A hydrocracking catalyst

Abstract

The present invention discloses a hydrocracking catalyst, which is prepared by a carrier-supported metal complex, wherein the carrier is prepared by a Y / SAPO-34 / ASP composite material containing a crystalline pore wall structure and an aluminum sol. The composite material preparation method comprises the following steps: (1) uniformly adsorbing a slurry obtained after a Y molecular sieve, a long-chain surfactant, and an alkaline aqueous solution mixed and treated onto macroporous silica gel to prepare a Y / silica gel solid mixture; (2) using the Y / silica gel solid mixture obtained in step (1) as a silicon and aluminum source, mixing the mixture with a template, phosphoric acid, an aluminum source, and water, adjusting the pH, and crystallizing the mixture to obtain a Y / SAPO-34 composite material slurry; and (3) mixing the Y / SAPO-34 composite material slurry obtained in step (2) with a silicon source and a long-chain surfactant, adjusting the pH to 8-10, and crystallizing the mixture to obtain a Y / SAPO-34 / ASP composite material containing a crystalline pore wall structure.

Description

Technical Field

[0001] The invention belongs to the technical field of catalysts, and particularly relates to a hydrocracking catalyst. Background Art

[0002] Hydrocracking technology has many advantages, such as strong adaptability to raw materials, flexible processing schemes, high yield of liquid products, and good product quality. In particular, heavy naphtha has a high potential content of aromatics, making it a high-quality raw material for producing aromatics or high-octane gasoline. Hydrogenated tail oil and light naphtha are rich in paraffins and are high-quality feeds for steam cracking ethylene units. At the same time, they can also produce high-quality No. 3 jet fuel and National VI diesel blending components. The core of hydrocracking technology is the hydrocracking catalyst. Hydrocracking catalysts generally adopt the equal volume impregnation method or the excess impregnation method to load the metal solution onto the carrier to obtain a hydrocracking catalyst. This technology currently has the problem of uneven solution in the impregnation process, and excessive metal can easily lead to catalyst drying and pore blockage after calcination, resulting in a large loss of specific surface area and pore volume of the catalyst.

[0003] CN201410711529 discloses a hydrocracking catalyst carrier and its preparation method. The catalyst carrier utilizes a modified Y-type molecular sieve with large crystals, high silicon content, and a concentrated effective pore size distribution as its primary cracking component. The hydrocracking catalyst prepared from this carrier is suitable as a hydrocracking catalyst for the flexible production of high-quality heavy naphtha, jet fuel, and diesel, exhibiting high activity and selectivity. This technology has the following drawbacks or shortcomings relative to the present invention: The metal loading method utilizes a conventional isovolumetric impregnation method, resulting in a high metal content and a low specific surface area of ​​the carrier material after metal loading. This technology also has the drawback of not forming a mesoporous structure rich in crystalline pore walls, resulting in a low content of mesopore channels.

[0004] CN201811521961.1 A hydrocracking catalyst, its preparation method, and application. The catalyst comprises a carrier, an active component, and silica formed by calcining after loading silane, wherein the carrier contains Y molecular sieve and SAPO-34 molecular sieve; the active component comprises a Group VIB metal and a Group VIII metal, and the weight content of silica formed by calcining after loading silane in the catalyst is 0.5wt% to 5wt%. The preparation method of the hydrocracking catalyst comprises: (1) uniformly mixing materials containing Y molecular sieve and SAPO-34 molecular sieve, adding an acidic solution, and drying and calcining after forming to obtain a carrier; (2) introducing active components into the carrier prepared in step (1), wherein the active components are Group VIB and Group VIII metals, and drying and calcining after introduction to obtain a hydrocracking catalyst. The catalyst prepared by this method has a good match between reaction activity and oil selectivity during the hydrocracking reaction, and the product has excellent properties. The defects of this technology or the shortcomings relative to the present invention are: this method is only a mechanical mixing of Y molecular sieve and SAPO-34 molecular sieve. The defect of this technology is that it does not form a mesoporous structure rich in crystal pore walls, the mesoporous channel content is low, and it is mainly used for the production of more intermediate distillates.

