Hydrogenation catalyst, process for its preparation and use

Abstract

This invention provides a hydrogenation catalyst, its preparation method, and its application, belonging to the field of catalyst technology. The method includes the following steps: S1, preparing an NH4-type ZSM-5 / SAPO-11 composite molecular sieve; S2, preparing a W-modified hydrogen-type composite molecular sieve; S3, adding the W-modified hydrogen-type composite molecular sieve to ethanol for ultrasonic treatment, then adding a Ni-Fe metal salt solution dropwise under stirring conditions, adjusting the pH to alkaline, aging to form a precipitate, washing, drying, calcining, and reducing and activating to obtain the hydrogenation catalyst. This invention can achieve efficient removal of heteroatoms such as sulfur and nitrogen while maintaining good hydrogenation activity.

Description

Technical Field

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

[0002] With the increasing demand for high-value utilization of heavy organic feedstocks and clean fuels, the importance of hydrotreating technology for heavy organic feedstocks in refining and coal chemical industries is becoming increasingly prominent. Heavy organic feedstocks typically have characteristics such as wide molecular weight distribution, high proportion of polar components and condensation structures, and high content of heteroatoms (S, N, O). Under hydrotreating conditions, quality improvement and product structure optimization often require multiple pathways such as hydrorefining, aromatic ring hydrogenation saturation, and hydrodesulfurization / denitrification / deoxygenation. This places higher demands on the pore structure, acidic site type and distribution, dispersion of metal active centers, and anti-sintering ability of hydrotreating catalysts.

[0003] Among the aforementioned heavy organic feedstocks, coal tar is a typical example. The polycyclic aromatic hydrocarbons and resinous / asphaltaceous components in coal tar are large in size and highly polar, making it difficult for them to enter the effective pores of the catalyst. This results in hydrogenation reactions occurring primarily at the pore openings and on the outer surface, leading to low utilization of the internal pores. Consequently, hydrogenation saturation and synergistic deimpurification reactions are incomplete, limiting the conversion depth. Furthermore, compared to heavy petroleum fractions, coal tar feedstock is characterized by high sulfur, high nitrogen, high ash, high aromatic hydrocarbon content, and high resinous and asphaltic content. During combustion, it easily generates large amounts of sulfur oxides and nitrogen oxides, causing environmental pollution. Therefore… The refining and efficient utilization of coal tar has become increasingly important, and hydrogenation catalysis can effectively remove impurities such as sulfur and nitrogen from coal tar. However, coal tar hydrogenation catalysts face challenges due to the adverse effects of water generated during deoxygenation on catalyst activity, stability, and strength. Furthermore, coal tar contains high levels of sulfur and nitrogen, as well as a large amount of aromatics. In heavy feedstock systems like coal tar, diffusion limitations, competitive adsorption of aromatics, and carbon buildup often make it difficult to achieve both high efficiency and long-term stability under relatively mild conditions. Therefore, to catalyze the removal of aromatics, sulfur, and nitrogen, catalysts must possess suitable pore structures and synergistic effects from the active components responsible for desulfurization and denitrification.

[0004] Chinese patent CN102626635A discloses the preparation and application of a coal tar denitrification catalyst. It is prepared by using Mo and W as hydrogenation active components and mesoporous alumina as a support, and by an equal-volume impregnation method. The catalyst in this invention is mainly developed for the high nitrogen content of coal tar. However, the use of mesoporous alumina as a support has limited pore connectivity and pore size distribution. When facing large molecular substrates such as polycyclic aromatic hydrocarbons and gums / asphaltene in coal tar, diffusion is easily restricted and the proportion of pore opening / outer surface reaction is too high, resulting in incomplete reaction and accelerated coking and pore blockage.

[0005] Therefore, there is a need to provide a hydrogenation catalyst, its preparation method, and its application to solve the above-mentioned technical problems. Summary of the Invention

[0006] In view of this, the present invention provides a hydrogenation catalyst, its preparation method and application, which can achieve efficient removal of heteroatoms such as sulfur and nitrogen while maintaining good hydrogenation activity.

[0007] To achieve the above objectives, the present invention provides a method for preparing a hydrogenation catalyst, comprising the following steps: S1. Hydrogen-type ZSM-5, deionized water, and di-n-propylamine were mixed and stirred, then added to P-Al-Si precursor gel and stirred. The mixture was hydrothermally treated, the precipitate was collected by centrifugation, washed, dried, calcined, added to ammonium nitrate solution, heated and stirred, filtered, washed, and dried to obtain NH4-type ZSM-5 / SAPO-11 composite molecular sieve. S2. Add the NH4 type ZSM-5 / SAPO-11 composite molecular sieve to the tungsten-containing precursor solution, stir and impregnate, let it stand for aging, filter, wash, dry and calcine to obtain the W modified hydrogen type composite molecular sieve. S3. The W-modified hydrogen-type composite molecular sieve was added to ethanol and ultrasonically treated. Under stirring conditions, Ni-Fe metal salt solution was added dropwise to adjust the pH to alkaline. The precipitate was aged, washed, dried, calcined, and reduced and activated to obtain the hydrogenation catalyst.

[0008] This invention introduces di-n-propylamine as a structure-directing agent into a P-Al-Si precursor gel system and uses hydrogen-form ZSM-5 particles as the nucleation core. Hydrothermal treatment induces the growth of SAPO-11 on the outer surface of ZSM-5, thus forming a composite molecular sieve structure with ZSM-5 as the core and SAPO-11 as the shell. Compared to conventional hydrogenation catalytic systems using single molecular sieves or ordinary oxides as supports, the SAPO-11 shell in this composite structure is formed by the stacking of fine crystallites. While maintaining the microporous framework, it also forms certain intergranular mesopores and external pores, which helps to increase the external specific surface area and pore connectivity. This alleviates the diffusion limitation problem of macromolecular components in heavy organic feedstocks such as coal tar, reduces the incomplete conversion caused by excessively high proportions of reactions at pore openings and external surfaces, thereby improving the utilization rate of active sites. This allows for more complete hydrogenation saturation of aromatic rings and hydrogenation conversion of sulfur- and nitrogen-containing compounds, providing a mass transfer and interfacial basis for achieving efficient desulfurization and denitrification. In addition, the ZSM-5 core retains its three-dimensional pore network and provides Brønsted acid sites, which is beneficial for the adsorption, activation and further transformation of heteroatom-containing components; the SAPO-11 shell, with its relatively mild acidity, can regulate the accessibility of the strong Brønsted acid sites on the outer surface of ZSM-5, making the acidity distribution more reasonable and more suitable for the reaction requirements of hydrorefining in heavy feedstock systems. Thus, while promoting desulfurization and denitrification reactions, it reduces the tendency of over-cracking, condensation polymerization and coking side reactions, and improves the stability of the catalyst.

