Hydrogenation catalyst, process for its preparation and use

Abstract

The application relates to the technical field of catalysts, and particularly discloses a hydrogenation catalyst as well as a preparation method and application thereof.A hydrogenation catalyst raw material comprises a carrier component and a catalytic component; the carrier component raw material comprises: 60-80 parts of gamma-alumina; 5-10 parts of titanium carbide; 5-10 parts of hydroxyapatite; 10-15 parts of chelated nanocapsules; 5-10 parts of zirconium oxide; and 3-5 parts of a stabilizer; the catalytic component raw material comprises: 20-30 parts of modified hydroxyl cobalt oxide; 5-10 parts of molybdenum trioxide; and 1-3 parts of rare earth oxide.The modified hydroxyl cobalt oxide is obtained by modifying hydroxyl cobalt oxide with lanthanum nitrate.The hydrogenation catalyst can avoid pollution and poisoning of the catalytic active component by the components such as the rare earth oxide, and realizes long-term stability of the catalytic performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of catalysts, and more particularly to a hydrogenation catalyst and a preparation method and application thereof. BACKGROUND

[0002] Hydrogenation reaction, as a core catalytic conversion technology in the chemical industry, is a process of addition of hydrogen to a compound under specific conditions, which can realize the directional modification of molecular structure and performance optimization. It has become an indispensable key conversion path in the industries of petroleum refining, fine chemical industry, and new energy conversion. In petroleum refining, hydrogenation reaction can realize the lightening of heavy oil, the removal of sulfur, nitrogen and metal from oil, and the saturation of aromatic hydrocarbons. It is the core process for producing clean fuel and improving oil quality to meet the environmental protection standards of fuel emissions. However, hydrogenation reaction usually requires harsh conditions such as high temperature and high pressure, and has low reaction efficiency and generates many by-products, which is difficult to meet the production needs of industrial scale and high efficiency. As the core support of the reaction, hydrogenation catalyst can significantly improve the rate and selectivity of hydrogenation reaction under mild conditions by reducing the reaction activation energy and controlling the reaction path, while reducing energy consumption and by-product generation. It is the key to break through the technical bottleneck of hydrogenation reaction and promote the industrial application and upgrading of hydrogenation process. Its performance directly determines the quality and yield of hydrogenation products, as well as the economy and environmental protection of the production process.

[0003] In related technologies, a hydrogenation cracking catalyst, a preparation method and application thereof are disclosed in a patent application with publication number CN120827891A. The catalyst in the scheme includes a carrier and an active metal component. The carrier includes modified Y molecular sieve and alumina. The modified Y molecular sieve has the following properties: the crystal particle size is less than 500 nm, the molar ratio of silicon oxide to aluminum oxide is 8-55, the specific surface area is 640-800 m 2 / g, the unit cell parameter is 2.433-2.460 nm, and the average pore size is 10-30 nm. The active metal component includes Mo and Group VIII metal elements. The Mo includes +5 valence Mo. The Group VIII metal elements exist in the catalyst in the form of metal phosphide. The catalyst has excellent isomerization performance and aromatic conversion capacity, and is suitable for the hydrogenation cracking process for producing special oil and lubricating oil base oil.

[0004] Although the hydrocracking catalyst disclosed in the above technical solution has certain isomerization and aromatic conversion advantages in the production of special oil and lubricating oil base oil, due to the limitations of carrier structure design and active component system, the hydrocracking catalyst still has obvious performance short boards and application limitations in the face of the core demand of heavy oil efficient lightening of the petroleum refining industry. Specifically, the catalyst has obvious short boards in terms of pollution resistance and stability. Since the phosphide of the Group VIII metal in the active component has weak resistance to sulfur, nitrogen compounds and vanadium, nickel and other metal impurities in the raw material, in the high-sulfur high-metal poor oil hydrogenation scene, vanadium, nickel and other metal impurities will be deposited in the form of elemental substance, oxide or sulfide (such as V2O5, NiS) under high temperature and high pressure reaction conditions, and the atomic size of these metal compounds is similar to the atomic size of the metal of the phosphide active center, which is easy to embed the phosphide crystal lattice and destroy its regular structure, resulting in sintering and agglomeration of the active center. At the same time, the deposition of metal impurities also blocks the pores of the catalyst, hindering the contact between the reactants and the active centers, and finally it is difficult to maintain the long-period stable catalytic performance. SUMMARY