[0005] CN201811522285.X, a hydrocracking catalyst carrier and its preparation method and application, the carrier contains Y molecular sieve and SAPO-34 molecular sieve, based on the carrier, the weight content of Y molecular sieve is 2wt% to 35wt%, and the content of SAPO-34 molecular sieve is 2wt% to 25wt%. The preparation method of the carrier comprises: mixing the materials containing Y molecular sieve and SAPO-34 molecular sieve evenly, adding an acidic solution for molding, and drying and calcining after molding to obtain a hydrocracking catalyst carrier. The catalyst prepared by this carrier has high reactivity, medium oil selectivity and excellent product properties during the hydrocracking reaction. The defects of this technology make this method only a mechanical mixing of Y molecular sieve and SAPO-34 molecular sieve. Compared with the present technology, no mesoporous structure rich in crystal pore walls is formed, the mesopore channel content is low, and it is mainly used to produce more middle distillates. Summary of the Invention

[0006] The object of the present invention is to provide a hydrocracking catalyst to solve the problem that the existing catalysts fail to form a mesoporous structure rich in crystal pore walls and have a low content of mesopore channels.

[0007] To achieve the above objectives, the present invention provides a hydrocracking catalyst prepared by a carrier-supported metal complex, wherein the carrier is prepared from a Y / SAPO-34 / ASP composite material having a crystalline pore wall structure and an aluminum sol. The preparation method of the Y / SAPO-34 / ASP composite material having a crystalline pore wall structure comprises the following steps:

[0008] (1) The slurry after the Y molecular sieve, long-chain surfactant, and alkaline aqueous solution are uniformly adsorbed on the macroporous silica gel to prepare a Y / silica gel solid mixture;

[0009] (2) The Y / silica gel solid mixture obtained in step (1) is used as a silicon-aluminum source, mixed with a template, phosphoric acid, an aluminum source, and water, wherein the silicon-aluminum source is calculated as SiO2, the phosphoric acid is calculated as P2O5, and the aluminum source is calculated as Al2O3, and the molar ratio of the feed materials is controlled to be (1-1.5)Al2O3:(1-1.5)P2O5:(1-1.5)SiO2:(1-2)template:(40-80)H2O, the pH is adjusted, and after crystallization, a Y / SAPO-34 composite material slurry is obtained;

[0010] (3) The Y / SAPO-34 composite material slurry obtained in step (2) is mixed with a silicon source and a long-chain surfactant in a mass ratio of 1:(0.01-0.1):(0.01-0.1), the pH is adjusted, and after crystallization, a Y / SAPO-34 / ASP composite material containing a crystalline pore wall structure is obtained.

[0011] The hydrocracking catalyst of the present invention comprises the following steps: step (1) preparing materials according to a mass ratio of Y molecular sieve: long-chain surfactant: alkali: water of 1: (0.05-0.1): (0.05-0.2): (5-10); mixing the materials; stirring at 70-90° C. for 4-10 hours to obtain a mixed slurry containing Y molecular sieve microcrystals; dispersing the mixed slurry in a container through a high-pressure, airflow crushing method to form a humid atmosphere; and then adsorbing the mixed slurry on macroporous silica gel to obtain a Y / silica gel solid mixture.

[0012] The hydrocracking catalyst of the present invention comprises the following steps: in step (2), phosphoric acid is added to water, and then an aluminum source is added and stirred to form a solution B; a Y / silica gel solid mixture, a template and water are mixed to obtain a solid-liquid mixture C; the solid-liquid mixture C is added to the solution B, the pH is adjusted and crystallization is carried out.

[0013] The hydrocracking catalyst of the present invention comprises the following steps: adjusting the pH value to 6.5-7.5, crystallizing at 150-200° C. for 12-24 hours, and obtaining a Y / SAPO-34 composite material slurry.

[0014] The hydrocracking catalyst of the present invention, in step (3), the pH is adjusted to 8-10, and crystallization is carried out at 80-100° C. with stirring for 10-24 hours to obtain a Y / SAPO-34 / ASP composite material having a crystalline pore wall structure, wherein ASP is a mesoporous amorphous silicon-phosphorus-aluminum oxide.

