then place the alumina spheres loaded with nickel hydroxide precipitate in a vacuum oven and dry at 60 °C for 6 h. Next, prepare a 50 mL mixed solution of dopamine hydrochloride and palladium chloride, where the concentration of palladium chloride is 0.025 mol / L and the concentration of dopamine hydrochloride is 1.25 mol / L. Dropwise add it to the cooled alumina spheres loaded with nickel hydroxide precipitate. After standing for 6 h, place it in a tubular furnace, introduce air with a flow rate of 500 mL / min, and program the temperature to rise to 350 °C at a rate of 2 °C / min and calcine for 6 h. Finally, cool the temperature to 250 °C, introduce 10% H2 / N2 mixed gas and reduce for 6 h. After cooling, the alumina sphere-supported core-shell palladium-nickel catalyst is obtained, where the molar ratio of palladium to nickel is 1:1600 and the loading amount based on the total amount of metals is 50%.

[0036] Example 4 (Catalyst Preparation):

[0037] Select 200 g of alumina spheres with a particle diameter of 1 - 2 mm. After drying and cooling, soak them in 300 mL of nickel chloride aqueous solution with a concentration of 5 mol / L. After 6 h, add 200 mL of NaOH solution with a concentration of 15 mol / L to the solution to form nickel hydroxide precipitate on the surface of the alumina spheres. After standing for aging for 6 h, filter and wash until the salt ion concentration in the filtrate is lower than 100 mg / L. Then place the alumina spheres loaded with nickel hydroxide precipitate in a vacuum oven and dry at 60 °C for 6 h. Next, prepare a 125 mL mixed solution of dopamine hydrochloride and palladium chloride, where the concentration of palladium chloride is 0.001 mol / L and the concentration of dopamine hydrochloride is 0.05 mol / L. Dropwise add it to the cooled alumina spheres loaded with nickel hydroxide precipitate. After standing for 6 h, place it in a tubular furnace, introduce air with a flow rate of 500 mL / min, and program the temperature to rise to 400 °C at a rate of 2 °C / min and calcine for 6 h. Finally, cool the temperature to 300 °C, introduce 10% H2 / N2 mixed gas and reduce for 6 h. After cooling, the alumina sphere-supported core-shell palladium-nickel catalyst is obtained, where the molar ratio of palladium to nickel is 1:1200 and the loading amount based on the total amount of metals is 30%.

[0038] Example 5 (Catalyst Application):

[0039] The catalyst obtained in Example 1 was applied to the hydrogenation reaction of naphthalene, and the reaction was carried out in a high-pressure reactor. The reaction conditions were as follows: the heating temperature of the raw material was 200 °C, the hydrogen pressure was 6 MPa, the weight ratio of the catalyst to the raw material was 0.1, and the heating was stopped after 4 h. The conversion rate of naphthalene measured by sampling was greater than 99%. The reaction product and the catalyst were separated by a stainless-steel screen with a mesh number of 170. All the materials passed through the screen within 10 minutes, and all the catalyst pellets remained on the screen (which could be used for the next batch of hydrogenation experiments). It was visually observed that there were no particulate matters in the separated material, and the material was in a clear state.

[0040] Comparative Example 1 (Preparation and application of a powdered single-nickel catalyst, compared with Examples 1 and 5):

[0041] The 150 - 300 μm alumina pellets in Example 1 were ground into powder, and alumina powder particles with a size of 40 - 75 μm were selected using a 200 - 400 mesh screen. Then, the catalyst was prepared according to the remaining same steps in Example 1, except that the addition of palladium chloride was cancelled. Finally, a single-nickel catalyst supported on alumina powder was obtained.

