阅读说明：本技术 一种加氢裂化催化剂及其制备方法与应用 (Hydrocracking catalyst, and preparation method and application thereof ) 是由 谢方明 刘百军 许庆峰 李海岩 张司雨 孙发民 田宏宇 于 2020-05-27 设计创作，主要内容包括：本发明公开了一种含Y/β/ASA复合材料的加氢裂化催化剂及其制备方法与应用。催化剂的载体中含有含Y/β/ASA复合材料,活性组分包括至少一种第VIB族金属和至少一种第VIII族金属。该发明将Y分子筛、β分子筛和无定形硅铝进行原位复合,合成含Y/β/ASA的具有微孔-介孔及核壳包覆结构的复合材料,进而与粘结剂、助挤剂混捏制得载体,再经含活性组分的浸渍液浸渍制备催化剂。本发明制备的催化剂的比表面积较大,孔容较大,孔径范围分布广,且红外酸量较大,具有原料适应性强,裂解活性好,产物收率高,产品质量好等优点,适用于加氢裂化反应生产不同目的产品的工艺过程。(The invention discloses a hydrocracking catalyst containing a Y/beta/ASA composite material and a preparation method and application thereof. The carrier of the catalyst contains a Y/beta/ASA-containing composite material, and the active components comprise at least one VIB group metal and at least one VIII group metal. The method comprises the steps of carrying out in-situ compounding on a Y molecular sieve, a beta molecular sieve and amorphous silica-alumina to synthesize a Y/beta/ASA-containing composite material with a micropore-mesopore and core-shell coating structure, further mixing and kneading the Y/beta/ASA-containing composite material with a binder and an extrusion aid to prepare a carrier, and then impregnating the carrier with an impregnation solution containing active components to prepare the catalyst. The catalyst prepared by the method has the advantages of large specific surface area, large pore volume, wide pore size range distribution, large infrared acid amount, strong raw material adaptability, good cracking activity, high product yield, good product quality and the like, and is suitable for the technological process of producing different target products by hydrocracking reaction.)

1. A hydrocracking catalyst contains a carrier and an active component, and is characterized in that the carrier comprises a Y/beta/ASA composite material, a binder and an extrusion aid, the carrier is formed by mixing a Y molecular sieve and a beta molecular sieve, then carrying out in-situ compounding on the mixture and amorphous silica-alumina to synthesize a Y/beta/ASA-containing composite material with a micropore-mesopore and core-shell coating structure, and the Y/beta/ASA-containing composite material is mixed and kneaded with the binder and the extrusion aid to prepare the carrier; the active component comprises at least one of VIB group metal tungsten or molybdenum and at least one of VIII group metal nickel or cobalt;

the hydrocracking catalyst comprises 60-90 wt% of a carrier and 40-10 wt% of an active component, based on the weight content of the catalyst;

the carrier comprises 60-94 wt% of Y/beta/ASA composite material, 35-5 wt% of binder and 5-1 wt% of extrusion aid according to the weight content of the carrier;

the Y/beta/ASA composite material comprises, by weight, 10-90 wt% of amorphous silica-alumina and 90-10 wt% of molecular sieve; in the molecular sieve, the content of the Y molecular sieve is 0-100 wt%, and the content of the beta molecular sieve is 100-0 wt%;

the active component comprises 3-37 wt% of VIB group metal and 37-3 wt% of VIII group metal based on the weight of the catalyst.

2. The hydrocracking catalyst according to claim 1, characterized in that: the specific surface area of the Y molecular sieve is 500-900 m²A total pore volume of 0.3 to 0.5mL/g, a unit cell constant of 2.426 to 2.682nm, SiO₂/Al₂O₃The molar ratio is 5-20, and the relative crystallinity is 80-90%; SiO of the beta molecular sieve₂/Al₂O₃The molar ratio is 10-120, and the specific surface area is 200-300 m²The total pore volume is 0.4-0.8 mL/g, and the pore diameter is 6-20 nm.

3. The hydrocracking catalyst according to claim 1, characterized in that: the specific surface area of the hydrocracking catalyst is 200-400 m²(iv) per gram, pore volume of 0.6-1.0 mL/g, pore diameter of 8.0-13.0 nm, and infrared acid amount of 100-500 [ mu ] mol/g.

4. A process for preparing a hydrocracking catalyst as claimed in any one of claims 1 to 3, characterized in that: a fractional precipitation method or a coprecipitation method is adopted.

5. The method of claim 4, wherein: the preparation process of the fractional precipitation method comprises the following steps:

(1) uniformly mixing the Y molecular sieve and the beta molecular sieve;

(2) adding an aluminum source and a precipitator into the molecular sieve in the step (1) at the same time, gelatinizing and aging to obtain a gelatinous mixture;

(3) adding a silicon source into the gel-like mixture obtained in the step (2), reacting and aging to obtain slurry;

(4) filtering, washing and drying the slurry obtained in the step (3) to obtain a Y/beta/ASA composite material;

(5) uniformly mixing the Y/beta/ASA composite material obtained in the step (4) with a binder and an extrusion aid, kneading, extruding, drying and roasting to obtain a carrier;

(6) and (3) dipping the carrier obtained in the step (5) by using a metal solution containing VIII group and VIB group metal compounds, drying and roasting to obtain the hydrocracking catalyst.

6. The method of claim 5, wherein: the aluminum source is at least one of sodium aluminate, aluminum sulfate, aluminum chloride and aluminum nitrate, preferably aluminum sulfate.