[0015] The hydrocracking catalyst of the present invention further comprises the steps of filtering, washing, ammonium ion exchange and calcination after crystallization in step (3).

[0016] The hydrocracking catalyst of the present invention is calcined at 500-550° C. for 3-5 hours.

[0017] The hydrocracking catalyst of the present invention is prepared by placing 10-20 wt% of aluminum sol into a high-pressure container, pressurizing it to 2-6 MPa, and then spraying it. 3 / min high-speed airflow is broken and carried out to form a wet atmosphere of aluminum sol in the container, so that the Y / SAPO-34 / ASP composite material with crystal pore wall structure and macroporous alumina in the container are fully and evenly adsorbed, and a hydrogenation catalyst carrier is obtained after molding.

[0018] The hydrocracking catalyst of the present invention has a specific surface area of ​​450-610m 2 / g, pore volume 0.50~0.80mL / g, pore size distribution 4~15nm.

[0019] In the hydrocracking catalyst of the present invention, the long-chain surfactant includes one or more of cetyltrimethylammonium bromide, PEG1000 and PEG2000; the aluminum source includes pseudo-boehmite; the silicon source includes silica sol and / or water glass; and the template agent includes one or more of triethylamine, morpholine and tetraethylammonium hydroxide.

[0020] The hydrocracking catalyst of the present invention has a unit cell of Y molecular sieve of 24.32 to 24.42.

[0021] The hydrocracking catalyst of the present invention is prepared by: pressurizing a 15-25 wt% metal complex solution to 2-6 MPa and then spraying it out; then spraying it vertically at a flow rate of 10-20 m / s. 3 / min high-speed air flow is ejected to form a moist atmosphere containing metal solution in the container, and then the carrier is placed in the container for full adsorption to obtain a hydrocracking catalyst with a specific surface area of ​​350-500m 2 / g, pore volume 0.35~0.65mL / g, pore size distribution 4~12nm.

[0022] The hydrocracking catalyst of the present invention is prepared by the following method: the metal complex solution includes a solution formed by one or more of tungsten salts, molybdenum salts and nickel salts and 2,2-bipyridine and / or 1,10-phenanthroline chelates.

[0023] Beneficial effects of the present invention:

[0024] The present invention uses a Y / SAPO-34 / ASP composite material containing a crystalline pore wall structure to prepare a hydrogenation catalyst, thereby improving the stability of the catalyst's mesoporous channels. Because the metal solution is highly dispersed into a humid atmosphere in this technology, the metal dispersion is improved during the metallization process, the number of effective active centers is increased, and the problem of catalyst pore blockage and loss of specific surface area and pore volume due to local excess metal is reduced, thereby improving the catalyst's specific surface area, pore volume, and pore diameter. The present invention uses a Y / SAPO-34 / ASP composite material containing a crystalline pore wall structure to prepare a hydrogenation catalyst carrier. The carrier contains a mesoporous structure of Y molecular sieve and SAPO-34 molecular sieve microcrystals and secondary structural unit microcrystals, which improves the mesopore stability of the carrier. DETAILED DESCRIPTION

[0025] The present invention is described in detail below by way of examples. It is necessary to point out that the following examples are only used to further illustrate the present invention and are not to be construed as limiting the scope of protection of the present invention. Those skilled in the art may make some non-essential improvements and adjustments to the present invention based on the above disclosure.

[0026] Example 1

[0027] (1) Using a unit cell of 24.32 and a specific surface area of ​​550m 2 / g, a pore volume of 0.40 mL / g, and an average pore diameter of 2.6 nm, Y molecular sieve, according to the mass ratio of Y molecular sieve: hexadecyltrimethylammonium bromide: potassium hydroxide: water of 1:0.05:0.05:5, the Y molecular sieve is dispersed in an aqueous solution of hexadecyltrimethylammonium bromide and potassium hydroxide, and stirred at a constant temperature of 70 ° C for 10 h to obtain a mixed slurry containing Y molecular sieve microcrystals;

[0028] (2) Add the mixed slurry containing Y molecular sieve microcrystals into the container, pressurize it to 2MPa, spray the solution, and then spray it at a flow rate of 10m / s perpendicular to the spray direction. 3 / min high-speed air flow is ejected to form a humid atmosphere in the container, and the macroporous silica gel with a pore volume of 1.0 ml / g is placed in the humid atmosphere, so that the macroporous silica gel fully absorbs the above mixed slurry to obtain Y / silica gel solid mixture A.

