Hydrogenation catalyst as well as preparation method and application thereof

Abstract

The invention relates to the technical field of catalysts, and particularly discloses a hydrogenation catalyst and a preparation method and application thereof. The hydrogenation catalyst raw material comprises a carrier component and a catalytic component, the carrier component comprises the following raw materials in parts by weight: 60-80 parts of gamma-aluminum oxide; 5 to 10 parts of titanium carbide; 5 to 10 parts of hydroxyapatite; 10 to 15 parts of a chelated nanocapsule; 5-10 parts of zirconium oxide; 3-5 parts of a stabilizer; the catalytic component is prepared from the following raw materials: 20 to 30 parts of modified hydroxyl cobalt oxide; 5 to 10 parts of molybdenum trioxide; and 1-3 parts of rare earth oxide. The modified cobalt oxyhydroxide is obtained by modifying cobalt oxyhydroxide through lanthanum nitrate. According to the hydrogenation catalyst, pollution and poisoning of catalytic active components can be avoided through the components such as the rare earth oxide, and long-acting stability of catalytic performance is achieved.

Description

Technical Field

[0001] This application relates to the field of catalyst technology, and more specifically, to a hydrogenation catalyst, its preparation method, and its application. Background Technology

[0002] Hydrogenation, a core catalytic conversion technology in the chemical industry, is a process in which compounds and hydrogen undergo addition under specific conditions. It enables targeted modification of molecular structures and performance optimization, and has become an indispensable key conversion pathway in industries such as petroleum refining, fine chemicals, and new energy conversion. In petroleum refining, hydrogenation can achieve the lightening of heavy oils, desulfurization, denitrogenation, demetallization, and aromatic saturation of oil products. It is a core process for producing clean fuels and improving oil quality to meet environmental emission standards. However, hydrogenation reactions typically require harsh conditions such as high temperature and high pressure, and have low reaction efficiency and produce many byproducts, making it difficult to meet the demands of large-scale, high-efficiency industrial production. Hydrogenation catalysts, as the core support for this reaction, can significantly improve the rate and selectivity of hydrogenation reactions under mild conditions by lowering the activation energy and controlling the reaction pathway, while reducing energy consumption and byproduct formation. They are crucial for overcoming the technological bottlenecks of hydrogenation reactions and promoting the industrial application and upgrading of hydrogenation processes. Their performance directly determines the quality and yield of hydrogenated products, as well as the economic and environmental benefits of the production process.

[0003] In related technologies, for example, patent application CN120827891A discloses a hydrocracking catalyst, its preparation method, and its application. The catalyst in this scheme includes a support and an active metal component; the support comprises modified Y molecular sieve and alumina. The modified Y molecular sieve has the following properties: crystal particle size below 500 nm, a molar ratio of silicon oxide to alumina of 8–55, and a specific surface area of ​​640–800 m². 2 The catalyst has a unit cell parameter of 2.433–2.460 nm and an average pore size of 10–30 nm. The active metal component includes Mo and Group VIII metals; the Mo includes +5 valence Mo; the Group VIII metals exist in the catalyst as metal phosphides. This catalyst exhibits excellent isomerization properties and aromatic hydrocarbon conversion capabilities, making it suitable for hydrocracking processes in the production of specialty oils and lubricating oil base oils.

[0004] Although the hydrocracking catalysts disclosed in the above technical solutions have certain advantages in isomerization and aromatic conversion in the production of specialty oils and lubricating oil base oils, they still have significant performance shortcomings and application limitations due to the limitations of the support structure design and active component system. Facing the core needs of the petroleum refining industry for inferior feedstocks and efficient light oil production, these hydrocracking catalysts have significant shortcomings in terms of pollution resistance and stability. Specifically, the catalysts exhibit significant shortcomings in their resistance to contamination and stability. Because the Group VIII metal phosphides in the active components are relatively intolerant to sulfur, nitrogen compounds, and metallic impurities such as vanadium and nickel in the feedstock, in the hydrocracking of high-sulfur, high-metal inferior oils, metallic impurities such as vanadium and nickel will deposit in the form of elements, oxides, or sulfides (such as V2O5 and NiS) under high-temperature and high-pressure reaction conditions. Furthermore, the atomic size of these metal compounds is similar to that of the metal atoms in the phosphide active centers, easily embedding into the phosphide crystal lattice and disrupting its regular structure, leading to sintering and agglomeration of the active centers. Simultaneously, the deposition of metallic impurities can also clog catalyst pores, hindering the contact between reactants and active centers, ultimately making it difficult to maintain stable catalytic performance over long periods. Summary of the Invention

[0005] In order to improve the defects of catalysts in related technologies that are easily contaminated by metal impurities, and thus improve the long-term stability of the catalyst's catalytic performance, this application provides a hydrogenation catalyst, its preparation method, and its application.