7. The method of claim 5, wherein: the precipitant is at least one of sodium hydroxide aqueous solution, ammonia aqueous solution and ammonium carbonate aqueous solution, preferably ammonia aqueous solution.

8. The method of claim 5, wherein: the silicon source is at least one of silica sol, water glass and white carbon black, and the water glass is preferred.

9. The method of claim 5, wherein: the binder is at least one of aluminum sol, silica sol, kaolin and methyl cellulose, and the aluminum sol is preferred.

10. The method of claim 5, wherein: the extrusion aid is sesbania powder.

11. The method of claim 5, wherein: the group VIII and VIB metal compounds are at least one of ammonium metatungstate, ammonium tungstate, ammonium molybdate, nickel nitrate and nickel chloride, and preferably ammonium metatungstate and nickel nitrate.

12. The method of claim 5, wherein: the content of ammonium metatungstate is 5-35 wt%, and the content of nickel nitrate is 35-5 wt%.

13. The method of claim 5, wherein: in the step (2), the gelling temperature is 40-100 ℃, and preferably 50-90 ℃; the gelling time is 0-240 min, preferably 10-180 min; the pH value of the gel is 5-10, preferably 6-9; the aging temperature is 40-100 ℃, preferably 50-90 ℃; the aging time is 0-240 min, preferably 10-180 min; the aging pH is 5-10, preferably 6-9.

14. The method of claim 5, wherein: in the step (3), the reaction temperature is 40-100 ℃, and preferably 50-90 ℃; the reaction time is 0-240 min, preferably 10-180 min; the reaction pH is 5-10, preferably 6-9; the aging temperature is 40-100 ℃, preferably 50-90 ℃; the aging time is 0-240 min, preferably 10-180 min; the aging pH is 5-10, preferably 6-9.

15. The method of claim 5, wherein: in the step (4), hot water with the temperature of 50-100 ℃ is adopted for washing until the filtrate is neutral.

16. The method of claim 5, wherein: in the step (5), the drying temperature is 100-150 ℃, and preferably 120 ℃; the drying time is 3-12 h, preferably 4-6 h; the roasting temperature is 450-600 ℃, and preferably 500-550 ℃; the roasting time is 2-5 h, preferably 3-4 h.

17. The method of claim 5, wherein: in the step (6), the drying temperature is 100-150 ℃, and preferably 120 ℃; the drying time is 3-12 h, preferably 4-6 h; the roasting temperature is 450-600 ℃, and preferably 500-550 ℃; the roasting time is 2-5 h, preferably 3-4 h.

18. An application of the catalyst according to any one of claims 1 to 17 in oil conversion in hydrocracking reactions.

Technical Field

The invention relates to a hydrocracking catalyst, and in particular relates to a hydrocracking catalyst containing a Y/beta/ASA composite material, and a preparation method and application thereof.

Background

With the increasing rigor of environmental regulations and fuel oil specification indexes, along with the problems of uneven oil product proportion distribution and high difficulty in oil product quality upgrading in China, the oil product distribution is changed by developing a new process, a new catalyst, optimizing a production scheme and the like, and the improvement of the oil product quality becomes a necessary way for the refining enterprises to realize the efficient development. The hydrocracking technology has the advantages of flexible production scheme, strong raw material adaptability, high target product selectivity, good product quality and the like, and has increasingly prominent importance and increasingly wide industrial application.

The core of hydrocracking technology is a hydrocracking catalyst. The hydrocracking catalyst is a bifunctional catalyst consisting of a hydrogenation component with a hydrogenation function and an acid component with a cracking function. The hydrogenation function is usually provided by a metal with hydrogenation function, which plays a role of hydrogenation/dehydrogenation in the reaction process, provides a reaction raw material for the acid center, and timely saturates the acid center product to prevent deep cracking. The cracking component is mainly provided by an acidic amorphous silica-alumina or zeolite molecular sieve. The cracking components of the hydrocracking catalysts which are currently commercialized are generally based on molecular sieves and amorphous silica-alumina. The most used molecular sieves are Y molecular sieves and beta molecular sieves. The Y-type molecular sieve has the characteristics of strong acidity, good structural stability, good activity, high cracking performance, strong ring opening performance and the like, but has the problems of small aperture, narrow and long pore channel and the like, reaction raw materials such as macromolecular organic matters are difficult to enter the inside of the pore channel, so the utilization rate of an acid position in the pore channel of the molecular sieve is reduced, meanwhile, the pore channel is narrow and long, diffusion resistance is increased, reaction can influence the rapid diffusion overflow of reaction products, the yield of distillate oil is low, the octane number of a product is low and the like. Compared with a Y molecular sieve, the beta molecular sieve has a three-dimensional twelve-membered ring pore channel structure, although the beta molecular sieve is similar to a super cage structure of the Y molecular sieve, the beta molecular sieve has a double six-membered ring unit crystal cavity structure of two four-membered rings and four five-membered rings, the diameter of a main pore channel is 0.56-0.75 nm, the pore channel of the beta molecular sieve is larger than that of the Y molecular sieve, the beta molecular sieve is favorable for molecular diffusion, and can have better selectivity and isomerization performance in a hydrocracking reaction. Compared with molecular sieve, amorphous silica-alumina is used as cracking component, although the number of acid centers is small and the cracking activity is low, the amorphous catalyst has the characteristics of good distillate oil selectivity, high liquid yield, low hydrogen consumption, small product distribution change in the operation period and the like, so that the amorphous catalyst is widely applied to industry.