[0029] (3) 23 g of phosphoric acid was added to 41 g of deionized water, followed by 13.5 g of aluminum sol (65% Al2O3), and the mixture was stirred thoroughly for 5 hours to form solution B. 6 g of Y / silica gel solid mixture A was mixed with 15 g of triethylamine and 50 g of water to obtain a solid-liquid mixture C. The solid-liquid mixture C was added to solution B, and the pH was adjusted to 6.5 to obtain a solid-liquid mixture D, which was crystallized at 200°C for 12 hours to obtain a Y / SAPO-34 molecular sieve composite slurry.

[0030] (4) 10 g of silica sol (SiO2 content 30 wt%) and 3 g of PEG2000 were added to the above Y / SAPO-34 molecular sieve composite material slurry, the pH value of the system was adjusted to 10, and the mixture was stirred and crystallized at 80 ° C for 24 hours. The product was filtered, washed, and ammonium ion exchanged, and calcined at 500 ° C for 4 hours to obtain a mesoporous Y / SAPO-34 / ASP composite material with a crystalline pore wall structure and a specific surface area of ​​680 m 2 / g, pore volume 0.60mL / g, pore size distribution 4~12nm.

[0031] (5) 27 g of the prepared Y / SAPO-34 / ASP composite material containing a crystalline pore wall structure and 27 g of macroporous alumina (specific surface area 400 m 2 / g, pore volume 1.0mL / g, pore size distribution 4-8nm) were mixed evenly and placed in a container, and then 50g of 10wt% aluminum sol was placed in the container and pressurized to 2MPa and then sprayed out, and then the flow rate was 10m 3 / min high-speed airflow is carried out to form a moist atmosphere of aluminum sol in the container, so that the composite material and alumina are fully and evenly adsorbed. After molding, a hydrogenation catalyst carrier with a specific surface area of ​​610m 2 / g, pore volume 0.50mL / g, pore size distribution 4~12nm.

[0032] (6) 15g of 17wt% ammonium molybdate, 5g of 3wt% ammonium metatungstate, 5g of 3wt% nickel nitrate aqueous solution and 4g of 12wt% 2,2-bipyridine form a metal complex solution, pressurize the metal complex solution to 6MPa and then spray it out, and then spray it vertically at a flow rate of 20m 3 / min high-speed air flow is ejected to form a humid atmosphere containing metal solution in the container, and then the carrier is placed in the container and fully adsorbed evenly to obtain a hydrocracking catalyst. The mass ratio of metal complex solution to carrier is 3:7, and the specific surface area of ​​the prepared catalyst is 500m 2 / g, pore volume 0.35mL / g, pore size distribution 4~12nm.

[0033] Example 2

[0034] (1) Using a unit cell of 24.37 and a specific surface area of ​​560m 2 / g, a pore volume of 0.41 mL / g, and an average pore size of 2.7 nm, Y molecular sieve, according to the mass ratio of Y molecular sieve: PEG2000: potassium hydroxide: water of 1:0.07:0.07:5, the Y molecular sieve was dispersed in an aqueous solution of PEG2000 and potassium hydroxide, and stirred at a constant temperature of 80 ° C for 7 h to obtain a mixed slurry containing Y molecular sieve microcrystals;

[0035] (2) Add the mixed slurry containing Y molecular sieve microcrystals into the container, pressurize it to 4MPa, spray the solution, and then spray it at a flow rate of 15m / s perpendicular to the spray direction. 3 A high-speed air flow of 1 / min was ejected to form a humidified atmosphere in the container. The macroporous silica gel with a pore volume of 2.5 ml / g was placed in the humidified atmosphere to fully absorb the mixed slurry to obtain a Y / silica gel solid mixture A.