[0005] In order to improve the defect that the catalyst is easily polluted by metal impurities in the related art, and further improve the long-term stability of the catalytic performance of the catalyst, the application provides a hydrogenation catalyst and a preparation method and application thereof.

[0006] The hydrogenation catalyst and the preparation method and application thereof provided by the application adopt the following technical solution:

[0007] A hydrogenation catalyst, comprising a carrier component and a catalytic component;

[0008] The carrier component comprises the following raw materials in parts by weight:

[0009] 60-80 parts of gamma-alumina;

[0010] 5-10 parts of titanium carbide;

[0011] 5-10 parts of titanium carbide;

[0012] 10-15 parts of chelated nanocapsule;

[0013] 5-10 parts of zirconium oxide;

[0014] 3-5 parts of stabilizer;

[0015] The carrier component comprises the following raw materials in parts by weight:

[0016] 20-30 parts of modified hydroxyl cobalt oxide;

[0017] 5-10 parts of molybdenum trioxide;

[0018] 1-3 parts of rare earth oxide;

[0019] The core material of the chelating nanocapsule is a complex of disodium ethylenediaminetetraacetate and sodium dithiocarbamate, and the shell material is a cross-linked polymer of polymethyl methacrylate dimethylaminoethyl and sodium alginate.

[0020] The modified cobalt hydroxide is obtained by modifying cobalt hydroxide with lanthanum nitrate.

[0021] By adopting the above technical solution, the modified cobalt hydroxide in the catalytic component is modified by lanthanum nitrate doping and citric acid complexing to form a "Co-La-O-citric acid" composite structure, and after calcination, a Co-based composite oxide containing La is generated. Since the atomic radius of La element is larger than that of V, Ni and other metal impurity atoms, and the binding energy with O is higher, an "isolated protective layer" can be formed on the surface of the Co-based active center. At the same time, the electronegativity of La is lower than that of Co, which will preferentially form stable La-V, La-Ni intermetallic compounds with V, Ni and other metal impurities, effectively avoiding the embedding of impurity atoms into the lattice structure of the Co-based active center, and from the root, inhibiting the sintering and agglomeration of the active center, and significantly improving the anti-pollution ability of the catalyst when facing high-sulfur and high-metal poor-quality oil, and ensuring the long-term stable operation of the catalyst.

[0022] In the carrier component, the core material of the chelating nanocapsule is a complex of disodium ethylenediaminetetraacetate and sodium dithiocarbamate, and the shell material is a cross-linked polymer of polymethyl methacrylate dimethylaminoethyl and sodium alginate. In the hydrogenation reaction, the deposition of metal impurities causes the pH value of the local pore channel to decrease, triggering the degradation of the shell material, releasing the chelating agent in the core material, and actively forming water-soluble chelates with deposited V2O5, NiS and the like and being discharged with the reaction products, realizing dynamic cleaning. Titanium carbide has a porous structure and high electrical conductivity, and its high electrical conductivity can promote charge transfer during the reaction process, reduce the generation of carbon deposition precursors, and the Ti 3+ sites on the surface can catalyze the oxidative decomposition of carbon deposition, reducing the risk of pore channel blockage. Hydroxyapatite has good adsorption performance and can assist in adsorbing part of the impurities. The three components work together to effectively solve the problem of pore channel blockage caused by metal impurity deposition, thereby helping to maintain the long-term stability of the catalytic performance of the catalyst.