[0009] Building upon this, the present invention selects tungsten modification on NH4-type ZSM-5 / SAPO-11 composite molecular sieves to form dispersed tungsten-containing active sites during subsequent heat treatment. Compared to unmodified composite molecular sieves, tungsten modification helps introduce Lewis acid centers, thereby improving the acidity distribution on the surface of the composite molecular sieve, enhancing its ability to disperse and deposit metal precursors, and its anchoring effect. This facilitates the uniform loading of Ni and Fe active components on the surface of the composite molecular sieve and reduces the tendency for local enrichment and agglomeration of active components. This further improves the utilization efficiency of metal active centers and helps maintain the activity and stability of the catalyst during hydrogenation reactions.

[0010] Furthermore, this invention employs a deposition-precipitation method to load nickel / iron active components onto a tungsten-modified hydrogen-type composite molecular sieve, which, after calcination and activation, forms bimetallic active centers. The mass transfer channels provided by the hierarchical pores of the composite molecular sieve, along with the enhanced anchoring effect of the tungsten-containing active sites, help improve the dispersibility of the nickel / iron active components and the number of available metal sites, thereby enhancing the catalyst's promoting effect on hydrodesulfurization, hydrodenitrogenation, and aromatic hydrogenation saturation reactions. Simultaneously, due to the good synergistic effect between the pore structure, acidic sites, and metal active centers, the catalyst is less prone to significant carbon buildup, pore blockage, and activity decay during long-term operation, thus achieving a balance between high desulfurization and denitrification efficiency and operational stability.

[0011] Optionally, the hydrogen form ZSM-5 is obtained by adding 2-5 parts by mass of ZSM-5 molecular sieve to 300-500 parts by mass of 0.5 mol / L ammonium nitrate solution, stirring at 60-80℃ for 4-6 hours for ion exchange, separating the solid by filtration, repeatedly washing with deionized water until the filtrate is nearly neutral, drying at 100-110℃ for 10-12 hours, and then calcining at 450-550℃ for 2-4 hours with a temperature increase of 2-5℃ / min.

[0012] This invention utilizes ammonium nitrate solution for ion exchange of exchangeable cations (such as Na+) within the ZSM-5 channels. + Replaced with NH4 + After calcination and deamination, Si-OH-Al Brønsted acid sites are formed, making the acid strength and density more controllable and reducing the risk of ordinary (such as Na-type) ZSM-5 acid sites being weakened by alkali metal neutralization. At the same time, the acidic hydroxyl groups and charge environment on the surface of hydrogen-type ZSM-5 are more conducive to the adsorption and initial nucleation / anchoring of precursor components in subsequent P-Al-Si gels, thereby promoting a more uniform and controllable epitaxial growth process.

[0013] Optionally, the P-Al-Si precursor gel is obtained by mixing 7-10 parts by weight of phosphoric acid and 30 parts by weight of deionized water and stirring for 30-50 min, then adding 4-8 parts by weight of pseudoboehmite and ultrasonically dispersing for 10-20 min, and finally adding 5-7 parts by weight of silica and stirring for 40-80 min.

[0014] Preferably, the pseudoboehmite is JHN-02 type mesoporous pseudoboehmite.

[0015] Using JHN-02 type mesoporous pseudoboehmite as the Al source can improve the wetting, dispersion and reaction uniformity of the aluminum source in the phosphoric acid-water system, promote the formation of a more stable P-Al-Si precursor gel, and facilitate the continuous epitaxial growth and grain refinement of the SAPO-11 shell during hydrothermal crystallization. At the same time, its mesoporous characteristics and high external specific surface area provide better pore connectivity and accessible interfaces for the composite support, further improving the mass transfer of macromolecular substrates and providing a dispersion anchoring basis for subsequent modification and metal loading, thereby enhancing the overall performance and stability of the catalyst.

[0016] Optionally, in step S1, 2-5 parts by weight of hydrogen-form ZSM-5, 20-50 parts by weight of deionized water, and 5-10 parts by weight of di-n-propylamine are mixed and stirred for 10-15 minutes, then added to the P-Al-Si precursor gel and mixed and stirred for 120-150 minutes. The mixture is then transferred to a stainless steel high-pressure reactor and hydrothermally reacted at 160-180°C for 20-24 hours. The precipitate is collected by centrifugation, washed 1-2 times with deionized water, and dried at 105-110°C. After 0-12 hours, the mixture is placed in air and calcined at 550-600℃ for 5-6 hours at a heating rate of 5℃ / min. Then, it is added to 300-500 parts by mass of 0.5mol / L ammonium nitrate solution and stirred at 60-80℃ for 4-6 hours for ion exchange. The solid is then separated by filtration and washed repeatedly with deionized water until the filtrate is nearly neutral. Finally, it is dried at 100-110℃ for 10-12 hours to obtain NH4 type ZSM-5 / SAPO-11 composite molecular sieve.

[0017] Optionally, the tungsten-containing precursor solution is obtained by adding 0.1-0.22 parts by weight of tungsten salt to 15-30 parts by weight of deionized water, stirring magnetically for 20-40 minutes, adjusting the pH to 2.5-3.5 with dilute nitric acid, adding 0.05-0.30 parts by weight of complexing dispersant, and stirring for another 10-20 minutes; the tungsten salt is one of ammonium metatungstate and ammonium paratungstate; the complexing dispersant is one of citric acid and oxalic acid; and the concentration of the dilute nitric acid is 0.5-1.0 mol / L.

[0018] This invention uses citric acid or oxalic acid as a complexing dispersant, which can complex and stabilize tungsten-containing precursor liquid under acidic conditions, inhibit the polymerization and precipitation of polytungstic acid, and improve the dispersibility and stability of the precursor liquid. At the same time, it promotes the uniform adsorption of tungsten-containing precursor on the carrier surface and enhances the anchoring effect, thereby making it easier to form a highly dispersed and stable tungsten-containing oxide structure in the subsequent calcination process, reducing the risk of agglomeration and sintering and improving the consistency of modification effect.