[0036] (3) 28.7 g of phosphoric acid was added to 51 g of deionized water, followed by 16.8 g of aluminum sol (65% Al2O3), and the mixture was stirred thoroughly for 7.5 hours to form solution B. 6.5 g of Y / silica gel solid mixture A was mixed with 17 g of tetraethylammonium hydroxide and 55 g of water to obtain a solid-liquid mixture C. The solid-liquid mixture C was added to solution B, and the pH was adjusted to 7.5 to obtain a solid-liquid mixture D, which was crystallized at 200°C for 18 hours to obtain a Y / SAPO-34 molecular sieve composite slurry.

[0037] (4) 10 g of silica sol (SiO2 content 30 wt%) and 5 g of PEG1000 were added to the above Y / SAPO-34 molecular sieve composite material slurry, the pH value of the system was adjusted to 8, and the mixture was stirred and crystallized at 90 ° C for 16 hours. The product was filtered, washed, and ammonium ion exchanged, and calcined at 550 ° C for 3 hours to obtain a mesoporous Y / SAPO-34 / ASP composite material with a crystalline pore wall structure and a specific surface area of ​​590 m 2 / g, pore volume 0.80mL / g, pore size distribution 4~14nm.

[0038] (5) 32.5 g of the prepared Y / SAPO-34 / ASP composite material containing a crystalline pore wall structure and 32.5 g of macroporous alumina (specific surface area 350 m 2 / g, pore volume 1.2mL / g, pore size distribution 6-10nm) were mixed evenly and placed in a container, and then 43g of 15wt% aluminum sol was placed in a high-pressure container and pressurized to 2MPa and then sprayed out, and then the flow rate was 10m 3 / min high-speed airflow is carried out to form a moist atmosphere of aluminum sol in the container, so that the composite material and alumina are fully and evenly adsorbed. After molding, a hydrogenation catalyst carrier with a specific surface area of ​​520m 2 / g, pore volume 0.65mL / g, pore size distribution 4~13nm.

[0039] (6) 15g of 14.5wt% ammonium molybdate, 5g of 3wt% ammonium metatungstate, 5g of 3wt% nickel nitrate aqueous solution and 4g of 10wt% 1,10-phenanthroline form a metal complex solution, pressurize the metal complex solution to 4MPa and then spray it out, and then spray it vertically at a flow rate of 15m 3 / min high-speed air flow is ejected to form a humid atmosphere containing metal solution in the container, and then the carrier is placed in the container and fully adsorbed evenly to obtain a hydrocracking catalyst. The mass ratio of metal complex solution to carrier is 3:7, and the specific surface area of ​​the prepared catalyst is 410m 2 / g, pore volume 0.55mL / g, pore size distribution 4~13nm.

[0040] Example 3

[0041] (1) Using a unit cell of 24.42 and a specific surface area of ​​580m 2 / g, a pore volume of 0.42 mL / g, and an average pore size of 3.0 nm, Y molecular sieve, according to the mass ratio of Y molecular sieve: PEG1000: potassium hydroxide: water of 1:0.1:0.2:10, the Y molecular sieve was dispersed in an aqueous solution of PEG1000 and potassium hydroxide, and stirred at a constant temperature of 90 ° C for 4 h to obtain a mixed slurry containing Y molecular sieve microcrystals;

[0042] (2) Add the mixed slurry containing Y molecular sieve microcrystals into the container, pressurize it to 6MPa, spray the high-pressure solution out, and then spray it vertically at a flow rate of 20m 3 A high-speed air flow of 1 / min was ejected to form a humidified atmosphere in the container. The macroporous silica gel with a pore volume of 3.5 ml / g was placed in the humidified atmosphere to fully absorb the mixed slurry to obtain a Y / silica gel solid mixture A.

[0043] (3) 34.5 g of phosphoric acid was added to 61.5 g of deionized water, and then 20.2 g of aluminum sol (65% Al2O3) was added, and the mixture was stirred thoroughly for 10 hours to form solution B. 9 g of Y / silica gel solid mixture A was mixed with 26 g of morpholine and 75 g of water to obtain solid-liquid mixture C. Solid-liquid mixture C was added to solution B, and the pH was adjusted to 7 to obtain solid-liquid mixture D, which was crystallized at 200°C for 24 hours to obtain a Y / SAPO-34 molecular sieve composite slurry.