Although the hydrocracking catalyst containing single cracking component has advantages, the disadvantages are obvious, and the catalyst containing composite cracking component can integrate the advantages, thereby not only improving the reaction activity, but also improving the yield of target products.

US6174429 discloses a hydrocracking catalyst, which comprises 1-99 wt% of at least one acidified aluminum-containing amorphous matrix, 0.1-80 wt% of a crystalline grain parameter of 2.438nm, and SiO₂/Al₂O₃The chemical mol ratio is about 8, and SiO is₂/Al₂O₃The framework molar ratio is about 20, 0.1-30 wt% of at least VIII group metal component, 1-40 wt% of at least one VIB group metal component, 0.1-20 wt% of auxiliary agent and 0-20 wt% of at least one VIIA group metal element. The catalyst is prepared by firstly preparing a carrier and then carrying hydrogenation metalThe catalyst has good activity and stability, but the yield of heavy naphtha and aviation kerosene is not high.

CN94117759.9 discloses a light oil type hydrocracking catalyst, which comprises 50-65 wt% of low-sodium high-silicon Y-type molecular sieve (prepared according to CN90102645. X), 10-26 wt% of small-pore alumina and WO₃18-26 wt% of NiO and 4-6 wt% of NiO. The preparation method comprises the steps of mixing the low-sodium high-silicon Y molecular sieve with the small-hole alumina, extruding the mixture into strips, forming, treating the formed product at a high temperature in an ammonia-water vapor atmosphere, soaking the treated carrier in a mixed solution containing tungsten and nickel, drying, and roasting to obtain a catalyst finished product. The catalyst prepared by the technology has higher cracking activity, but the liquid yield is low.

CN1393521A discloses a hydrocracking catalyst, which comprises 20-50 wt% of amorphous silica-alumina, 25-35 wt% of alumina, 10-30 wt% of combined zeolite, 30-90 wt% of Y zeolite and 10-70 wt% of beta zeolite. The preparation process includes the mechanical mixing of Y zeolite and beta zeolite, treating with solution containing H + and NH3+ cation, mechanical mixing of the treated composite zeolite with amorphous silica-alumina and alumina, extruding to form, drying and roasting, soaking the carrier in mixed solution containing tungsten and nickel, drying and roasting to obtain the catalyst. The catalyst has the advantages of flexible production scheme, strong raw material adaptability and the like, but the catalyst has smaller pore volume and lower light oil yield.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a hydrocracking catalyst containing a Y/beta/ASA composite material, and a preparation method and application thereof. Mixing a Y molecular sieve and a beta molecular sieve, then carrying out in-situ compounding with prepared amorphous silica-alumina to synthesize a composite material containing Y/beta/ASA and having a micropore-mesopore and core-shell coating structure, further mixing and kneading the composite material with a binder and an extrusion aid, drying and roasting to prepare a carrier, impregnating the carrier with an impregnating solution containing metals of VIB group and VIII group, drying and roasting to prepare the hydrocracking catalyst containing the Y/beta/ASA composite material. The catalyst has strong adaptability to raw materials, has high cracking activity and hydrogenation activity, and is suitable for the technological process for producing different target products.

In order to achieve the purpose, the invention provides a hydrocracking catalyst containing a Y/beta/ASA composite material, which comprises a carrier and an active component. The catalyst carrier contains a Y/beta/ASA composite material, a binder and an extrusion aid, and active components comprise at least one VIB group metal tungsten or molybdenum and at least one VIII group metal nickel or cobalt; the catalyst comprises 60-90 wt% of carrier and 40-10 wt% of metal component according to the weight content of the catalyst. The weight content of the carrier is 60-94 wt% of the composite material, 35-5 wt% of the binder and 5-1 wt% of the extrusion aid. The weight content of the composite material is 10-90 wt% of amorphous silica-alumina, 90-10 wt% of molecular sieve, and in the molecular sieve, 0-100 wt% of Y molecular sieve and 100-0 wt% of beta molecular sieve. In the metal components, 3-37 wt% of VIB group metal component and 37-3 wt% of VIII group metal component.

The invention also provides a preparation method of the hydrocracking catalyst containing the Y/beta/ASA composite material, which adopts a fractional precipitation method and a coprecipitation method for preparation, and preferably adopts the fractional precipitation method for preparation. The preparation process of the fractional precipitation method comprises the following steps:

(1) uniformly mixing the Y molecular sieve and the beta molecular sieve according to requirements;

(2) simultaneously adding an aluminum source and a precipitator into the uniformly mixed molecular sieve in the step (1), and carrying out gelling and aging for a period of time at a certain temperature and under an acidic condition;

(3) adding a silicon source into the gel-like mixture obtained in the step (2), and carrying out reaction aging for a period of time under a certain temperature and acidic condition;

(4) filtering, washing and drying the slurry obtained in the step (3) to obtain a composite material;

(5) and (4) uniformly mixing the composite material prepared in the step (4) with a binder and an extrusion aid, kneading, extruding, drying and roasting to obtain the carrier.

(6) And (4) dipping the carrier obtained in the step (5) by using a metal solution prepared by VIII and VIB group metal compounds, drying and roasting to obtain the hydrocracking catalyst.