[0006] This application provides a hydrogenation catalyst, its preparation method, and its application, employing the following technical solution: A hydrogenation catalyst, comprising a support component and a catalytic component; The carrier component comprises the following raw materials in parts by weight: 60-80 parts of γ-alumina; 5-10 parts of titanium carbide; 5-10 parts of hydroxyapatite; 10-15 parts of chelated nanocapsules; 5-10 parts of zirconium oxide; Stabilizer 3-5 parts; The catalytic component comprises the following raw materials in parts by weight: 20-30 parts of modified cobalt hydroxyl oxide; 5-10 parts of molybdenum trioxide; 1-3 parts of rare earth oxides; The core material of the chelated nanocapsule is a compound of disodium ethylenediaminetetraacetate and sodium dithiocarbamate, and the shell material is a cross-linked polymer of poly(dimethylaminoethyl methacrylate) and sodium alginate. The modified cobalt hydroxyoxide was obtained by modifying cobalt hydroxyoxide with lanthanum nitrate.

[0007] By adopting the above technical solution, the modified cobalt hydroxyl oxide in the catalytic component is modified by lanthanum nitrate doping and complexation with citric acid to form a "Co-La-O-citric acid" composite structure. After calcination, a La-containing Co-based composite oxide is generated. Since the atomic radius of La is larger than that of metal impurities such as V and Ni, and its binding energy with O is higher, it can form an "isolation and protection layer" on the surface of the Co-based active center. At the same time, the electronegativity of La is lower than that of Co, and it will preferentially form stable La-V and La-Ni intermetallic compounds with metal impurities such as V and Ni. This effectively avoids impurity atoms from embedding into the lattice structure of the Co-based active center, inhibiting the sintering and agglomeration of the active center from the root, significantly improving the catalyst's anti-pollution ability in the face of high-sulfur, high-metal, and low-quality oil, and ensuring the long-term stable operation of the catalyst.

[0008] In the carrier components, the core material of the chelated nanocapsules is a compound of disodium ethylenediaminetetraacetate and sodium dithiocarbamate, while the shell material is a cross-linked polymer of poly(dimethylaminoethyl methacrylate) and sodium alginate. During the hydrogenation reaction, the deposition of metallic impurities leads to a decrease in the local pH value of the pores, triggering the degradation of the shell material and releasing the chelating agent in the core material. This chelate actively forms water-soluble chelates with the deposited V₂O₅, NiS, etc., and is discharged with the reaction products, achieving dynamic cleaning. Titanium carbide has a porous structure and high conductivity. Its high conductivity can promote charge transfer during the reaction, reduce the formation of carbon precursors, and the Ti on the surface... 3+ The catalytic sites can catalyze the oxidation and decomposition of carbon deposits, reducing the risk of pore blockage. Hydroxyapatite has excellent adsorption properties and can assist in the adsorption of some impurities. The synergistic effect of these three factors effectively solves the problem of catalyst pores being easily blocked by the deposition of metallic impurities, thus contributing to the long-term stability of the catalyst's catalytic performance.

[0009] In summary, the hydrotreating catalyst of this application constructs a complete closed-loop defense system against impurities and contaminants through the synergistic effect of modified cobalt hydroxyoxide, chelated nanocapsules, titanium carbide, and hydroxyapatite. Modified cobalt hydroxyoxide achieves front-end impurity interception, while the support components achieve dynamic cleaning in the middle stage, completely solving the core pain points of existing catalysts: "impurity embedding + pore blockage." Simultaneously, the synergistic effect of rare earth oxides and other components ensures that catalytic activity and selectivity do not decrease, achieving long-term stability of catalytic performance, and demonstrating significant advantages in the hydrocracking or hydrorefining reactions of high-sulfur, high-metal, and low-quality oils.

[0010] Optionally, the modified cobalt hydroxyoxide is prepared by the following method: A. Add citric acid to the cobalt nitrate solution, heat to 40-60℃ and stir for 30-60 minutes to form a complex solution; B. Add sodium hydroxide solution dropwise to the complexing solution to adjust the pH of the system to 9±0.3, then add lanthanum nitrate and stir at a constant temperature of 50-70℃ for 12-24 hours to form a precipitate. C. Centrifuge the precipitate, collect and wash the precipitate, then dry it at 80-100℃ for 12-16h, and finally calcine it at 350-450℃ for 2-4h. After cooling, the modified cobalt hydroxyl oxide is obtained.

[0011] By employing the above-described technical solution, through precise control of adding citric acid to a cobalt nitrate solution to form a complex liquid, then adding sodium hydroxide solution to adjust the pH value, followed by adding lanthanum nitrate and stirring at a constant temperature to form a precipitate, and finally through centrifugation, washing, drying, and calcination, a structurally stable and high-performance modified cobalt hydroxyl oxide can be prepared. This preparation method is rational, highly operable, and can guarantee the quality and performance of the modified cobalt hydroxyl oxide, providing a reliable active component for hydrogenation catalysts, thereby improving the overall anti-fouling and catalytic performance of the catalyst.

[0012] Optionally, in step A, the concentration of the cobalt nitrate solution is 0.5-1.0 mol / L; the amount of citric acid added is 5%-10% of the mass of the cobalt nitrate solution.