[0023] In summary, the hydrogenation catalyst of the present application cooperates the components of modified cobalt hydroxide, chelating nanocapsule, titanium carbide and hydroxyapatite to build a complete impurity pollutant closed-loop defense system. The modified cobalt hydroxide realizes front-end impurity interception, and the carrier component realizes middle-end dynamic cleaning, completely solving the core pain point of "impurity embedding + pore channel blockage" of the existing catalyst. At the same time, the synergistic effect of the rare earth oxide and other components ensures that the catalytic activity and selectivity do not decrease, and realizes the long-term stability of the catalytic performance, which has a significant advantage in the hydrogenation cracking or hydrogenation refining reaction of high-sulfur and high-metal poor-quality oil.

[0024] Optionally, the modified cobalt oxyhydroxide is prepared by the following method:

[0025] A. Citric acid is added to the cobalt nitrate solution, and the temperature is raised to 40-60℃ and stirred for 30-60min to form a complex solution;

[0026] B. Sodium hydroxide solution is added dropwise to the complex solution, and the pH value of the system is adjusted to 9±0.3, then lanthanum nitrate is added, and the temperature is kept at 50-70℃ and stirred for 12-24h to form a precipitate solution;

[0027] C. The precipitate solution is centrifuged, the precipitate is collected and washed, then dried at 80-100℃ for 12-16h, and finally calcined at 350-450℃ for 2-4h to obtain the modified cobalt oxyhydroxide.

[0028] By using the above technical solution, by accurately controlling the addition of citric acid to the cobalt nitrate solution to form a complex solution, then adding sodium hydroxide solution to adjust the pH value, and then adding lanthanum nitrate for constant temperature stirring to form a precipitate solution, and finally through centrifugation, washing, drying and calcination, a modified cobalt oxyhydroxide with stable structure and excellent performance can be prepared. The preparation method is reasonable and operable, which can ensure the quality and performance of the modified cobalt oxyhydroxide, and provide reliable active components for hydrogenation catalysts, thereby improving the overall anti-pollution and catalytic performance of the catalyst.

[0029] Optionally, 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.

[0030] By using the above technical solution, the above-mentioned concentration of cobalt nitrate solution and the amount of citric acid added are the key to forming a stable complex solution, which can ensure that lanthanum nitrate and cobalt oxyhydroxide are fully doped and complexed in the subsequent reaction, generating an ideal "Co-La-O-citric acid" composite structure, thereby ensuring that the La-containing Co-based composite oxide obtained after calcination has good anti-pollution performance, effectively inhibiting the sintering and agglomeration of active centers, and improving the stability and service life of the catalyst.

[0031] Optionally, 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.

[0032] Optionally, the chelated nanocapsule is prepared by the following method:

[0033] (1) Dissolve disodium ethylenediaminetetraacetate, sodium dithiocarbamate and water by stirring, then add sodium alginate, raise the temperature to 40-50℃ and stir for 20-30min to form a core material complex solution;

[0034] (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;

[0035] (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.

[0036] 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.

[0037] 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).

[0038] 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.

[0039] 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.

[0040] Secondly, this application also provides a method for preparing a hydrogenation catalyst, employing the following technical solution:

[0041] A method for preparing a hydrogenation catalyst includes the following steps:

[0042] 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.

[0043] 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;

[0044] 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.

[0045] 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.

[0046] Thirdly, this application provides an application of a hydrogenation catalyst, employing the following technical solution:

[0047] Application of a hydrogenation catalyst, said hydrogenation catalyst being used in the hydrocracking or hydrorefining reaction of inferior oils.

[0048] 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.

[0049] In summary, this application has the following beneficial effects:

[0050] 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.

[0051] 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.

[0052] 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

[0053] The present application will be further described in detail below with reference to the embodiments.

[0054] Preparation example of modified cobalt hydroxyoxide

[0055] Preparation Example 1

[0056] Modified cobalt hydroxyoxide was prepared using the following method:

[0057] 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;

[0058] 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.

[0059] 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.

[0060] Preparation Example 2

[0061] Modified cobalt hydroxyoxide was prepared using the following method:

[0062] 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;

[0063] 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.

[0064] 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.