The preparation method of the hydrocracking catalyst containing the Y/beta/ASA composite material comprises the step (2) of preparing a hydrocracking catalyst containing the Y/beta/ASA composite material, wherein an aluminum source in the step (2) is one or more of sodium aluminate, aluminum sulfate, aluminum chloride and aluminum nitrate, and preferably aluminum sulfate. The precipitant is at least one of sodium hydroxide aqueous solution, ammonia aqueous solution and ammonium carbonate aqueous solution, preferably ammonia aqueous solution.

The preparation method of the hydrocracking catalyst containing the Y/beta/ASA composite material comprises the step (3) of selecting one or more silicon sources from silica sol, water glass and white carbon black, and preferably selecting the water glass.

The preparation method of the hydrocracking catalyst containing the Y/beta/ASA composite material comprises the step (5) of using one or more of aluminum sol, silica sol, kaolin and methyl cellulose as a binder, and preferably using the aluminum sol.

The preparation method of the hydrocracking catalyst containing the Y/beta/ASA composite material comprises the step (5) of using sesbania powder as an extrusion aid.

The preparation method of the hydrocracking catalyst containing the Y/beta/ASA composite material comprises the step (6) of adding one or more of ammonium metatungstate, ammonium tungstate, ammonium molybdate, nickel nitrate and nickel chloride to the hydrogenation metal salt, preferably ammonium metatungstate and nickel nitrate. The catalyst comprises 10-40 wt% of metal components, by weight, of 3-37 wt% of ammonium metatungstate, 37-3 wt% of nickel nitrate, preferably 5-35 wt% of ammonium metatungstate and 35-5 wt% of nickel nitrate.

The preparation method of the hydrocracking catalyst containing the Y/beta/ASA composite material comprises the steps of adding the Y molecular sieve and the beta molecular sieve into a reaction tank for fully mixing, then simultaneously feeding an aluminum source and a precipitator for gelling, and finally adding a silicon source.

The preparation method of the hydrocracking catalyst containing the Y/beta/ASA composite material comprises the following steps of (2) gelatinizing at the temperature of 40-100 ℃, preferably 50-90 ℃; the gelling time is 0-240 min, preferably 10-180 min; the pH value of the gel is 5-10, preferably 6-9; the aging temperature is 40-100 ℃, and preferably 50-90 ℃; the aging time is 0-240 min, preferably 10-180 min; the aging pH is 5-10, preferably 6-9.

The preparation method of the hydrocracking catalyst containing the Y/beta/ASA composite material comprises the following steps of (3) reacting at 40-100 ℃, preferably 50-90 ℃; the reaction time is 0-240 min, preferably 10-180 min; the reaction pH is 5-10, preferably 6-9; the aging temperature is 40-100 ℃, and preferably 50-90 ℃; the aging time is 0-240 min, preferably 10-180 min; the aging pH is 5-10, preferably 6-9.

The preparation method of the hydrocracking catalyst containing the Y/beta/ASA composite material comprises the step (4) of washing with hot water at the temperature of 50-100 ℃ until filtrate is neutral. The drying temperature is 100-150 ℃, and preferably 120 ℃; the drying time is 3-12 h, preferably 4-6 h.

The preparation method of the hydrocracking catalyst containing the Y/beta/ASA composite material comprises the following steps of (5) drying at 100-150 ℃, preferably at 120 ℃; the drying time is 3-12 h, preferably 4-6 h; the roasting temperature is 450-600 ℃, and preferably 500-550 ℃; the roasting time is 2-5 h, preferably 3-4 h.

The preparation method of the hydrocracking catalyst containing the Y/beta/ASA composite material comprises the following steps of (6), wherein the drying temperature is 100-150 ℃, and preferably 120 ℃; the drying time is 3-12 h, preferably 4-6 h; the roasting temperature is 450-600 ℃, and preferably 500-550 ℃; the roasting time is 2-5 h, preferably 3-4 h.

The preparation method of the hydrocracking catalyst containing the Y/beta/ASA composite material comprises the following steps of (1): the specific surface area is 500-900 m²A total pore volume of 0.3 to 0.5mL/g, a unit cell constant of 2.426 to 2.682nm, and a skeleton of SiO₂/Al₂O₃The molar ratio is 5-20, the relative crystallinity is 80-90%, and an industrial Y molecular sieve can be adopted; beta molecular sieve SiO adopted₂/Al₂O₃The molar ratio is 10-120, and the specific surface area is 200-300 m²The total pore volume is 0.4-0.8 mL/g, the pore diameter is 6-20 nm, and an industrially produced beta molecular sieve can be adopted.

The hydrocracking catalyst has a specific surface area of 200-400 m²The specific surface area is 0.6-1.0 mL/g, the pore diameter is 8.0-13.0 nm, and the infrared acid content is 100-500 mu mol/g.

The Y molecular sieve, the beta molecular sieve and the amorphous silica-alumina are jointly used as a cracking center, so that the respective performances of the three cracking components are fully exerted, and the three cracking components can generate a synergistic catalytic action, namely the Y molecular sieve has high ring-opening selectivity on aromatic hydrocarbon and strong cracking selectivity on long-chain alkane olefin, and the yield of a target product is improved; the beta molecular sieve has good isomerism and selectivity performance, and the quality of a target product is improved; the amorphous silica-alumina has the characteristics of good selectivity, high liquid yield, low hydrogen consumption, small product distribution change in the operation period and the like. The catalyst prepared by the invention has the characteristics of high activity, good selectivity and the like, and can be used for the technological process of producing different target products by hydrocracking reaction.