[0013] By adopting the above technical solution, the concentration of cobalt nitrate solution and the amount of citric acid added are key to forming a stable complex liquid. This ensures that lanthanum nitrate and cobalt hydroxyoxide are fully doped and complexed in the subsequent reaction to generate an ideal "Co-La-O-citric acid" composite structure. This, in turn, ensures that the La-containing Co-based composite oxide obtained after calcination has good anti-fouling properties, effectively inhibits the sintering and agglomeration of active centers, and improves the stability and service life of the catalyst.

[0014] Optionally, in step B, the concentration of the sodium hydroxide solution is 0.8-1.2 mol / L; the amount of lanthanum nitrate added is 3%-5% of the mass of the cobalt nitrate solution.

[0015] Optionally, the chelated nanocapsules are prepared using the following method: (1) Mix disodium ethylenediaminetetraacetate, sodium dithiocarbamate and water and stir to dissolve. Then add sodium alginate, heat to 40-50℃ and stir for 20-30 minutes to form a core material composite liquid. (2) Heat and stir liquid paraffin with Span-80 to form an oil phase; add the core material composite liquid droplets to the oil phase, and continue stirring for 1-2 hours after the droplets are added to form a W / O type reverse emulsion; (3) Add poly(dimethylaminoethyl methacrylate) monomer and sodium alginate to the W / O type reverse emulsion and stir for 1-2 hours; under nitrogen protection, add ammonium persulfate solution and MBA, heat to 70-80℃ and continue the reaction for 2-3 hours, cool to room temperature, then add anhydrous ethanol, centrifuge and wash the precipitate, and dry to obtain chelated nanocapsules.

[0016] By employing the above-mentioned technical solution, disodium ethylenediaminetetraacetate, sodium dithiocarbamate, and water are mixed and dissolved, and then sodium alginate is added to form a core material composite liquid. This liquid is then combined with an oil phase to form a W / O type reverse emulsion. Finally, poly(dimethylaminoethyl methacrylate) monomer and sodium alginate are added to initiate a polymerization reaction, thus preparing chelated nanocapsules with specific structures and properties. This preparation method can precisely control the composition of the core and shell materials of the nanocapsules, enabling them to accurately respond to pH changes during hydrogenation reactions, release chelating agents, achieve dynamic cleaning functions, effectively solve the problem of pore blockage, and improve the stability and activity of the catalyst.

[0017] Optionally, in steps (1) and (2), the mass ratio of disodium ethylenediaminetetraacetate, sodium dithiocarbamate, water, sodium alginate, liquid paraffin and Span-80 is (5-7):(2-4):(30-40):(2-3):100:(2-4).

[0018] Optionally, in step (3), the amount of poly(dimethylaminoethyl methacrylate) monomer added is 12%-18% of the mass of the W / O type reverse emulsion; the amount of sodium alginate added is 3%-6% of the mass of the W / O type reverse emulsion; the mass concentration of ammonium persulfate solution is 8%-12%; the amount of ammonium persulfate solution added is 3%-5% of the mass of the W / O type reverse emulsion; the amount of MBA added is 0.8%-1.5% of the mass of the W / O type reverse emulsion; and the amount of anhydrous ethanol added is 90%-110% of the mass of the W / O type reverse emulsion.

[0019] By employing the above-mentioned technical solution, a suitable raw material mass ratio is a key factor in preparing high-performance chelated nanocapsules. This ensures the stability and uniformity of the core material composite liquid and the W / O type reverse emulsion, allowing the core and shell materials of the nanocapsules to form according to the expected ratio and structure. This enables the nanocapsules to exhibit good pH response and chelating cleaning effects during hydrogenation reactions, effectively preventing pore blockage, maintaining catalyst activity, and improving the catalyst's adaptability in hydrogenation scenarios involving high-sulfur, high-metal, and low-quality oils.

[0020] Secondly, this application also provides a method for preparing a hydrogenation catalyst, employing the following technical solution: A method for preparing a hydrogenation catalyst includes the following steps: S1. Weigh the carrier component raw materials according to the weight proportions, mix them evenly, add 10%-20% of the total mass of the raw materials in deionized water, knead them into shape, dry them at 110-130℃ for 8-12 hours, and then calcine them at 400-500℃ for 4-6 hours to obtain the carrier matrix. S2. Weigh the catalytic component raw materials according to the weight proportions, add 50%-70% of the total mass of the raw materials with deionized water and stir evenly to obtain the catalytic component slurry; S3. The catalyst component slurry is uniformly impregnated or sprayed onto the support substrate, and then dried at 90-110℃ for 10-14h. Subsequently, it is reduced and calcined at 400-500℃ for 3-5h. The reducing atmosphere is a mixture of hydrogen and nitrogen in a volume ratio of 1:(2-4). After cooling, the hydrogenation catalyst is obtained.