[0019] Optionally, in step S2, 8-10 parts by weight of NH4-type ZSM-5 / SAPO-11 composite molecular sieve are added to a tungsten-containing precursor solution and stirred for 1-3 hours, followed by static aging for 4-12 hours. The solid is separated by filtration, washed quickly 1-2 times with deionized water, dried at 100-110°C for 10-12 hours, and then placed in air to be heated to 450-550°C at a heating rate of 2-5°C / min and kept at that temperature for 2-4 hours to obtain W-modified hydrogen-type composite molecular sieve.

[0020] Optionally, the Ni-Fe metal salt solution is obtained by mixing ferric nitrate, nickel nitrate, deionized water, and dimethylformamide, and stirring magnetically for 20-40 minutes.

[0021] Optionally, in step S3, 8-10 parts by mass of W-modified hydrogen-type composite molecular sieve are added to 40-50 parts by mass of ethanol and ultrasonically treated for 5-10 minutes. Under stirring conditions, 200-300 parts by mass of Ni-Fe metal salt solution are added dropwise, followed by the addition of 3wt% ammonia until the pH of the system reaches 8.5-9.5. The system is then magnetically stirred and aged for 30-60 minutes to form a precipitate. The precipitate is washed 3-5 times with deionized water, dried in an oven at 100-110℃ for 4-5 hours, calcined at 350-450℃ for 2-4 hours, and then placed in a hydrogen atmosphere and heated to 400-500℃ at a rate of 3℃ / min and held at that temperature for 5-6 hours to obtain the hydrogenation catalyst.

[0022] The hydrogen atmosphere reduction and activation process described in this invention is used to convert the Ni and Fe oxidized precursors formed after calcination into active phases with hydrogenation function. Under controlled heating and isothermal conditions, it improves the reduction uniformity, inhibits the migration and agglomeration of metal particles, increases the density of usable metal surface sites and the stability of the metal-support interface, thereby enhancing the hydrogenation activity and long-term stability of the catalyst.

[0023] The present invention also provides a hydrogenation catalyst comprising the following raw materials in parts by weight: 8-10 parts of W-modified hydrogen-type composite molecular sieve, 40-50 parts of ethanol, and 200-300 parts of Ni-Fe metal salt solution; wherein the Ni-Fe metal salt solution comprises the following raw materials in parts by weight: 7-10 parts of ferric nitrate, 2-3.5 parts of nickel nitrate, 150-200 parts of deionized water, and 50-100 parts of dimethylformamide.

[0024] The hydrogenation catalyst prepared by the present invention with the above mass ratio can ensure a sufficient supply of Ni / Fe active metal precursors, making it easier to control the metal component loading and increase the number of available metal sites.

[0025] This invention also provides an application of a hydrogenation catalyst, which is used in the hydrogenation refining and upgrading process of heavy organic feedstocks such as coal tar.

[0026] This application can promote the hydrogenation removal of aromatic ring saturation and heteroatom compounds containing sulfur and nitrogen under hydrogenation conditions. By improving mass transfer channels, optimizing the distribution of acidic sites and stabilizing metal active centers, it reduces the tendency of coking and pore blockage, slows down the activity decay, thereby improving the hydrogenation and upgrading efficiency of heavy organic feedstocks such as coal tar and extending the operating cycle.

[0027] The above-described technical solution of the present invention has at least the following beneficial effects: 1. This invention constructs a composite molecular sieve structure of ZSM-5 core / SAPO-11 shell. The intercrystalline mesopores in the shell and the pores on the outer surface help to increase the external specific surface area and pore connectivity, alleviate the limitation of macromolecular diffusion in heavy organic raw materials such as coal tar, reduce the incomplete conversion caused by excessively high pore reaction ratio, and improve the utilization rate of active sites, thereby facilitating the in-depth hydrogenation conversion of aromatic ring saturation and sulfur- and nitrogen-containing compounds.

[0028] 2. In this invention, ZSM-5 provides Brønsted acid sites to facilitate the adsorption and activation of impurity components. SAPO-11 moderately acidifies the accessibility of strong acid sites on the outer surface of ZSM-5, making the distribution of acid sites more conducive to the hydrorefining reaction. While promoting desulfurization, denitrification and other impurity removal reactions, it weakens the strong acid-dominated over-cracking and condensation polymerization, reduces coking and pore blockage, and improves long-term operational stability.

[0029] 3. In this invention, tungsten modification is performed on NH4-type ZSM-5 / SAPO-11 composite molecular sieves to form tungsten-containing active sites on the surface of the composite molecular sieves. This helps to introduce Lewis acid centers and improve the acidity distribution on the surface of the composite molecular sieves. At the same time, it improves the utilization efficiency of Ni / Fe active components and helps to maintain the activity and stability of the catalyst during the hydrogenation reaction. Attached Figure Description

[0030] Figure 1 This is a SEM image of the hydrogenation catalyst prepared in Example 2 of the present invention; Figure 2 This is a TEM image of the hydrogenation catalyst prepared in Example 2 of the present invention. Detailed Implementation

[0031] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. The described embodiments are some embodiments of the present invention, and all other embodiments obtained by those skilled in the art based on the described embodiments of the present invention are within the scope of protection of the present invention.

[0032] Example 1 2g of ZSM-5 molecular sieve (CAS No.: 1318-02-1, silica-alumina ratio 300) was added to 300g of 0.5mol / L ammonium nitrate solution. After ion exchange by stirring at 60℃ for 4h, the solid was separated by filtration. The solid was repeatedly washed with deionized water until the filtrate was nearly neutral. It was then dried at 100℃ for 10h, followed by calcination at 450℃ for 2h at a rate of 2℃ / min to obtain hydrogen-form ZSM-5. 7g of phosphoric acid was mixed with 30g of deionized water and stirred for 30min. Then, 4g of… JHN-02 type mesoporous pseudoboehmite was ultrasonically dispersed for 10 min, and 5g of silica was added and stirred for another 40 min to obtain P-Al-Si precursor gel. 2g of hydrogen-type ZSM-5, 20g of deionized water, and 5g of di-n-propylamine were mixed and stirred for 10 min, then added to the P-Al-Si precursor gel and stirred for 120 min. The mixture was then transferred to a stainless steel high-pressure reactor and hydrothermally reacted at 160℃ for 20 h. The precipitate was collected by centrifugation, washed once with deionized water, dried at 105℃ for 10 h, and then calcined in air at a heating rate of 5℃ / min to 550℃ for 5 h. The precipitate was added to 300g of 0.5mol / L ammonium nitrate solution and stirred at 60℃ for 4 h for ion exchange. The solid was separated by filtration, repeatedly washed with deionized water until the filtrate was nearly neutral, and dried at 100℃ for 10 h to obtain NH4 type ZSM-5 / SAPO-11 composite molecular sieve.