Detailed Description

In order to better illustrate the invention, the invention is further described below in conjunction with specific embodiments. The scope of the invention is not limited to only these examples. The analysis method of the invention comprises the following steps: the specific surface area, the pore volume and the pore diameter are analyzed and measured by adopting a low-temperature liquid nitrogen physical absorption method, adopting an X-ray diffraction method for relative crystallinity and unit cell parameters, adopting a chemical method for a silicon-aluminum molar ratio and adopting pyridine infrared for infrared analysis and measurement. In the present invention, wt% is mass%.

Example 1

(1) Weighing 20g Y molecular sieve according to the adding amount of the total weight of the molecular sieve accounting for 50 wt% of the weight of the composite material, and adding the molecular sieve into a reaction kettle.

(2) Solid aluminum sulfate is prepared into 500mL of Al with the concentration of 20g₂O₃Adding a proper amount of deionized water into concentrated ammonia water to dilute into a 10 wt% dilute ammonia water solution (b), and adding a proper amount of deionized water into a concentrated water glass solution to dilute into 72mL of a 14 wt% water glass solution (c).

(3) Adding 100mL of deionized water into a reaction kettle, heating to 75 ℃, simultaneously adding the (a) and the (b), adjusting the pH value to be 8-9, gelatinizing for 30min, keeping the temperature unchanged after feeding, and aging for 30 min.

(4) After the aging is finished, adding the (c) into the aged solution, keeping the temperature unchanged, and after the feeding is finished, aging at the same temperature for 30 min.

(5) And (3) carrying out suction filtration on the aged product, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the composite material.

(6) And adding 4.7g of alumina sol and 2.4g of sesbania powder into the composite material, kneading, extruding into strips, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the carrier.

(7) The carrier is soaked in a soaking solution prepared from 13.4g of ammonium metatungstate and 6.7g of nickel nitrate for 12 hours in equal volume, dried at 50 ℃ for 4 hours, dried at 120 ℃ for 5 hours and roasted at 550 ℃ for 3 hours to obtain the hydrocracking catalyst.

The texture properties and acid properties of the catalyst are shown in table 1.

Example 2

(1) According to the addition of the total weight of the molecular sieve accounting for 50 wt% of the weight of the composite material, the weight ratio of the Y molecular sieve to the beta molecular sieve is 7: 3 weigh 14g Y molecular sieves and 6g beta molecular sieves, respectively, into the reactor.

(2) Solid aluminum sulfate is prepared into 500mL of Al with the concentration of 20g₂O₃Adding a proper amount of deionized water into concentrated ammonia water to dilute into a 10 wt% dilute ammonia water solution (b), and adding a proper amount of deionized water into a concentrated water glass solution to dilute into 72mL of a 14 wt% water glass solution (c).

(3) Adding 100mL of deionized water into a reaction kettle, heating to 75 ℃, simultaneously adding the (a) and the (b), adjusting the pH value to be 8-9, gelatinizing for 30min, keeping the temperature unchanged after feeding, and aging for 30 min.

(4) After the aging is finished, adding the (c) into the aged solution, keeping the temperature unchanged, and after the feeding is finished, aging at the same temperature for 30 min.

(5) And (3) carrying out suction filtration on the aged product, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the composite material.

(6) And adding 4.7g of alumina sol and 2.4g of sesbania powder into the composite material, kneading, extruding into strips, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the carrier.

(7) The carrier is soaked in a soaking solution prepared from 13.4g of ammonium metatungstate and 6.7g of nickel nitrate for 12 hours in equal volume, dried at 50 ℃ for 4 hours, dried at 120 ℃ for 5 hours and roasted at 550 ℃ for 3 hours to obtain the hydrocracking catalyst.

The texture properties and acid properties of the catalyst are shown in table 1.

Example 3

(1) According to the addition of the total weight of the molecular sieve accounting for 50 wt% of the weight of the composite material, the weight ratio of the Y molecular sieve to the beta molecular sieve is 1: 1 weigh 10g Y molecular sieves and 10g beta molecular sieves, respectively, into the reactor.

(2) Solid aluminum sulfate is prepared into 500mL of Al with the concentration of 20g₂O₃Adding a proper amount of deionized water into concentrated ammonia water to dilute into a 10 wt% dilute ammonia water solution (b), and adding a proper amount of deionized water into a concentrated water glass solution to dilute into 72mL of a 14 wt% water glass solution (c).

(3) Adding 100mL of deionized water into a reaction kettle, heating to 75 ℃, simultaneously adding the (a) and the (b), adjusting the pH value to be 8-9, gelatinizing for 30min, keeping the temperature unchanged after feeding, and aging for 30 min.

(4) After the aging is finished, adding the (c) into the aged solution, keeping the temperature unchanged, and after the feeding is finished, aging at the same temperature for 30 min.

(5) And (3) carrying out suction filtration on the aged product, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the composite material.

(6) And adding 4.7g of alumina sol and 2.4g of sesbania powder into the composite material, kneading, extruding into strips, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the carrier.

(7) The carrier is soaked in a soaking solution prepared from 13.4g of ammonium metatungstate and 6.7g of nickel nitrate for 12 hours in equal volume, dried at 50 ℃ for 4 hours, dried at 120 ℃ for 5 hours and roasted at 550 ℃ for 3 hours to obtain the hydrocracking catalyst.