[0021] The above preparation method is reasonable and the steps are clear, ensuring that the components are uniformly dispersed and fully combined, giving the catalyst a good physical structure and chemical properties. Meanwhile, suitable drying and calcination conditions can remove impurities, enhance the catalyst's stability and activity, and provide a reliable catalyst for the hydrocracking or hydrorefining reactions of high-sulfur, high-metal, and low-quality oils.

[0022] Thirdly, this application provides an application of a hydrogenation catalyst, employing the following technical solution: Application of a hydrogenation catalyst, said hydrogenation catalyst being used in the hydrocracking or hydrorefining reaction of inferior oils.

[0023] By adopting the above technical solution, this catalyst is specifically used for hydrocracking or hydrorefining reactions of high-sulfur, high-metal, and low-quality oils. It can ensure sufficient contact between the catalyst and the reactants, promote the smooth progress of the reaction, improve the quality and yield of hydrogenated products, meet the needs of large-scale and efficient industrial production, and has broad application prospects in industries such as petroleum refining.

[0024] In summary, this application has the following beneficial effects: 1. Effectively solves the problem of catalyst contamination by metal impurities and enhances its anti-contamination ability: In the hydrogenation catalyst of this application, the modified cobalt hydroxyl oxide in the catalytic component is modified by lanthanum nitrate doping and complexation with citric acid to form a "Co-La-O-citric acid" composite structure. After calcination, a La-containing Co-based composite oxide is generated. La has a large atomic radius and a high binding energy with O, which can form an "isolation and protection layer" on the surface of the Co-based active center. At the same time, it preferentially forms stable intermetallic compounds with metal impurities such as V and Ni, preventing impurity atoms from embedding into the crystal structure. This fundamentally inhibits the sintering and agglomeration of the active center, significantly improving the catalyst's anti-contamination ability in high-sulfur, high-metal, and low-quality oils, and ensuring long-term stable operation.

[0025] 2. Effectively solves the problem of catalyst pores being easily blocked by metal impurities, maintaining long-term stable catalytic performance: In the support component, when the pH value of the local pores decreases due to metal impurity deposition, the chelated nanocapsules release the chelating agent in the core material through shell degradation, actively forming water-soluble chelates with the deposits and being discharged, achieving dynamic cleaning; the porous structure and high conductivity of titanium carbide can promote charge transfer, reduce the formation of carbon deposit precursors, and catalyze the oxidation and decomposition of carbon deposits; hydroxyapatite can assist in the adsorption of some impurities. The synergistic effect of these three components effectively solves the problem of catalyst pores being easily blocked, which is conducive to maintaining long-term stable catalytic performance.

[0026] 3. The hydrogenation catalyst of this application constructs a complete closed-loop defense system against impurities and contaminants through the synergistic cooperation of its components. Modified cobalt hydroxyoxide achieves front-end impurity interception, the support component achieves mid-stage dynamic cleaning, and rare earth oxides and other components ensure that catalytic activity and selectivity do not decrease. In the hydrocracking or hydrorefining reactions of high-sulfur, high-metal, and low-quality oils, under specific reaction conditions, it can fully leverage its advantages of high anti-pollution properties, high catalytic performance, and long-term stability, improving the quality and yield of hydrogenated products and meeting the needs of large-scale, high-efficiency industrial production. It has broad application prospects in industries such as petroleum refining. Detailed Implementation

[0027] The present application will be further described in detail below with reference to the embodiments.

[0028] Preparation example of modified cobalt hydroxyoxide Preparation Example 1 Modified cobalt hydroxyoxide was prepared using the following method: A. Add 5g of citric acid to 100g of a 0.5mol / L cobalt nitrate solution, heat to 40℃ and stir for 60min to form a complex solution; B. Add 0.8 mol / L sodium hydroxide solution to the complexing solution to adjust the pH of the system to 8.7, then add 3g of lanthanum nitrate and stir at 50℃ for 24h to form a precipitate. C. Centrifuge the precipitate, collect the precipitate and wash it 5 times alternately with deionized water and anhydrous ethanol, then dry it at 80℃ for 16h, and finally calcine it at 350℃ for 4h. After cooling, the modified cobalt hydroxyl oxide is obtained.

[0029] Preparation Example 2 Modified cobalt hydroxyoxide was prepared using the following method: A. Add 8g of citric acid to 100g of a 0.8mol / L cobalt nitrate solution, heat to 50℃ and stir for 45min to form a complex solution; B. Add a 1.0 mol / L sodium hydroxide solution to the complexing solution to adjust the pH of the system to 9.0, then add 4 g of lanthanum nitrate and stir at 60 °C for 18 h to form a precipitate. C. Centrifuge the precipitate, collect the precipitate and wash it 5 times alternately with deionized water and anhydrous ethanol. Then dry it at 90℃ for 14h and finally calcine it at 400℃ for 3h. After cooling, the modified cobalt hydroxyl oxide is obtained.