[0033] 0.10 g of ammonium metatungstate was added to 15 g of deionized water and magnetically stirred for 20 min. The pH was adjusted to 3.5 with 0.5 mol / L dilute nitric acid, and 0.05 g of oxalic acid was added and stirred for another 10 min to obtain a tungsten-containing precursor solution. 8 g of NH4-type ZSM-5 / SAPO-11 composite molecular sieve was added to the tungsten-containing precursor solution and stirred and impregnated for 1 h. Then, it was allowed to stand and age for 4 h. The solid was separated by vacuum filtration, washed once with deionized water, dried at 100 °C for 10 h, and then placed in air and heated to 450 °C at a heating rate of 2 °C / min and kept at that temperature for 2 h to obtain W-modified hydrogen-type composite molecular sieve.

[0034] 7g of ferric nitrate, 2g of nickel nitrate, 150g of deionized water, and 50g of dimethylformamide were mixed and magnetically stirred for 20min to obtain a Ni-Fe metal salt solution. 8g of W-modified hydrogen-type composite molecular sieve was added to 40g of ethanol and ultrasonically treated for 5min. Under stirring, 200g of Ni-Fe metal salt solution was added dropwise, followed by the addition of 3wt% ammonia until the pH of the system reached 8.5. The mixture was then magnetically stirred and aged for 30min to form a precipitate. The precipitate was washed three times with deionized water, dried in an oven at 100℃ for 4h, calcined at 350℃ for 2h, and then placed in a hydrogen atmosphere and heated to 400℃ at a rate of 3℃ / min and held at that temperature for 5h to obtain the hydrogenation catalyst.

[0035] Example 2 2.5 g of ZSM-5 molecular sieve (CAS No.: 1318-02-1, silica-alumina ratio 300) was added to 350 g of 0.5 mol / L ammonium nitrate solution. After ion exchange by stirring at 65 °C for 4.5 h, the solid was separated by filtration and repeatedly washed with deionized water until the filtrate was nearly neutral. The filtrate was dried at 102 °C for 11 h and then calcined at 475 °C for 2.5 h at a rate of 3 °C / min to obtain hydrogen form ZSM-5. 7.8 g of phosphoric acid was mixed with 30 g of deionized water and stirred for 35 min. Then, 5 g of... JHN-02 type mesoporous pseudoboehmite was ultrasonically dispersed for 12 min, and 5.5 g of silica was added and stirred for another 50 min to obtain P-Al-Si precursor gel. 2.5 g of hydrogen-form ZSM-5, 30 g of deionized water, and 6 g of di-n-propylamine were mixed and stirred for 12 min, and then added to the P-Al-Si precursor gel and stirred for 130 min. The mixture was transferred to a stainless steel high-pressure reactor and hydrothermally reacted at 165 °C for 21 h. The precipitate was collected by centrifugation, washed once with deionized water, dried at 106 °C for 11 h, and then calcined in air at a heating rate of 5 °C / min to 560 °C for 5.5 h. The precipitate was added to 350 g of 0.5 mol / L ammonium nitrate solution and stirred at 65 °C for 4.5 h for ion exchange. The solid was separated by filtration, repeatedly washed with deionized water until the filtrate was nearly neutral, and dried at 102 °C for 11 h to obtain NH4 type ZSM-5 / SAPO-11 composite molecular sieve.

[0036] 0.12 g of ammonium paratungstate was added to 18 g of deionized water and magnetically stirred for 25 min. The pH was adjusted to 3.3 with 0.6 mol / L dilute nitric acid, and 0.10 g of citric acid was added and stirring was continued for 12 min to obtain a tungsten-containing precursor solution. 8.5 g of NH4 type ZSM-5 / SAPO-11 composite molecular sieve was added to the tungsten-containing precursor solution and stirred and impregnated for 1.5 h. Then, it was allowed to stand and age for 6 h. The solid was separated by vacuum filtration, washed once with deionized water, dried at 102 °C for 11 h, and then placed in air and heated to 475 °C at a heating rate of 3 °C / min and kept at that temperature for 2.5 h to obtain W-modified hydrogen-type composite molecular sieve.

[0037] 7.5g ferric nitrate, 2.3g nickel nitrate, 160g deionized water, and 60g dimethylformamide were mixed and magnetically stirred for 25 min to obtain a Ni-Fe metal salt solution. 8.5g W-modified hydrogen-type composite molecular sieve was added to 42g ethanol and ultrasonically treated for 6 min. Under stirring, 220g Ni-Fe metal salt solution was added dropwise, followed by the addition of 3wt% ammonia until the pH of the system reached 8.8. The mixture was then magnetically stirred and aged for 35 min to form a precipitate. The precipitate was washed four times with deionized water, dried in an oven at 102℃ for 4.2 h, calcined at 370℃ for 2.5 h, and then heated to 420℃ at a rate of 3℃ / min and held at that temperature for 5.2 h in a hydrogen atmosphere to obtain the hydrogenation catalyst.

[0038] Example 3 3.5 g of ZSM-5 molecular sieve (CAS No.: 1318-02-1, silica-alumina ratio 300) was added to 400 g of 0.5 mol / L ammonium nitrate solution. After ion exchange by stirring at 70 °C for 5 h, the solid was separated by filtration. The solid was repeatedly washed with deionized water until the filtrate was nearly neutral. It was then dried at 105 °C for 11 h, followed by calcination at 500 °C for 3 h at a rate of 3 °C / min to obtain hydrogen-form ZSM-5. 8.5 g of phosphoric acid was mixed with 30 g of deionized water and stirred for 40 min, then 6 g of... JHN-02 type mesoporous pseudoboehmite was ultrasonically dispersed for 15 min, and 6g of silica was added and stirred for another 60 min to obtain P-Al-Si precursor gel. 3.5g of hydrogen-type ZSM-5, 35g of deionized water, and 7g of di-n-propylamine were mixed and stirred for 12 min, and then added to the P-Al-Si precursor gel and stirred for 135 min. The mixture was transferred to a stainless steel high-pressure reactor and hydrothermally reacted at 170℃ for 22 h. The precipitate was collected by centrifugation, washed twice with deionized water, dried at 108℃ for 11 h, and then calcined in air at a heating rate of 5℃ / min to 575℃ for 5.5 h. The precipitate was added to 400g of 0.5mol / L ammonium nitrate solution and stirred at 70℃ for 5 h for ion exchange. The solid was separated by filtration, and the filtrate was repeatedly washed with deionized water until it was nearly neutral. The filtrate was dried at 105℃ for 11 h to obtain NH4 type ZSM-5 / SAPO-11 composite molecular sieve.