[0044] (4) 15 g of water glass (SiO2 content 35 wt%) and 8 g of cetyltrimethylammonium bromide were added to the above Y / SAPO-34 molecular sieve composite material slurry, the pH value of the system was adjusted to 9, and crystallization was carried out at 100 ° C for 10 hours. The product was filtered, washed, and ammonium ion exchanged, and calcined at 600 ° C for 2 hours to obtain a mesoporous Y / SAPO-34 / ASP composite material with a crystalline pore wall structure and a specific surface area of ​​500 m 2 / g, pore volume 1.0mL / g, pore size distribution 4~15nm.

[0045] (5) 40 g of the prepared Y / SAPO-34 / ASP composite material containing a crystalline pore wall structure and 40 g of macroporous alumina (specific surface area 300 m 2 / g, pore volume 1.4mL / g, pore size distribution 8-12nm) were mixed evenly and placed in a container, 40g of 20wt% aluminum sol was placed in a high-pressure container and pressurized to 2MPa and then sprayed out, and then the flow rate was 10m 3 / min high-speed airflow is carried out to form a moist atmosphere of aluminum sol in the container, so that the composite material and alumina are fully and evenly adsorbed. After molding, a hydrogenation catalyst carrier with a specific surface area of ​​450m 2 / g, pore volume 0.80mL / g, pore size distribution 4~15nm.

[0046] (6) The carrier is placed in a container, 15g of 13wt% ammonium metatungstate and 5g of 2wt% nickel salt aqueous solution are mixed with 4g of 8wt% 1,10-phenanthroline to form a metal complex solution, the metal complex solution is pressurized to 2MPa and then sprayed out, and then the flow rate is perpendicular to the spray direction at 10m 3 / min high-speed air flow is ejected to form a moist atmosphere containing metal solution in the container, so that the carrier is fully adsorbed to obtain a hydrocracking catalyst. The mass ratio of metal complex solution to carrier is 3:7. The specific surface area of ​​the prepared catalyst is 350m 2 / g, pore volume 0.65mL / g, pore size distribution 4~14nm.

[0047] Comparative Example 1

[0048] (1) Using a unit cell of 24.44 and a specific surface area of ​​530m 2 / g, a pore volume of 0.39 mL / g, and an average pore diameter of 2.2 nm, Y molecular sieve, according to the mass ratio of Y molecular sieve: hexadecyltrimethylammonium bromide: potassium hydroxide: water of 1:0.03:0.03:15, the Y molecular sieve is dispersed in an aqueous solution of hexadecyltrimethylammonium bromide and potassium hydroxide, and stirred at a constant temperature of 100 ° C for 5 h to obtain a mixed slurry containing Y molecular sieve microcrystals;

[0049] (2) Add the mixed slurry containing Y molecular sieve microcrystals into the container, pressurize it to 1.5MPa, spray the solution, and then spray it at a flow rate of 5m / s perpendicular to the spray direction. 3 / min high-speed air flow is ejected to form a humid atmosphere in the container, and the macroporous silica gel with a pore volume of 1.0 ml / g is placed in the humid atmosphere, so that the macroporous silica gel fully absorbs the above mixed slurry to obtain Y / silica gel solid mixture A.

[0050] (3) 11 g of phosphoric acid was added to 20 g of deionized water, followed by 7 g of aluminum sol (65% Al2O3), and the mixture was stirred thoroughly for 3 hours to form solution B. 3 g of Y / silica gel solid mixture A was mixed with 7 g of triethylamine and 25 g of water to obtain a solid-liquid mixture C. The solid-liquid mixture C was added to solution B, and the pH was adjusted to 6.2 to obtain a solid-liquid mixture D, which was crystallized at 180°C for 15 hours to obtain a Y / SAPO-34 molecular sieve composite slurry.