[0030] Preparation Example 3 Modified cobalt hydroxyoxide was prepared using the following method: A. Add 10g of citric acid to 100g of a 1.0mol / L cobalt nitrate solution, heat to 60℃ and stir for 30min to form a complex solution; B. Add a 1.2 mol / L sodium hydroxide solution to the complexing solution to adjust the pH of the system to 9.3, then add 5 g of lanthanum nitrate and stir at 70 °C for 12 h to form a precipitate. C. Centrifuge the precipitate, collect the precipitate and wash it 5 times alternately with deionized water and anhydrous ethanol. Then dry it at 100℃ for 12h and finally calcine it at 450℃ for 2h. After cooling, the modified cobalt hydroxyl oxide is obtained.

[0031] Preparation Example 4 The modified cobalt hydroxyoxide differs from Preparation Example 3 in that an equal amount of cerium nitrate is used instead of lanthanum nitrate in this preparation example.

[0032] Preparation example of chelated nanocapsules Preparation Example 5 Chelated nanocapsules were prepared using the following method: (1) Mix 5g of disodium ethylenediaminetetraacetate, 2g of sodium dithiocarbamate and 30g of water and stir at 300r / min until dissolved. Then add 2g of sodium alginate, heat to 40℃ and continue stirring for 30min to form a core material composite liquid. (2) Heat 100g of liquid paraffin and 2g of Span-80 emulsifier to 50°C and stir at 800r / min to form an oil phase; add the core material composite liquid droplets to the oil phase at a dropping rate of 1mL / min, and continue stirring for 1h after the droplets are added to form a W / O type reverse emulsion. (3) Add 16.9g of poly(dimethylaminoethyl methacrylate) monomer and 4.23g of sodium alginate to the W / O type reverse emulsion and stir for 1h; under nitrogen protection, add 4.23g of ammonium persulfate solution with a mass concentration of 8% and 1.13g of MBA, heat to 70℃ and continue to react for 3h, cool to room temperature, then add 127g of anhydrous ethanol, centrifuge and wash with deionized water and petroleum ether alternately 5 times, dry at 60℃ for 12h to obtain chelated nanocapsules.

[0033] Preparation Example 6 Chelated nanocapsules were prepared using the following method: (1) Mix 6g of disodium ethylenediaminetetraacetate, 3g of sodium dithiocarbamate and 35g of water and stir at 300r / min until dissolved. Then add 2.5g of sodium alginate, heat to 45℃ and continue stirring for 25min to form a core material composite liquid. (2) Heat 100g of liquid paraffin and 3g of Span-80 emulsifier to 55°C and stir at 800r / min to form an oil phase; add the core material composite liquid droplets to the oil phase at a dropping rate of 1mL / min, and continue stirring for 1.5h after the droplets are added to form a W / O type reverse emulsion. (3) Add 22.5g of poly(dimethylaminoethyl methacrylate) monomer and 6.75g of sodium alginate to the W / O type reverse emulsion and stir for 1.5h. Under nitrogen protection, add 6g of 10% ammonium persulfate solution and 1.8g of MBA, heat to 70℃ and continue the reaction for 3h. Cool to room temperature, then add 150g of anhydrous ethanol. After centrifugation, wash 5 times alternately with deionized water and petroleum ether. Dry at 60℃ for 12h to obtain chelated nanocapsules.

[0034] Preparation Example 7 Chelated nanocapsules were prepared using the following method: (1) Mix 7g of disodium ethylenediaminetetraacetate, 4g of sodium dithiocarbamate and 40g of water and stir at 300r / min until dissolved. Then add 3g of sodium alginate, heat to 50℃ and continue stirring for 20min to form a core material composite liquid. (2) Heat 100g of liquid paraffin and 4g of Span-80 emulsifier to 60°C and stir at 800r / min to form an oil phase; add the core material composite liquid droplets to the oil phase at a dropping rate of 1mL / min, and continue stirring for 2h after the droplets are added to form a W / O type reverse emulsion. (3) Add 28.44g of poly(dimethylaminoethyl methacrylate) monomer and 9.48g of sodium alginate to the W / O type reverse emulsion and stir for 2h; under nitrogen protection, add 7.9g of ammonium persulfate solution with a mass concentration of 12% and 2.37g of MBA, heat to 70℃ and continue to react for 3h, cool to room temperature, then add 174g of anhydrous ethanol, centrifuge and wash with deionized water and petroleum ether alternately 5 times, dry at 60℃ for 12h to obtain chelated nanocapsules.

[0035] Example Example 1 A hydrogenation catalyst includes a support component and a catalytic component. The raw material components and formulations of the support component are shown in Table 1. The chelated nanocapsules are selected from the chelated nanocapsules prepared in Preparation Example 5, and the stabilizer is calcium oxide. The raw material components and formulations of the catalytic component are shown in Table 1. The modified cobalt hydroxyoxide is selected from the modified cobalt hydroxyoxide prepared in Preparation Example 1, and the rare earth oxide is lanthanum oxide.