[0039] 0.16 g of ammonium metatungstate was added to 22 g of deionized water and magnetically stirred for 30 min. The pH was adjusted to 3.0 with 0.8 mol / L dilute nitric acid, and 0.15 g of citric acid was added and stirring was continued for 15 min to obtain a tungsten-containing precursor solution. 9 g of NH4 type ZSM-5 / SAPO-11 composite molecular sieve was added to the tungsten-containing precursor solution and stirred and impregnated for 2 h. Then it was allowed to stand and age for 8 h. The solid was separated by vacuum filtration, washed once with deionized water, dried at 105 °C for 11 h, and then placed in air and heated to 500 °C at a heating rate of 3 °C / min and kept at that temperature for 3 h to obtain W-modified hydrogen-type composite molecular sieve.

[0040] 8.5g ferric nitrate, 3.0g nickel nitrate, 170g deionized water, and 80g dimethylformamide were mixed and magnetically stirred for 30 min to obtain a Ni-Fe metal salt solution. 9g W-modified hydrogen-type composite molecular sieve was added to 45g ethanol and ultrasonically treated for 8 min. Under stirring conditions, 250g Ni-Fe metal salt solution was added dropwise, followed by the addition of 3wt% ammonia until the pH of the system reached 9.0. The mixture was then magnetically stirred and aged for 45 min to form a precipitate. The precipitate was washed four times with deionized water, dried in an oven at 105℃ for 4.5 h, calcined at 400℃ for 3 h, and then placed in a hydrogen atmosphere and heated to 450℃ at a rate of 3℃ / min and held at that temperature for 5.5 h to obtain the hydrogenation catalyst.

[0041] Example 4 4g of ZSM-5 molecular sieve (CAS No.: 1318-02-1, silica-alumina ratio 300) was added to 450g of 0.5mol / L ammonium nitrate solution. After ion exchange by stirring at 75℃ for 5.5h, the solid was separated by filtration. The filtrate was repeatedly washed with deionized water until nearly neutral, dried at 108℃ for 11.5h, and then calcined at 525℃ for 3.5h at a rate of 4℃ / min to obtain hydrogen-form ZSM-5. 9.2g of phosphoric acid was mixed with 30g of deionized water and stirred for 45min, then 7g of... JHN-02 type mesoporous pseudoboehmite was ultrasonically dispersed for 18 min, and 6.5 g of silica was added and stirred for another 70 min to obtain P-Al-Si precursor gel. 4 g of hydrogen-type ZSM-5, 40 g of deionized water, and 8 g of di-n-propylamine were mixed and stirred for 14 min, and then added to the P-Al-Si precursor gel and stirred for 145 min. The mixture was transferred to a stainless steel high-pressure reactor and hydrothermally reacted at 175 °C for 23 h. The precipitate was collected by centrifugation, washed twice with deionized water, dried at 109 °C for 11.5 h, and then calcined in air at a heating rate of 5 °C / min to 590 °C for 5.8 h. The precipitate was added to 450 g of 0.5 mol / L ammonium nitrate solution and stirred at 75 °C for 5.5 h for ion exchange. The solid was separated by filtration, repeatedly washed with deionized water until the filtrate was nearly neutral, and dried at 108 °C for 11.5 h to obtain NH4 type ZSM-5 / SAPO-11 composite molecular sieve.

[0042] 0.18 g of ammonium paratungstate was added to 25 g of deionized water and magnetically stirred for 35 min. The pH was adjusted to 2.8 with 0.9 mol / L dilute nitric acid, and 0.20 g of oxalic acid was added and stirring was continued for 18 min to obtain a tungsten-containing precursor solution. 9.5 g of NH4-type ZSM-5 / SAPO-11 composite molecular sieve was added to the tungsten-containing precursor solution and stirred and impregnated for 2.5 h. Then, it was allowed to stand and age for 10 h. The solid was separated by filtration, washed twice with deionized water, dried at 108 °C for 11.5 h, and then calcined in air at a heating rate of 4 °C / min to 525 °C and held for 3.5 h to obtain W-modified hydrogen-type composite molecular sieve.

[0043] 9.2 g of ferric nitrate, 3.2 g of nickel nitrate, 180 g of deionized water, and 90 g of dimethylformamide were mixed and magnetically stirred for 35 min to obtain a Ni-Fe metal salt solution. 9.5 g of W-modified hydrogen-type composite molecular sieve was added to 48 g of ethanol and ultrasonically treated for 9 min. Under stirring conditions, 280 g of Ni-Fe metal salt solution was added dropwise, followed by the addition of 3 wt% ammonia water until the pH of the system reached 9.2. The mixture was then magnetically stirred and aged for 55 min to form a precipitate. The precipitate was washed five times with deionized water, dried in an oven at 108 °C for 4.8 h, calcined at 430 °C for 3.5 h, and then placed in a hydrogen atmosphere and heated to 480 °C at a rate of 3 °C / min and held at that temperature for 5.8 h to obtain the hydrogenation catalyst.

[0044] Example 5 4.5 g of ZSM-5 molecular sieve (CAS No.: 1318-02-1, silica-alumina ratio 300) was added to 480 g of 0.5 mol / L ammonium nitrate solution. After ion exchange by stirring at 78 °C for 5.8 h, the solid was separated by filtration. The filtrate was repeatedly washed with deionized water until nearly neutral, dried at 109 °C for 11.8 h, and then calcined at 540 °C for 3.8 h at a rate of 4.5 °C / min to obtain hydrogen-form ZSM-5. 9.6 g of phosphoric acid was mixed with 30 g of deionized water and stirred for 48 min, then 7.5 g of... JHN-02 type mesoporous pseudoboehmite was ultrasonically dispersed for 19 min, and 6.8 g of silica was added and stirred for another 75 min to obtain P-Al-Si precursor gel. 4.5 g of hydrogen-form ZSM-5, 45 g of deionized water, and 9 g of di-n-propylamine were mixed and stirred for 15 min, then added to the P-Al-Si precursor gel and stirred for 148 min. The mixture was then transferred to a stainless steel high-pressure reactor and hydrothermally reacted at 178 °C for 23.5 h. The precipitate was collected by centrifugation, washed twice with deionized water, dried at 110 °C for 12 h, and then calcined in air at a heating rate of 5 °C / min to 595 °C for 5.9 h. Finally, 480 g of silica was added to the mixture. Ion exchange was carried out by stirring at 78℃ for 5.8 h in a 0.5 mol / L ammonium nitrate solution. The solid was then separated by filtration and washed repeatedly with deionized water until the filtrate was nearly neutral. The filtrate was then dried at 109℃ for 11.8 h to obtain the NH4 type ZSM-5 / SAPO-11 composite molecular sieve.