The texture properties and acid properties of the catalyst are shown in table 1.

Example 4

(1) According to the addition of the total weight of the molecular sieve accounting for 50 wt% of the weight of the composite material, the weight ratio of the Y molecular sieve to the beta molecular sieve is 6: 14 weigh 6g Y molecular sieves and 14g beta molecular sieves, respectively, into the reactor.

(2) Solid aluminum sulfate is prepared into 500mL of Al with the concentration of 20g₂O₃Adding a proper amount of deionized water into concentrated ammonia water to dilute into a 10 wt% dilute ammonia water solution (b), taking a proper amount of concentrated sodium silicate solution to addThe ionized water was diluted to 72mL of a 14 wt% water glass solution (c).

(3) Adding 100mL of deionized water into a reaction kettle, heating to 75 ℃, simultaneously adding the (a) and the (b), adjusting the pH value to be 8-9, gelatinizing for 30min, keeping the temperature unchanged after feeding, and aging for 30 min.

(4) After the aging is finished, adding the (c) into the aged solution, keeping the temperature unchanged, and after the feeding is finished, aging at the same temperature for 30 min.

(5) And (3) carrying out suction filtration on the aged product, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the composite material.

(6) And adding 4.7g of alumina sol and 2.4g of sesbania powder into the composite material, kneading, extruding into strips, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the carrier.

(7) The carrier is soaked in a soaking solution prepared from 13.4g of ammonium metatungstate and 6.7g of nickel nitrate for 12 hours in equal volume, dried at 50 ℃ for 4 hours, dried at 120 ℃ for 5 hours and roasted at 550 ℃ for 3 hours to obtain the hydrocracking catalyst.

The texture properties and acid properties of the catalyst are shown in table 1.

Example 5

(1) Weighing 20g of beta molecular sieve according to the adding amount of the total weight of the molecular sieve accounting for 50 wt% of the weight of the composite material, and adding the beta molecular sieve into a reaction kettle.

(2) Solid aluminum sulfate is prepared into 500mL of Al with the concentration of 20g₂O₃Adding a proper amount of deionized water into concentrated ammonia water to dilute into a 10 wt% dilute ammonia water solution (b), and adding a proper amount of deionized water into a concentrated water glass solution to dilute into 72mL of a 14 wt% water glass solution (c).

(3) Adding 100mL of deionized water into a reaction kettle, heating to 75 ℃, simultaneously adding the (a) and the (b), adjusting the pH value to be 8-9, gelatinizing for 30min, keeping the temperature unchanged after feeding, and aging for 30 min.

(4) After the aging is finished, adding the (c) into the aged solution, keeping the temperature unchanged, and after the feeding is finished, aging at the same temperature for 30 min.

(5) And (3) carrying out suction filtration on the aged product, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the composite material.

(6) And adding 4.7g of alumina sol and 2.4g of sesbania powder into the composite material, kneading, extruding into strips, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the carrier.

(7) The carrier is soaked in a soaking solution prepared from 13.4g of ammonium metatungstate and 6.7g of nickel nitrate for 12 hours in equal volume, dried at 50 ℃ for 4 hours, dried at 120 ℃ for 5 hours and roasted at 550 ℃ for 3 hours to obtain the hydrocracking catalyst.

The texture properties and acid properties of the catalyst are shown in table 1.

Example 6

(1) According to the addition of the total weight of the molecular sieve accounting for 20 wt% of the weight of the composite material, the weight ratio of the Y molecular sieve to the beta molecular sieve is 1: 1 weigh 2.5g Y molecular sieves and 2.5g beta molecular sieve, respectively, into the reactor.

(2) Solid aluminum sulfate is prepared into 500mL of Al with the concentration of 20g₂O₃Adding a proper amount of deionized water into concentrated ammonia water to dilute into a 10 wt% dilute ammonia water solution (b), and adding a proper amount of deionized water into a concentrated water glass solution to dilute into 72mL of a 14 wt% water glass solution (c).

(3) Adding 100mL of deionized water into a reaction kettle, heating to 75 ℃, simultaneously adding the (a) and the (b), adjusting the pH value to be 8-9, gelatinizing for 30min, keeping the temperature unchanged after feeding, and aging for 30 min.

(4) After the aging is finished, adding the (c) into the aged solution, keeping the temperature unchanged, and after the feeding is finished, aging at the same temperature for 30 min.

(5) And (3) carrying out suction filtration on the aged product, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the composite material.

(6) Adding 2.9g of alumina sol and 1.5g of sesbania powder into the composite material, kneading, extruding into strips, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the carrier.

(7) The carrier is soaked in an impregnation liquid prepared from 8.4g of ammonium metatungstate and 4.2g of nickel nitrate in equal volume for 12 hours, dried at 50 ℃ for 4 hours, dried at 120 ℃ for 5 hours, and roasted at 550 ℃ for 3 hours to obtain the hydrocracking catalyst.

The texture properties and acid properties of the catalyst are shown in table 1.

Example 7

(1) According to the addition of the molecular sieve accounting for 30 wt% of the composite material, the weight ratio of the Y molecular sieve to the beta molecular sieve is 1: 1 weigh 4.3g Y molecular sieves and 4.3g beta molecular sieve, respectively, into the reactor.