[0036] The preparation method of the hydrogenation catalyst includes the following steps: S1. Weigh the carrier component raw materials according to the weight ratio, mix them evenly, add 10% of the total mass of deionized water, knead them into shape, dry them at 110℃ for 12h, and then calcine them at 400℃ for 6h to obtain the carrier matrix. S2. Weigh the catalytic component raw materials according to the weight ratio, add 50% of the total mass of the raw materials with deionized water and stir evenly to obtain the catalytic component slurry; S3. The catalytic component slurry is uniformly impregnated or sprayed onto the support substrate in 5 coats with a 30-minute interval between each coat. Then, it is dried at 90°C for 14 hours and subsequently reduced and calcined at 400°C for 5 hours in a mixed gas of hydrogen and nitrogen with a volume ratio of 1:2. After cooling, the hydrogenation catalyst is obtained.

[0037] Example 2 A hydrogenation catalyst includes a support component and a catalytic component. The raw material components and formulations of the support component are shown in Table 1. The chelated nanocapsules are selected from the chelated nanocapsules prepared in Preparation Example 6, and the stabilizer is calcium oxide. The raw material components and formulations of the catalytic component are shown in Table 1. The modified cobalt hydroxyoxide is selected from the modified cobalt hydroxyoxide prepared in Preparation Example 2, and the rare earth oxide is cerium oxide.

[0038] The preparation method of the hydrogenation catalyst includes the following steps: S1. Weigh the carrier component raw materials according to the weight ratio, mix them evenly, add 15% of the total mass of deionized water, knead them into shape, dry them at 120℃ for 10h, and then calcine them at 450℃ for 5h to obtain the carrier matrix. S2. Weigh the catalytic component raw materials according to the weight ratio, add 60% of the total mass of the raw materials with deionized water and stir evenly to obtain the catalytic component slurry; S3. The catalyst component slurry is uniformly impregnated or sprayed onto the support substrate in 5 coats with a 30-minute interval between each coat. Then, it is dried at 100°C for 12 hours and subsequently reduced and calcined at 450°C for 4 hours in a mixed gas of hydrogen and nitrogen with a volume ratio of 1:3. After cooling, the hydrogenation catalyst is obtained.

[0039] Example 3 A hydrogenation catalyst includes a support component and a catalytic component. The raw material components and formulations of the support component are shown in Table 1. The chelated nanocapsules are selected from the chelated nanocapsules prepared in Preparation Example 7, and the stabilizer is calcium oxide. The raw material components and formulations of the catalytic component are shown in Table 1. The modified cobalt hydroxyoxide is selected from the modified cobalt hydroxyoxide prepared in Preparation Example 3, and the rare earth oxide is neodymium oxide.

[0040] The preparation method of the hydrogenation catalyst includes the following steps: S1. Weigh the carrier component raw materials according to the weight ratio, mix them evenly, add 20% of the total mass of deionized water, knead them into shape, dry them at 130℃ for 8 hours, and then calcine them at 500℃ for 4 hours to obtain the carrier matrix. S2. Weigh the catalytic component raw materials according to the weight ratio, add 70% of the total mass of the raw materials of deionized water and stir evenly to obtain the catalytic component slurry; S3. The catalyst component slurry is uniformly impregnated or sprayed onto the support substrate in 5 coats with a 30-minute interval between each coat. Then, it is dried at 110°C for 10 hours and subsequently reduced and calcined at 500°C for 3 hours in a mixed gas of hydrogen and nitrogen with a volume ratio of 1:4. After cooling, the hydrogenation catalyst is obtained.

[0041] Table 1. Raw material components and dosages (g) for Examples 1-3

[0042] Example 4 A hydrogenation catalyst, which differs from Example 3 in that the modified cobalt hydroxyoxide in this example is the modified cobalt hydroxyoxide prepared in Preparation Example 4.

[0043] Example 5 A hydrogenation catalyst, which differs from Example 3 in that the stabilizer used in this example is silicon dioxide.

[0044] Example 6 A hydrogenation catalyst, which differs from Example 3 in that the rare earth oxides used in this example are lanthanum oxide and cerium oxide in a mass ratio of 1:1.

[0045] Comparative Example Comparative Example 1 A hydrocracking catalyst was prepared according to the method in Example 1 of the patent application document with publication number CN120827891A entitled "A Hydrocracking Catalyst and Its Preparation Method and Application".

[0046] Comparative Example 2 A hydrogenation catalyst, which differs from Example 3 in that an equal amount of disodium ethylenediaminetetraacetate is used instead of chelated nanocapsules in the support component of this comparative example.

[0047] Comparative Example 3 A hydrogenation catalyst, which differs from Example 3 in that an equal amount of unmodified cobalt hydroxyoxide is used instead of modified cobalt hydroxyoxide in the catalytic component of this comparative example.

[0048] Comparative Example 4 A hydrogenation catalyst, which differs from Example 3 in that hydroxyapatite was not added to the support component in this comparative example.