[0051] (4) 5 g of silica sol (SiO2 content 35 wt%) and 2 g of PEG2000 were added to the above Y / SAPO-34 molecular sieve composite material slurry, the pH value of the system was adjusted to 10, and the mixture was stirred and crystallized at 85 ° C for 20 hours. The product was filtered, washed, and ammonium ion exchanged, and calcined at 470 ° C for 5 hours to obtain a mesoporous Y / SAPO-34 / ASP composite material with a crystalline pore wall structure and a specific surface area of ​​640 m 2 / g, pore volume 0.50mL / g, pore size distribution 4~8nm.

[0052] (5) 27 g of the prepared Y / SAPO-34 / ASP composite material containing a crystalline pore wall structure and 27 g of macroporous alumina (specific surface area 300 m 2 / g, pore volume 0.8mL / g, pore size distribution 4-8nm) were mixed evenly and placed in a container, 50g of 10wt% aluminum sol was placed in a high-pressure container and pressurized to 2MPa and then sprayed out, and then the flow rate was 10m 3 / min high-speed airflow is carried out to form a wet atmosphere of aluminum sol in the container, so that the composite material and alumina are fully and evenly adsorbed. After molding, a hydrogenation catalyst carrier with a specific surface area of ​​410m 2 / g, pore volume 0.45mL / g, pore size distribution 4~8nm.

[0053] (6) The carrier is placed in a container, 15 g of 13 wt% tungsten salt and 5 g of 2 wt% nickel salt aqueous solution are mixed with 4 g of 8 wt% 1,10-phenanthroline to form a metal complex solution, the metal complex solution is pressurized to 2 MPa and then sprayed out, and then the flow rate is perpendicular to the spray direction at 10 m 3 / min high-speed air flow is ejected to form a moist atmosphere containing metal solution in the container, so that the carrier is fully adsorbed to obtain a hydrocracking catalyst. The mass ratio of metal complex solution to carrier is 3:7. The obtained catalyst has a specific surface area of ​​350m 2 / g, pore volume 0.43mL / g, pore size distribution 4~9nm.

[0054] The catalysts prepared in Examples 1 to 3 and Comparative Example 1 were subjected to hydrocracking performance tests.

[0055] Table 1 Properties of crude oil

[0056]

[0057] Table 2 Catalyst evaluation results

[0058] project Example 1 Example 2 Example 3 Comparative Example 1 Reaction temperature, °C 378 375 372 378 Light naphtha, wt% 9.0 13.7 11.80 6.0 Heavy naphtha, wt% 17.5 34.4 52.50 15.5 Jet fuel, wt% 34 43.9 15.00 35 Diesel, wt% 38 8.0 5.5 41 Tail oil, wt% / / 12.70 /

[0059] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art may make various corresponding changes and modifications based on the present invention, but these corresponding changes and modifications should all fall within the scope of protection of the claims of the present invention.

Claims

1. A hydrocracking catalyst, characterized in that The metal complex is prepared by loading the carrier, wherein the carrier is prepared from a Y / SAPO-34 / ASP composite material having a crystalline pore wall structure and aluminum sol, wherein the ASP is a mesoporous amorphous silicon-phosphorus-aluminum oxide. The preparation method of the Y / SAPO-34 / ASP composite material having a crystalline pore wall structure comprises the following steps: (1) The slurry after the Y molecular sieve, long-chain surfactant, and alkaline aqueous solution are uniformly adsorbed on the macroporous silica gel to prepare a Y / silica gel solid mixture; (2) The Y / silica gel solid mixture obtained in step (1) is used as a silicon-aluminum source, mixed with a template, phosphoric acid, an aluminum source, and water, wherein the silicon-aluminum source is calculated as SiO2, the phosphoric acid is calculated as P2O5, and the aluminum source is calculated as Al2O3, and the molar ratio of the feed materials is controlled to be (1-1.5) Al2O3: (1-1.5) P2O5: (1-1.5) SiO2: (1-2) template: (40-80) H2O, and the pH is adjusted. After crystallization, a Y / SAPO-34 composite material slurry is obtained; (3) The Y / SAPO-34 composite material slurry obtained in step (2) is mixed with a silicon source and a long-chain surfactant in a mass ratio of 1:(0.01-0.1):(0.01-0.1), the pH is adjusted, and after crystallization, a Y / SAPO-34 / ASP composite material containing a crystalline pore wall structure is obtained.