[0042] The obtained catalyst was applied to the hydrogenation reaction of naphthalene. The reaction was carried out in a high-pressure reactor, and the reaction conditions were the same as those in Example 5. After the reaction, the conversion rate of naphthalene measured by sampling was lower than 70% (the low conversion rate was due to the lack of palladium-nickel synergy). The reaction product and the catalyst were separated by a stainless-steel screen, but a 400-mesh screen was used instead. Since the catalyst powder particles were too fine and the liquid viscosity was relatively high, the two were mixed to form a viscous fluid. Therefore, it was very difficult to separate the two with a screen, and there were many suspended particulate matters in the liquid flowing out of the screen, and the liquid was in a turbid state.

[0043] Example 6 (Catalyst application):

[0044] The catalyst obtained in Example 2 was applied to the hydrogenation reaction of dibenzyltoluene. The reaction was carried out in a fixed-bed reactor. The heating temperature of the raw material was 200 °C, the hydrogen pressure was 5 MPa, the volume ratio of hydrogen to the raw material was 1000:1, and the liquid space time of the catalyst bed was 2 h. Samples were taken at the reactor outlet, and the conversion rate of dibenzyltoluene analyzed was greater than 98%.

[0045] Example 7 (Catalyst application):

[0046] The catalyst obtained in Example 3 was applied to the hydrogenation reaction of terphenyl. The reaction was carried out in a slurry bed reactor. The reaction conditions were as follows: the raw material heating temperature was 300 °C, the hydrogen pressure was 8 MPa, the weight ratio of the catalyst to the raw material was 0.5, the reaction liquid space time was 1 h, and a sieve with a mesh size lower than 40 meshes (mesh diameter greater than 400 μm) was installed at the reactor outlet. After the reaction, the material flowed out smoothly and was in a clarified state. The conversion rate of terphenyl measured by sampling was greater than 98%.

[0047] Example 8 (Catalyst Application):

[0048] The catalyst obtained in Example 4 was applied to the hydrogenation reaction of benzyltoluene. The reaction was carried out in a trickle bed reactor. The raw material heating temperature was 220 °C, the hydrogen pressure was 4 MPa, the volume ratio of hydrogen to the raw material was 800:1, and the liquid space time of the catalyst bed was 2 h. Sampling was carried out at the reactor outlet, and the conversion rate of benzyltoluene analyzed was greater than 98%.

[0049] Comparative Example 2 (Preparation and Application of Single Palladium Catalyst, Compared with Examples 2 and 6):

[0050] The catalyst was prepared according to the steps of adding palladium chloride in Example 2, that is: preparing 400 mL of a mixed solution of dopamine hydrochloride and palladium chloride, where the concentration of palladium chloride was 0.005 mol / L and the concentration of dopamine hydrochloride was 0.25 mol / L, and dropping it on 500 g of alumina spheres with a diameter of 2 - 3 mm after drying and cooling. After standing for 6 h, it was placed in a tubular furnace, and air with a flow rate of 500 mL / min was introduced, and the temperature was raised to 550 °C at a rate of 2 °C / min and calcined for 6 h; finally, the temperature was lowered to 350 °C, and a 10% H2 / N2 mixed gas was introduced for reduction for 6 h. After cooling, the single palladium catalyst supported on the alumina spheres was obtained, and the loading amount based on the metal mass was 0.04%.

[0051] The obtained catalyst was applied to the hydrogenation reaction of dibenzyltoluene. The reaction was carried out in a fixed bed reactor. The raw material heating temperature was 200 °C, the hydrogen pressure was 5 MPa, the volume ratio of hydrogen to the raw material was 1000:1, and the liquid space time of the catalyst bed was 2 h. Sampling was carried out at the reactor outlet, and the conversion rate of dibenzyltoluene analyzed was lower than 5% (the extremely low conversion rate was due to too little palladium usage and the lack of palladium-nickel synergy).