[0045] 0.20 g of ammonium metatungstate was added to 28 g of deionized water and magnetically stirred for 38 min. The pH was adjusted to 2.7 with 1.0 mol / L dilute nitric acid, and 0.25 g of citric acid was added and stirring was continued for 19 min to obtain a tungsten-containing precursor solution. 9.8 g of NH4 type ZSM-5 / SAPO-11 composite molecular sieve was added to the tungsten-containing precursor solution and stirred and impregnated for 2.8 h. Then, it was allowed to stand and age for 11 h. The solid was separated by vacuum filtration, washed twice with deionized water, dried at 110 °C for 12 h, and then placed in air and heated to 540 °C at a heating rate of 5 °C / min and kept at that temperature for 3.8 h to obtain W-modified hydrogen-type composite molecular sieve.

[0046] 9.6 g of ferric nitrate, 3.4 g of nickel nitrate, 185 g of deionized water, and 95 g of dimethylformamide were mixed and magnetically stirred for 38 min to obtain a Ni-Fe metal salt solution. 9.8 g of W-modified hydrogen-type composite molecular sieve was added to 49 g of ethanol and ultrasonically treated for 10 min. Under stirring conditions, 295 g of Ni-Fe metal salt solution was added dropwise, followed by the addition of 3 wt% ammonia until the pH of the system reached 9.4. The mixture was then magnetically stirred and aged for 58 min to form a precipitate. The precipitate was washed five times with deionized water, dried in an oven at 110 °C for 5 h, calcined at 445 °C for 3.8 h, and then heated to 495 °C at a rate of 3 °C / min and held at that temperature for 5.9 h to obtain the hydrogenation catalyst.

[0047] Example 6 5g of ZSM-5 molecular sieve (CAS No.: 1318-02-1, silica-alumina ratio 300) was added to 500g of 0.5mol / L ammonium nitrate solution. After ion exchange by stirring at 80℃ for 6h, the solid was separated by filtration. The solid was repeatedly washed with deionized water until the filtrate was nearly neutral. It was then dried at 110℃ for 12h, followed by calcination at 550℃ for 4h at a rate of 5℃ / min to obtain hydrogen-form ZSM-5. 10g of phosphoric acid was mixed with 30g of deionized water and stirred for 50min. Then, 8g of… JHN-02 type mesoporous pseudoboehmite was ultrasonically dispersed for 20 min, and 7g of silica was added and stirred for another 80 min to obtain P-Al-Si precursor gel. 5g of hydrogen-type ZSM-5, 50g of deionized water, and 10g of di-n-propylamine were mixed and stirred for 15 min, and then added to the P-Al-Si precursor gel and stirred for 150 min. The mixture was then transferred to a stainless steel high-pressure reactor and hydrothermally reacted at 180℃ for 24 h. The precipitate was collected by centrifugation, washed twice with deionized water, dried at 110℃ for 12 h, and then calcined in air at a heating rate of 5℃ / min to 600℃ for 6 h. The precipitate was added to 500g of 0.5mol / L ammonium nitrate solution and stirred at 80℃ for 6 h for ion exchange. The solid was separated by filtration, repeatedly washed with deionized water until the filtrate was nearly neutral, and dried at 110℃ for 12 h to obtain NH4 type ZSM-5 / SAPO-11 composite molecular sieve.

[0048] 0.22 g of ammonium paratungstate was added to 30 g of deionized water and magnetically stirred for 40 min. The pH was adjusted to 2.5 with 1.0 mol / L dilute nitric acid, and 0.30 g of citric acid was added and stirring was continued for 20 min to obtain a tungsten-containing precursor solution. 10 g of NH4 type ZSM-5 / SAPO-11 composite molecular sieve was added to the tungsten-containing precursor solution and stirred and impregnated for 3 h. Then it was allowed to stand and age for 12 h. The solid was separated by vacuum filtration, washed twice with deionized water, dried at 110 °C for 12 h, and then placed in air and heated to 550 °C at a heating rate of 5 °C / min and kept at that temperature for 4 h to obtain W-modified hydrogen-type composite molecular sieve.

[0049] 10g of ferric nitrate, 3.5g of nickel nitrate, 180g of deionized water, and 90g of dimethylformamide were mixed and magnetically stirred for 40min to obtain a Ni-Fe metal salt solution. 10g of W-modified hydrogen-type composite molecular sieve was added to 50g of ethanol and ultrasonically treated for 10min. Under stirring, 300g of Ni-Fe metal salt solution was added dropwise, followed by the addition of 3wt% ammonia until the pH of the system reached 9.5. The mixture was then magnetically stirred and aged for 60min to form a precipitate. The precipitate was washed five times with deionized water, dried in an oven at 110℃ for 5h, calcined at 450℃ for 4h, and then placed in a hydrogen atmosphere and heated to 500℃ at a rate of 3℃ / min and held at that temperature for 6h to obtain the hydrogenation catalyst.

[0050] The present invention also includes comparative examples and related experiments.

[0051] Comparative Example 1 Compared with Example 2, the only difference is that conventional ZSM-5 molecular sieve is used instead of W-modified hydrogen-type composite molecular sieve. The other preparation methods and components are completely consistent, and the hydrogenation catalyst is finally obtained.

[0052] Comparative Example 2 Compared with Example 2, the only difference is that the NH4 type ZSM-5 / SAPO-11 composite molecular sieve is used instead of the W modified hydrogen type composite molecular sieve. The other preparation methods and components are completely consistent, and the hydrogenation catalyst is finally obtained.

[0053] Comparative Example 3 Compared with Example 2, the only difference is that W-modified hydrogen-type composite molecular sieve is used directly as a hydrogenation catalyst.

[0054] Performance testing I. Physicochemical Properties of Hydrogenation Catalysts: The hydrogenation catalysts prepared in Examples 1-6 and Comparative Examples 1-3 were tested according to GB / T19587-2017 gas adsorption BET method to determine the specific surface area of ​​solid materials, and GB / T21650.2-2008 mercury porosimetry and gas adsorption method to determine the pore size distribution and porosity of solid materials. The specific surface area and pore volume were calculated by t-plot method and BJH model. The specific test results are shown in Table 1.