(2) Solid aluminum sulfate is prepared into 500mL of Al with the concentration of 20g₂O₃Adding a proper amount of deionized water into concentrated ammonia water to dilute into a 10 wt% dilute ammonia water solution (b), and adding a proper amount of deionized water into a concentrated water glass solution to dilute into 72mL of a 14 wt% water glass solution (c).

(3) Adding 100mL of deionized water into a reaction kettle, heating to 75 ℃, simultaneously adding the (a) and the (b), adjusting the pH value to be 8-9, gelatinizing for 30min, keeping the temperature unchanged after feeding, and aging for 30 min.

(4) After the aging is finished, adding the (c) into the aged solution, keeping the temperature unchanged, and after the feeding is finished, aging at the same temperature for 30 min.

(5) And (3) carrying out suction filtration on the aged product, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the composite material.

(6) And adding 3.4g of alumina sol and 1.7g of sesbania powder into the composite material, kneading, extruding into strips, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the carrier.

(7) The carrier is soaked in an impregnation liquid prepared from 9.6g of ammonium metatungstate and 4.8g of nickel nitrate in equal volume for 12 hours, dried at 50 ℃ for 4 hours, dried at 120 ℃ for 5 hours, and roasted at 550 ℃ for 3 hours to obtain the hydrocracking catalyst.

The texture properties and acid properties of the catalyst are shown in table 1.

Example 8

(1) According to the addition of the total weight of the molecular sieve accounting for 40 wt% of the weight of the composite material, the weight ratio of the Y molecular sieve to the beta molecular sieve is 1: 1 weigh 6.7g Y molecular sieves and 6.7g beta molecular sieves, respectively, into the reactor.

(2) Solid aluminum sulfate is prepared into 500mL of Al with the concentration of 20g₂O₃Adding a proper amount of deionized water into concentrated ammonia water to dilute into a 10 wt% dilute ammonia water solution (b), taking a concentrated sodium silicate solution, adding a proper amount of deionized water to dilute72mL of a 14 wt% water glass solution (c) was obtained.

(3) Adding 100mL of deionized water into a reaction kettle, heating to 75 ℃, simultaneously adding the (a) and the (b), adjusting the pH value to be 8-9, gelatinizing for 30min, keeping the temperature unchanged after feeding, and aging for 30 min.

(4) After the aging is finished, adding the (c) into the aged solution, keeping the temperature unchanged, and after the feeding is finished, aging at the same temperature for 30 min.

(5) And (3) carrying out suction filtration on the aged product, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the composite material.

(6) And adding 3.9g of alumina sol and 2.0g of sesbania powder into the composite material, kneading, extruding into strips, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the carrier.

(7) The carrier is soaked in an impregnation liquid prepared from 11.2g of ammonium metatungstate and 5.6g of nickel nitrate in equal volume for 12 hours, dried at 50 ℃ for 4 hours, dried at 120 ℃ for 5 hours, and roasted at 550 ℃ for 3 hours to obtain the hydrocracking catalyst.

The texture properties and acid properties of the catalyst are shown in table 1.

Example 9

(1) According to the addition of the total weight of the molecular sieve accounting for 60 wt% of the weight of the composite material, the weight ratio of the Y molecular sieve to the beta molecular sieve is 1: 1 weigh 15g Y molecular sieves and 15g beta molecular sieves, respectively, into the reactor.

(2) Solid aluminum sulfate is prepared into 500mL of Al with the concentration of 20g₂O₃Adding a proper amount of deionized water into concentrated ammonia water to dilute into a 10 wt% dilute ammonia water solution (b), and adding a proper amount of deionized water into a concentrated water glass solution to dilute into 72mL of a 14 wt% water glass solution (c).

(3) Adding 100mL of deionized water into a reaction kettle, heating to 75 ℃, simultaneously adding the (a) and the (b), adjusting the pH value to be 8-9, gelatinizing for 30min, keeping the temperature unchanged after feeding, and aging for 30 min.

(4) After the aging is finished, adding the (c) into the aged solution, keeping the temperature unchanged, and after the feeding is finished, aging at the same temperature for 30 min.

(5) And (3) carrying out suction filtration on the aged product, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the composite material.

(6) And adding 5.8g of alumina sol and 2.9g of sesbania powder into the composite material, kneading, extruding into strips, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the carrier.

(7) The carrier is soaked in a soaking solution prepared from 16.8g of ammonium metatungstate and 8.4g of nickel nitrate for 12 hours in equal volume, dried at 50 ℃ for 4 hours, dried at 120 ℃ for 5 hours and roasted at 550 ℃ for 3 hours to obtain the hydrocracking catalyst.

The texture properties and acid properties of the catalyst are shown in table 1.

Example 10

(1) According to the addition of the total weight of the molecular sieve accounting for 50 wt% of the weight of the composite material, the weight ratio of the Y molecular sieve to the beta molecular sieve is 1: 1 weigh 8.3g Y molecular sieves and 8.3g beta molecular sieve, respectively, into the reactor.

(2) Solid aluminum sulfate is prepared into 500mL of Al with the concentration of 20g₂O₃Adding a proper amount of deionized water into concentrated ammonia water to dilute into a 10 wt% dilute ammonia water solution (b), and adding a proper amount of deionized water into a concentrated water glass solution to dilute into 47mL of a 14 wt% water glass solution (c).

(3) Adding 100mL of deionized water into a reaction kettle, heating to 75 ℃, simultaneously adding the (a) and the (b), adjusting the pH value to be 8-9, gelatinizing for 30min, keeping the temperature unchanged after feeding, and aging for 30 min.