2. The hydrocracking catalyst according to claim 1, characterized in that Step (1) preparing materials according to a mass ratio of Y molecular sieve: long-chain surfactant: alkali: water of 1: (0.05-0.1): (0.05-0.2): (5-10), mixing the above materials, stirring at 70-90° C. for 4-10 hours to obtain a mixed slurry containing Y molecular sieve microcrystals, dispersing the mixed slurry in a container through a high-pressure, airflow crushing method to form a humid atmosphere, and then adsorbing the mixed slurry on macroporous silica gel to obtain a Y / silica gel solid mixture.

3. The hydrocracking catalyst according to claim 1, characterized in that In step (2), phosphoric acid is added to water, and then an aluminum source is added and stirred to form a solution B; a Y / silica gel solid mixture, a template and water are mixed to obtain a solid-liquid mixture C, and the solid-liquid mixture C is added to the solution B, the pH is adjusted, and crystallization is carried out.

4. The hydrocracking catalyst according to claim 1 or 3, characterized in that Step (2) adjusting the pH value to 6.5-7.5, crystallizing at 150-200° C. for 12-24 hours to obtain a Y / SAPO-34 composite material slurry.

5. The hydrocracking catalyst according to claim 1, characterized in that Step (3) adjusting the pH to 8-10, stirring and crystallizing at 80-100° C. for 10-24 hours to obtain a Y / SAPO-34 / ASP composite material containing a crystal pore wall structure, wherein ASP is a mesoporous amorphous silicon-phosphorus-aluminum oxide.

6. The hydrocracking catalyst according to claim 1, characterized in that After crystallization in step (3), the process further includes filtering, washing, ammonium ion exchange and calcination steps.

7. The hydrocracking catalyst according to claim 6, characterized in that The calcination conditions are 500-550°C for 3-5 hours.

8. The hydrocracking catalyst according to claim 1, characterized in that The preparation method of the carrier is as follows: 10-20 wt% aluminum sol is placed in a high pressure container and pressurized to 2-6 MPa and then sprayed; and then a flow rate of 10-20 m / s is perpendicular to the spraying direction of the aluminum sol. 3 / min high-speed airflow is broken and carried out to form a wet atmosphere of aluminum sol in the container, so that the Y / SAPO-34 / ASP composite material with crystal pore wall structure and macroporous alumina in the container are fully and evenly adsorbed, and a hydrogenation catalyst carrier is obtained after molding.

9. The hydrocracking catalyst according to claim 1, characterized in that The specific surface area of ​​the catalyst carrier is 450-610m 2 / g, pore volume 0.50~0.80 mL / g, pore size distribution 4~15nm.

10. The hydrocracking catalyst according to claim 1, characterized in that The long-chain surfactant includes one or more of cetyltrimethylammonium bromide, PEG1000 and PEG2000; the aluminum source includes pseudo-boehmite; the silicon source includes silica sol and / or water glass; and the template includes one or more of triethylamine, morpholine and tetraethylammonium hydroxide.

11. The hydrocracking catalyst according to claim 1, characterized in that The unit cell of Y molecular sieve is 24.32~24.

42.

12. The hydrocracking catalyst according to claim 1, characterized in that The preparation method of the catalyst is as follows: pressurizing a 15-25 wt% metal complex solution to 2-6 MPa and then spraying it out; then, spraying the solution vertically at a flow rate of 10-20 m / s. 3 / min high-speed air flow is ejected to form a moist atmosphere containing metal solution in the container, and then the carrier is placed in the container for full adsorption to obtain a hydrocracking catalyst with a specific surface area of ​​350-500m 2 / g, pore volume 0.35~0.65 mL / g, pore size distribution 4~12nm.

13. The hydrocracking catalyst according to claim 12, characterized in that The preparation method of the catalyst is as follows: the metal complex solution includes a solution formed by one or more of tungsten salt, molybdenum salt and nickel salt and 2,2-bipyridine and / or 1,10-phenanthroline chelate.

Images