[0055] Table 1: Physicochemical properties of hydrogenation catalysts

[0056] As shown in Table 1, the specific surface area of ​​the hydrogenation catalysts in Examples 1-6 is 332.45-345.10 m². 2 / g, total pore volume is 0.68~0.73cm³ 3 / g, and with a high proportion of mesoporous volume, in addition to combining Figure 1 and Figure 2 The SEM and TEM images of Example 2 show that the hydrogenation catalyst particles prepared in this invention are short rod-shaped, with a rough shell formed by fine grains on the outer surface accompanied by intergranular pores. The relatively uniform distribution of nanoscale particles on the outer surface indicates that the Ni and Fe metal-supported phases have good dispersibility. This demonstrates that the prepared ZSM-5 / SAPO-11 composite molecular sieve, while maintaining the microporous framework of the molecular sieve, forms a relatively significant intergranular mesoporous and external pore structure, which is beneficial to the diffusion and mass transfer of macromolecular components in heavy coal tar and improves the accessibility of active sites. In contrast, the specific surface area and total pore volume of Comparative Example 1 are significantly reduced, and the mesopore volume is only 0.05 cm³. 3 / g indicates that the conventional system has a more microporous pore structure, which can easily lead to an excessive proportion of macromolecules reacting at the pore opening or outer surface, and may induce coking and deactivation; although the pore structure of Comparative Example 2 has been improved, it is still lower than that of the Example system.

[0057] II. Hydrogenation performance of the hydrogenation catalyst: The reaction temperature and hydrogen pressure were adjusted to 360℃ and 12MPa, respectively, in a 30mL high-pressure fixed-bed reactor. Hydrogen and coal tar were introduced into the reactor to evaluate the hydrogenation performance, with a coal tar volume hourly space velocity of 0.6 h⁻¹. -1 The hydrogen-to-oil volume ratio was 1200:1; the unit operated stably for 200 hours, and samples were taken for analysis at 50 and 200 hours. The properties of the coal tar feedstock are shown in Table 2. (1) Sulfur and nitrogen content: Sulfur content was determined by ultraviolet fluorescence method and nitrogen content was determined by chemiluminescence method, respectively, in accordance with GB / T38395-2019 Determination of sulfur and nitrogen content in coal tar; (2) Carbon residue content: Carbon residue was determined by the micro-method of determination of carbon residue in petroleum products in accordance with GB / T17144-2021. The removal rates of sulfur, nitrogen, and residual carbon are calculated using the following formula:

[0058] The specific calculation results of sulfur, nitrogen and residual carbon removal rates are shown in Table 3; In addition, long-term stability and deactivation resistance were evaluated for Example 2 and Comparative Examples 1-2, and the desulfurization / denitrification activity retention rate was calculated using the following formula:

[0059] The calculation results of the desulfurization / denitrification activity retention rate of the hydrogenation catalyst sample after 200 hours of operation are shown in Table 4.

[0060] Table 2: Properties of Coal Tar Feedstock

[0061] Table 3: Removal rates of sulfur, nitrogen, and residual carbon

[0062] Table 4: Desulfurization / Denitrification Activity Retention Rate of Hydrogenation Catalyst Samples after 200h of Operation

[0063] As shown in Table 3, the hydrogenation catalysts prepared in Examples 1-6 of this invention exhibit significant hydrogenation and depurification capabilities for coal tar: desulfurization rates of 98.43-99.21%, denitrification rates of 95.12-97.01%, and residual carbon removal rates of 87.98-90.33%. Comparative Examples 1 and 2, due to the absence of the W-modified hydrogen-type composite molecular sieve prepared in this invention as a support, showed a significant decrease in hydrogenation and depurification capabilities. Furthermore, Table 4 also shows that Example 2 of this invention maintained high activity after a 200-hour long-term operation, with a desulfurization activity retention rate of 98.2% and a denitrification activity retention rate of 97.4%, demonstrating excellent resistance to deactivation and operational stability. In contrast, the activity retention rates of Comparative Examples 1 and 2 were significantly reduced.

[0064] III. Testing and analysis of the composition and physicochemical properties of the coal tar products in performance test (II): The composition and hydrorefining effect of the reaction raw material coal tar and the hydrogenated oil were evaluated. The distillation range was determined according to GB / T6536-2010 Petroleum Products Atmospheric Distillation Characteristics Determination Method, and the generated oil was cut to obtain fraction samples with boiling points below 315℃. The content of aromatics and olefins in the fraction samples was determined according to GB / T11132-2022 Liquid Petroleum Products Hydrocarbons Determination Fluorescent Indicator Adsorption Method. In addition, the density of the generated oil was determined according to GB / T1884-2000 Petroleum Density Determination, and the kinematic viscosity of the generated oil was determined according to GB / T265-1988 Petroleum Products Kinematic Viscosity Determination Method and Dynamic Viscosity Calculation Method. The specific test results are shown in Table 5.

[0065] Table 5: Composition and Physicochemical Properties of Coal Tar Products

[0066] As shown in Table 5, the density of the final product oil obtained using Examples 1-6 of the present invention was significantly reduced to 874.1-888.5 kg / m³. 3 The kinematic viscosity decreased to 10.6~13.1 mm. 2At the same time, the aromatics mass fraction decreased to 14.2-20.1%, and the olefins mass fraction was only 0.5-0.9%, indicating that the catalyst in the examples could effectively promote aromatics hydrogenation saturation and improve the lightness and fluidity of the generated oil. In contrast, the generated oils obtained using Comparative Examples 1-2 had significantly higher density and kinematic viscosity, and significantly higher aromatics and olefins content, indicating insufficient aromatics saturation and heavy conversion; Comparative Example 3 even showed a density of 1123 kg / m³. 3 Viscosity 85.5 mm 2 The high content of aromatics (67.0%) indicates that it is difficult to effectively promote aromatic hydrogenation saturation, resulting in poor quality of the produced oil.

[0067] In summary, the hydrogenation catalyst prepared by this invention can be well applied to the hydrogenation refining and upgrading process of heavy organic raw materials such as coal tar, achieving a comprehensive effect of efficient deimpurification, inhibition of deactivation, and improvement of product quality in the process of coal tar hydrogenation and upgrading.