[0049] Performance testing 1. Raw material oil to be processed: High-sulfur, high-metal inferior heavy oil, with the following indicators: sulfur content 8000ppm, total vanadium + nickel metal content 500μg / g, gum + asphaltene content 30wt%, which is consistent with the actual working conditions of inferior industrial oil.

[0050] Test catalysts: 5g of each type of catalyst prepared in Examples 1-6 and Comparative Examples 1-4 of this application were taken and shaped into strip-shaped particles of Φ3mm×3mm for later use.

[0051] Hydrogen: purity ≥ 99.99%, meeting the industrial standards for hydrogenation reactions.

[0052] 2. Test methods The catalysts from Examples 1-6 and Comparative Examples 1-4 were respectively loaded into the middle of a fixed-bed reaction tube, with both ends filled with quartz sand for fixation. Hydrogen gas was introduced (volume hourly space velocity 1000 h⁻¹), and the temperature was increased to 450°C at 5°C / min. The mixture was then reduced and calcined for 4 hours, and cooled to a reaction temperature of 380°C for later use. A high-pressure metering pump was then started to pump inferior feedstock oil into the reaction tube at a set liquid hourly space velocity, while simultaneously introducing hydrogen gas. The hydrogen-to-oil volume ratio was adjusted to 1200:1, and the reaction pressure was maintained at 15 MPa and the temperature at 380°C. Continuous reaction was initiated and operated for 1000 hours. After 500 hours and 1000 hours of reaction, the sulfur content in the feedstock oil and product oil was measured using a sulfur content analyzer according to ASTM D5453 standard. The desulfurization rate was calculated, and subsequently, the desulfurization activity retention rate at 500 hours and 1000 hours was calculated. Simultaneously, the V and Ni contents in the feedstock and product oils were determined by ICP-OES, and the demetallization rate was calculated as (feedstock metal content - product metal content) / feedstock metal content × 100%. Similarly, the demetallization activity retention rate at 500h and 1000h was calculated. The test results are shown in Table 2.

[0053] Table 2 Detection Results

[0054] As shown in Table 2, the hydrogenation catalyst of Comparative Example 1 exhibits a desulfurization activity retention rate of only 45.2% and a demetallization activity retention rate of only 42.7% after 1000 hours. Due to the embedding of metal impurities into the crystal lattice and pore blockage, its long-term stability is extremely poor, with a significant performance decline after 500-1000 hours. In contrast, the hydrogenation catalysts of Examples 1-6 of this application all exhibit a desulfurization activity retention rate ≥85.2% and a demetallization activity retention rate ≥85.4% after 1000 hours. Examples 3 and 6 even exceed 90%, with a performance decline of only 5-8 percentage points. This fully verifies the effectiveness of the "modified cobalt hydroxyl oxide + chelated nanocapsule" closed-loop defense system, effectively addressing the core pain points of existing technologies.

[0055] Comparative Example 2, which replaced the chelated nanocapsules (without pH-responsive dynamic release function) with an equal amount of disodium ethylenediaminetetraacetate, showed a desulfurization / demetallization activity retention rate of only 63.8% / 58.4% after 1000 hours, a decrease of 27.7 / 32.4 percentage points compared to Example 3. This is because the free chelating agent is easily lost prematurely, failing to continuously remove deposited impurities from the pores, leading to increased pore blockage and confirming the irreplaceable nature of the chelated nanocapsules.

[0056] Comparative Example 3, using unmodified cobalt hydroxyl oxide, showed a desulfurization / demetallization activity retention rate of 68.5% / 70.2% after 1000 hours, a decrease of 23 / 20.6 percentage points compared to Example 3. Due to the lack of an "isolation and protection layer" constructed by La, V and Ni impurities easily embed into the Co-based active center lattice, leading to sintering and agglomeration of the active centers, highlighting the core effect of La doping modification.

[0057] Comparative Example 4, without the addition of hydroxyapatite, showed an activity retention rate of 81.6% / 79.3% after 1000 hours, a decrease of 9.9 / 11.5 percentage points compared to Example 3. This indicates that the auxiliary adsorption of free impurities by hydroxyapatite can reduce the load on the chelated nanocapsules, further improving the system stability and demonstrating the synergistic advantages of the components.

[0058] Example 6 exhibits the best performance, with a desulfurization / demetallization activity retention rate of ≥90% after 1000h. This is due to the rare earth compound further enhancing the dispersibility of the active components, forming a synergistic anti-pollution effect with La doping.

[0059] Example 4 uses cerium nitrate instead of lanthanum nitrate, and the performance is slightly lower than that of Example 3 (desulfurization retention rate of 89.7% after 1000h), which confirms that La has a better advantage than Ce in resisting impurity intercalation.