[0065] Preparation Example 3

[0066] Modified cobalt hydroxyoxide was prepared using the following method:

[0067] 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;

[0068] 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.

[0069] 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.

[0070] Preparation Example 4

[0071] 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.

[0072] Preparation example of chelated nanocapsules

[0073] Preparation Example 5

[0074] Chelated nanocapsules were prepared using the following method:

[0075] (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.

[0076] (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.

[0077] (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.

[0078] Preparation Example 6

[0079] Chelated nanocapsules were prepared using the following method:

[0080] (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.

[0081] (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.

[0082] (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.

[0083] Preparation Example 7

[0084] Chelated nanocapsules were prepared using the following method:

[0085] (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.

[0086] (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.

[0087] (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.

[0088] Example

[0089] Example 1

[0090] 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.

[0091] The preparation method of the hydrogenation catalyst includes the following steps:

[0092] 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.

[0093] 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;

[0094] 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.

[0095] Example 2

[0096] 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.

[0097] The preparation method of the hydrogenation catalyst includes the following steps:

[0098] 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.

[0099] 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;

[0100] 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.

[0101] Example 3

[0102] 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.

[0103] The preparation method of the hydrogenation catalyst includes the following steps:

[0104] 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.

[0105] 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;

[0106] 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.

[0107] Table 1. Raw material components and dosages (g) for Examples 1-3

[0108]

[0109] Example 4

[0110] 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.

[0111] Example 5

[0112] A hydrogenation catalyst, which differs from Example 3 in that the stabilizer used in this example is silicon dioxide.

[0113] Example 6

[0114] 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.

[0115] Comparative Example

[0116] Comparative Example 1

[0117] 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".

[0118] Comparative Example 2

[0119] 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.

[0120] Comparative Example 3

[0121] 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.

[0122] Comparative Example 4

[0123] A hydrogenation catalyst, which differs from Example 3 in that hydroxyapatite was not added to the support component in this comparative example.

[0124] Performance testing

[0125] 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.

[0126] 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.

[0127] Hydrogen: purity ≥ 99.99%, meeting the industrial standards for hydrogenation reactions.

[0128] 2. Test methods

[0129] 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.

[0130] Table 2 Detection Results

[0131]

[0132] 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.

[0133] 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.

[0134] 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.

[0135] 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.

[0136] 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.

[0137] 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.

[0138] 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 in that, Includes support components and catalytic components; The carrier component comprises the following raw materials in parts by weight: 60-80 parts γ-alumina; 5-10 parts titanium carbide; 5-10 parts hydroxyapatite; 10-15 parts chelated nanocapsules; 5-10 parts zirconium oxide; and 3-5 parts stabilizer. The catalytic component comprises the following raw materials in parts by weight: 20-30 parts modified cobalt hydroxyoxide; 5-10 parts molybdenum trioxide; and 1-3 parts 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 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 12-16 hours, and finally calcine it at 350-450℃ for 2-4 hours. After cooling, the precipitate is obtained. 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. The preparation method of the 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 catalytic component slurry is uniformly impregnated or sprayed onto the carrier substrate, then dried at 90-110℃ for 10-14h, followed by reduction calcination at 400-500℃ for 3-5h. The reduction atmosphere is a mixture of hydrogen and nitrogen in a volume ratio of 1:(2-4). After cooling, the product is obtained.

2. The hydrogenation catalyst according to claim 1, characterized in that: 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.

3. The hydrogenation catalyst according to claim 1, characterized in that, The chelated nanocapsules were 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.

4. A hydrogenation catalyst according to claim 3, characterized in that, 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).

5. A hydrogenation catalyst according to claim 3, characterized in that, 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.

6. A hydrogenation catalyst according to claim 1, characterized in that, The rare earth oxide is at least one of lanthanum oxide, cerium oxide, and neodymium oxide.

7. The application of a hydrogenation catalyst as described in any one of claims 1-6, characterized in that, The hydrogenation catalyst is used for the hydrocracking or hydrorefining of inferior oils.

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