[0068] The above are preferred embodiments of the present invention. Those skilled in the art can make several improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a hydrogenation catalyst, characterized in that, Includes the following steps: S1. Hydrogen-type ZSM-5, deionized water, and di-n-propylamine were mixed and stirred, then added to P-Al-Si precursor gel and stirred. The mixture was hydrothermally treated, the precipitate was collected by centrifugation, washed, dried, calcined, added to ammonium nitrate solution, heated and stirred, filtered, washed, and dried to obtain NH4-type ZSM-5 / SAPO-11 composite molecular sieve. The P-Al-Si precursor gel was obtained by mixing 7-10 parts by weight of phosphoric acid and 30 parts by weight of deionized water and stirring for 30-50 min, then adding 4-8 parts by weight of pseudoboehmite and ultrasonically dispersing for 10-20 min, and then adding 5-7 parts by weight of silica and stirring for 40-80 min. S2. NH4-type ZSM-5 / SAPO-11 composite molecular sieve is added to a tungsten-containing precursor solution and stirred for impregnation. After standing and aging, it is filtered, washed, dried, and calcined to obtain a W-modified hydrogen-type composite molecular sieve. The tungsten-containing precursor solution is prepared by adding 0.1-0.22 parts by weight of tungsten salt to 15-30 parts by weight of deionized water, magnetically stirring for 20-40 minutes, adjusting the pH to 2.5-3.5 with dilute nitric acid, adding 0.05-0.30 parts by weight of complexing dispersant, and continuing stirring for 10-20 minutes. S3. The W-modified hydrogen-type composite molecular sieve was added to ethanol and ultrasonically treated. Under stirring conditions, Ni-Fe metal salt solution was added dropwise to adjust the pH to alkaline. The precipitate was aged, washed, dried, calcined, and reduced and activated to obtain the hydrogenation catalyst.

2. The method for preparing a hydrogenation catalyst according to claim 1, characterized in that, The hydrogen form ZSM-5 is obtained by adding 2-5 parts by mass of ZSM-5 molecular sieve to 300-500 parts by mass of 0.5 mol / L ammonium nitrate solution, stirring at 60-80℃ for 4-6 hours for ion exchange, separating the solid by filtration, repeatedly washing with deionized water until the filtrate is nearly neutral, drying at 100-110℃ for 10-12 hours, and then calcining at 450-550℃ for 2-4 hours with a temperature increase of 2-5℃ / min.

3. The method for preparing a hydrogenation catalyst according to claim 1, characterized in that, The pseudoboehmite is JHN-02 type mesoporous pseudoboehmite.

4. The method for preparing a hydrogenation catalyst according to claim 1, characterized in that, In step S1, 2-5 parts by weight of hydrogen-form ZSM-5, 20-50 parts by weight of deionized water, and 5-10 parts by weight of di-n-propylamine are mixed and stirred for 10-15 minutes, then added to the P-Al-Si precursor gel and mixed and stirred for 120-150 minutes. The mixture is then transferred to a stainless steel high-pressure reactor and hydrothermally reacted at 160-180℃ for 20-24 hours. The precipitate is collected by centrifugation, washed 1-2 times with deionized water, and dried at 105-110℃ for 10 minutes. After 12 hours, the mixture is placed in air and calcined at 550-600℃ for 5-6 hours at a heating rate of 5℃ / min. Then, it is added to 300-500 parts by mass of 0.5mol / L ammonium nitrate solution and stirred at 60-80℃ for 4-6 hours for ion exchange. The solid is then separated by filtration and washed repeatedly with deionized water until the filtrate is nearly neutral. Finally, it is dried at 100-110℃ for 10-12 hours to obtain NH4 type ZSM-5 / SAPO-11 composite molecular sieve.

5. The method for preparing a hydrogenation catalyst according to claim 1, characterized in that, The tungsten salt is one of ammonium metatungstate and ammonium paratungstate; the complexing dispersant is one of citric acid and oxalic acid; and the concentration of the dilute nitric acid is 0.5~1.0 mol / L.

6. The method for preparing a hydrogenation catalyst according to claim 1, characterized in that, In step S2, 8-10 parts by mass of NH4-type ZSM-5 / SAPO-11 composite molecular sieve are added to a tungsten-containing precursor solution and stirred and impregnated for 1-3 hours. Then, the mixture is allowed to stand and age for 4-12 hours. The solid is separated by filtration, washed quickly with deionized water 1-2 times, dried at 100-110°C for 10-12 hours, and then placed in air and heated to 450-550°C at a heating rate of 2-5°C / min and kept at that temperature for 2-4 hours to obtain W-modified hydrogen-type composite molecular sieve.

7. The method for preparing a hydrogenation catalyst according to claim 1, characterized in that, The Ni-Fe metal salt solution is obtained by mixing ferric nitrate, nickel nitrate, deionized water, and dimethylformamide, and stirring magnetically for 20-40 minutes.

8. The method for preparing a hydrogenation catalyst according to claim 1, characterized in that, In step S3, 8-10 parts by mass of W-modified hydrogen-type composite molecular sieve are added to 40-50 parts by mass of ethanol and ultrasonically treated for 5-10 minutes. Under stirring conditions, 200-300 parts by mass of Ni-Fe metal salt solution are added dropwise, followed by the addition of 3wt% ammonia water until the pH of the system reaches 8.5-9.

5. The system is then magnetically stirred and aged for 30-60 minutes to form a precipitate. The precipitate is washed 3-5 times with deionized water, dried in an oven at 100-110℃ for 4-5 hours, calcined at 350-450℃ for 2-4 hours, and then placed in a hydrogen atmosphere and heated to 400-500℃ at a rate of 3℃ / min and held at that temperature for 5-6 hours to obtain the hydrogenation catalyst.

9. A hydrogenation catalyst, characterized in that, The catalyst is prepared using the method described in any one of claims 1 to 8, comprising the following raw materials in parts by weight: 8 to 10 parts of W-modified hydrogen-type composite molecular sieve, 40 to 50 parts of ethanol, and 200 to 300 parts of Ni-Fe metal salt solution; wherein the Ni-Fe metal salt solution comprises the following raw materials in parts by weight: 7 to 10 parts of ferric nitrate, 2 to 3.5 parts of nickel nitrate, 150 to 200 parts of deionized water, and 50 to 100 parts of dimethylformamide.

10. The application of a hydrogenation catalyst, characterized in that, The hydrogenation catalyst described in claim 9 is used in the hydrogenation refining and upgrading process of heavy organic feedstocks such as coal tar.

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