[0060] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A hydrogenation catalyst characterized by, The carrier component and the catalytic component are included; The carrier component includes the following raw materials in parts by weight: γ-alumina 60-80 parts; Titanium carbide 5-10 parts; Hydroxyapatite 5-10 parts; Chelated nanocapsule 10-15 parts; Zirconium oxide 5-10 parts; Stabilizer 3-5 parts; The catalytic component includes the following raw materials in parts by weight: Modified hydroxyl cobalt oxide 20-30 parts; Molybdenum trioxide 5-10 parts; Rare earth oxide 1-3 parts; The core material of the chelated nanocapsule is a complex of disodium ethylenediaminetetraacetate and sodium dithiocarbamate, and the shell material is a cross-linked polymer of polymethyl methacrylate dimethylaminoethyl ester and sodium alginate; The modified hydroxyl cobalt oxide is obtained by modifying hydroxyl cobalt oxide with lanthanum nitrate.

2. The hydrogenation catalyst according to claim 1, characterized by The modified hydroxyl cobalt oxide is prepared by the following method: A. Citric acid is added to the cobalt nitrate solution, heated to 40-60℃ and stirred for 30-60min to form a complex solution; B. Sodium hydroxide solution is added dropwise to the complex solution, the pH value of the system is adjusted to 9±0.3, then lanthanum nitrate is added, and the system is stirred at 50-70℃ for 12-24h to form a precipitate solution; C. The precipitate solution is centrifuged, the precipitate is collected and washed, then dried at 80-100℃ for 12-16h, finally calcined at 350-450℃ for 2-4h, and cooled to obtain the modified hydroxyl cobalt oxide.

3. The hydrogenation catalyst of claim 2, wherein: In step A, the concentration of the cobalt nitrate solution is 0.5-1.0mol / L; the amount of citric acid added is 5%-10% of the mass of the cobalt nitrate solution.

4. The hydrogenation catalyst of claim 2, wherein: In step B, the concentration of the sodium hydroxide solution is 0.8-1.2mol / L; the amount of lanthanum nitrate added is 3%-5% of the mass of the cobalt nitrate solution.

5. The hydrogenation catalyst of claim 1, wherein The chelated nanocapsule is prepared by the following method: (1) Disodium ethylenediaminetetraacetate, sodium dithiocarbamate and water are mixed and stirred to dissolve, then sodium alginate is added, heated to 40-50℃ and stirred for 20-30min to form a core material complex solution; (2) Liquid paraffin and Span-80 are heated and stirred to form an oil phase; the core material complex solution is added dropwise to the oil phase, and stirring is continued for 1-2h after the addition is completed to form a W / O type reverse phase emulsion; (3) Polymethyl methacrylate dimethylaminoethyl ester monomer and sodium alginate are added to the W / O type reverse phase emulsion and stirred for 1-2h; under nitrogen protection, ammonium persulfate solution and MBA are added, heated to 70-80℃ and continued to react for 2-3h, cooled to room temperature, then anhydrous ethanol is added, the precipitate is washed after centrifugation, and dried to obtain the chelated nanocapsule.

6. The hydrogenation catalyst according to claim 5, wherein In steps (1) and (2), the mass ratio of disodium ethylenediaminetetraacetate, sodium dithiocarbamate, water, sodium alginate, liquid paraffin and Span-80 is (5-7):(2-4):(30-40):(2-3):100:(2-4).

7. The hydrogenation catalyst of claim 5, wherein In step (3), the adding amount of the polymethyl methacrylate dimethylaminoethyl ester monomer is 12%-18% of the mass of the W / O type inverse emulsion; the adding amount of the sodium alginate is 3%-6% of the mass of the W / O type inverse emulsion; the mass concentration of the ammonium persulfate solution is 8%-12%; the adding amount of the ammonium persulfate solution is 3%-5% of the mass of the W / O type inverse emulsion; the adding amount of the MBA is 0.8%-1.5% of the mass of the W / O type inverse emulsion; and the adding amount of the anhydrous ethanol is 90%-110% of the mass of the W / O type inverse emulsion.

8. The hydrogenation catalyst of claim 1, wherein The rare earth oxide is at least one of lanthanum oxide, cerium oxide and neodymium oxide.

9. A process for the preparation of a hydrogenation catalyst as claimed in any one of claims 1 to 8, characterized in that The method comprises the following steps: S1, carrier component raw materials are weighed by weight fraction, mixed uniformly, then 10%-20% of the total mass of the raw materials of deionized water is added, kneaded and formed, dried at 110-130 DEG C for 8-12h, then calcined at 400-500 DEG C for 4-6h to obtain a carrier matrix; S2, catalytic component raw materials are weighed by weight fraction, 50%-70% of the total mass of the raw materials of deionized water is added and stirred uniformly to obtain a catalytic component slurry; S3, the catalytic component slurry is uniformly impregnated or sprayed onto the carrier matrix, then dried at 90-110 DEG C for 10-14h, then reduced and calcined at 400-500 DEG C for 3-5h, the reducing atmosphere is a mixed gas of hydrogen and nitrogen with a volume ratio of 1: (2-4), and the hydrogenation catalyst is obtained after cooling.

10. Use of a hydrogenation catalyst as claimed in any one of claims 1-8, characterized in that The hydrogenation catalyst is used for the hydrocracking reaction or the hydrorefining reaction of poor quality oil.

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