[0052] Comparative Example 3 (Using a High-Pressure Reactor, Compared with Example 6):

[0053] The catalyst obtained in Example 2 was applied to the hydrogenation reaction of dibenzyltoluene. The reaction was carried out in a high-pressure reactor. The heating temperature of the raw material was 200 °C, the hydrogen pressure was 5 MPa, the weight ratio of the catalyst to the raw material was 0.2, and the reaction was carried out for 10 h (equivalent to a liquid space time of 2 h for the catalyst in the fixed bed layer). Sampling showed that the conversion rate of dibenzyltoluene was lower than 75% (the reason for the low conversion rate was related to the too large particle size of the catalyst, which was easily aggregated at the bottom of the reaction kettle due to gravitational sedimentation and could not contact the material sufficiently).

[0054] As described above, the above are only specific embodiments of the present disclosure, but the protection scope of the present disclosure is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present disclosure can easily think of changes or substitutions, which should be covered by the protection scope of the present disclosure. Therefore, the protection scope of the present disclosure should be subject to the protection scope of the claims.

Claims

1. A preparation method of an organic liquid hydrogenation catalyst, characterized in that, The hydrogenation catalyst is a core-shell palladium-nickel catalyst supported on alumina spheres, and the preparation method is as follows: Step S1: Select alumina spheres with particle diameters of 150 - 300 μm, 400 - 600 μm, 1 - 2 mm, 2 - 3 mm, and 3 - 5 mm; Step S2: Immerse the five specifications of alumina spheres in an aqueous nickel salt solution with a certain concentration, add an alkali solution with a certain concentration to form nickel hydroxide on the surface of the alumina spheres, and then perform precipitation, filtration, washing, and drying and cooling; Step S3: Drop a mixed solution of dopamine hydrochloride and palladium chloride onto the alumina spheres loaded with nickel hydroxide precipitate, place it in a tubular furnace, introduce air with a certain flow rate, heat it up to 350 - 550 °C for calcination, cool it down to 250 - 350 °C, introduce a H2 / N2 mixed gas for reduction, and obtain the alumina sphere-supported core-shell palladium-nickel catalyst after cooling.

2. The preparation method of the organic liquid hydrogenation catalyst according to claim 1, characterized in that, In step S1, the specific surface area of the alumina spheres determined by the N2 low-temperature physical adsorption method is not less than 150 m 2 / g, and the pore volume is not less than 0.4 mL / g.

3. The preparation method of the organic liquid hydrogenation catalyst according to claim 1, characterized in that, The nickel salt is one of halogen salts, nitrates, or acetates, the concentration of the nickel salt is 1 - 10 mol / L, and the weight percentage of nickel hydroxide precipitate on the alumina spheres is 20% - 80%.

4. The preparation method of the organic liquid hydrogenation catalyst according to claim 1, characterized in that, In Step S2, the alkali solution is a NaOH solution, and the concentration of the NaOH solution is 8 - 16 mol / L.

5. The preparation method of the organic liquid hydrogenation catalyst according to claim 1, characterized in that, In the mixed solution of dopamine hydrochloride and palladium chloride, the concentration of palladium chloride is 0.001 - 0.1 mol / L, the molar ratio of dopamine hydrochloride to palladium chloride is 50:1, and the molar ratio of palladium chloride to nickel hydroxide is 1:500 - 1:2000.

6. Application of the hydrogenation catalyst for organic liquids, characterized in that, Application of the alumina sphere-supported core-shell palladium-nickel catalyst prepared by the preparation method of the organic liquid hydrogenation catalyst according to any one of claims 1 - 5 in the hydrogenation reaction process of the organic liquid.

7. Use of the organic liquid hydrogenation catalyst according to claim 6, characterized in that, The organic liquid is naphthalene, biphenyl, terphenyl, benzyltoluene, or dibenzyltoluene.

8. Use of the organic liquid hydrogenation catalyst according to claim 6, characterized in that, The reactor used in the hydrogenation reaction process of the organic liquid is an autoclave reactor, a slurry bed reactor, a fixed bed reactor, or a trickle bed reactor.