(4) After the aging is finished, adding the (c) into the aged solution, keeping the temperature unchanged, and after the feeding is finished, aging at the same temperature for 30 min.

(5) And (3) carrying out suction filtration on the aged product, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the composite material.

(6) And adding 4.3g of alumina sol and 2.2g of sesbania powder into the composite material, kneading, extruding into strips, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the carrier.

(7) The carrier is soaked in a soaking solution prepared from 12.2g of ammonium metatungstate and 6.1g of nickel nitrate for 12 hours in equal volume, dried at 50 ℃ for 4 hours, dried at 120 ℃ for 5 hours, and roasted at 550 ℃ for 3 hours to obtain the hydrocracking catalyst.

The texture properties and acid properties of the catalyst are shown in table 1.

Example 11

(1) According to the addition of the total weight of the molecular sieve accounting for 50 wt% of the weight of the composite material, the weight ratio of the Y molecular sieve to the beta molecular sieve is 1: 1 weigh 9.1g Y molecular sieves and 9.1g beta molecular sieve, respectively, into the reactor.

(2) Solid aluminum sulfate is prepared into 500mL of Al with the concentration of 20g₂O₃Adding a proper amount of deionized water into concentrated ammonia water to dilute into a 10 wt% dilute ammonia water solution (b), and adding a proper amount of deionized water into a concentrated water glass solution to dilute into 59mL of a 14 wt% water glass solution (c).

(3) Adding 100mL of deionized water into a reaction kettle, heating to 75 ℃, simultaneously adding the (a) and the (b), adjusting the pH value to be 8-9, gelatinizing for 30min, keeping the temperature unchanged after feeding, and aging for 30 min.

(4) After the aging is finished, adding the (c) into the aged solution, keeping the temperature unchanged, and after the feeding is finished, aging at the same temperature for 30 min.

(5) And (3) carrying out suction filtration on the aged product, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the composite material.

(6) And adding 4.5g of alumina sol and 2.2g of sesbania powder into the composite material, kneading, extruding into strips, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the carrier.

(7) The carrier is soaked in a soaking solution prepared from 12.8g of ammonium metatungstate and 6.4g of nickel nitrate for 12 hours in equal volume, dried at 50 ℃ for 4 hours, dried at 120 ℃ for 5 hours and roasted at 550 ℃ for 3 hours to obtain the hydrocracking catalyst.

The texture properties and acid properties of the catalyst are shown in table 1.

Example 12

(1) According to the addition of the total weight of the molecular sieve accounting for 50 wt% of the weight of the composite material, the weight ratio of the Y molecular sieve to the beta molecular sieve is 1: 1 weigh 11.1g Y molecular sieves and 11.1g beta molecular sieve, respectively, into the autoclave.

(2) Solid aluminum sulfate is prepared into 500mL of Al with the concentration of 20g₂O₃Adding a proper amount of deionized water into concentrated ammonia water to dilute into a 10 wt% dilute ammonia water solution(b) And adding a proper amount of deionized water into the concentrated water glass solution to dilute the concentrated water glass solution into 88mL of 14 wt% water glass solution (c).

(3) Adding 100mL of deionized water into a reaction kettle, heating to 75 ℃, simultaneously adding the (a) and the (b), adjusting the pH value to be 8-9, gelatinizing for 30min, keeping the temperature unchanged after feeding, and aging for 30 min.

(4) After the aging is finished, adding the (c) into the aged solution, keeping the temperature unchanged, and after the feeding is finished, aging at the same temperature for 30 min.

(5) And (3) carrying out suction filtration on the aged product, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the composite material.

(6) And adding 5.0g of alumina sol and 2.5g of sesbania powder into the composite material, kneading, extruding into strips, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the carrier.

(7) The carrier is soaked in a soaking solution prepared from 14.2g of ammonium metatungstate and 7.1g of nickel nitrate for 12 hours in equal volume, dried at 50 ℃ for 4 hours, dried at 120 ℃ for 5 hours and roasted at 550 ℃ for 3 hours to obtain the hydrocracking catalyst.

The texture properties and acid properties of the catalyst are shown in table 1.

Example 13

(1) According to the addition of the total weight of the molecular sieve accounting for 50 wt% of the weight of the composite material, the weight ratio of the Y molecular sieve to the beta molecular sieve is 1: 1 weigh 12.5g Y molecular sieves and 12.5g beta molecular sieve, respectively, into the autoclave.

(2) Solid aluminum sulfate is prepared into 500mL of Al with the concentration of 20g₂O₃Adding a proper amount of deionized water into concentrated ammonia water to dilute into a 10 wt% dilute ammonia water solution (b), and adding a proper amount of deionized water into the concentrated sodium silicate solution to dilute into 108mL of a 14 wt% sodium silicate solution (c).

(3) Adding 100mL of deionized water into a reaction kettle, heating to 75 ℃, simultaneously adding the (a) and the (b), adjusting the pH value to be 8-9, gelatinizing for 30min, keeping the temperature unchanged after feeding, and aging for 30 min.

(4) After the aging is finished, adding the (c) into the aged solution, keeping the temperature unchanged, and after the feeding is finished, aging at the same temperature for 30 min.

(5) And (3) carrying out suction filtration on the aged product, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the composite material.

(6) And adding 5.3g of alumina sol and 2.6g of sesbania powder into the composite material, kneading, extruding into strips, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the carrier.

(7) Soaking the carrier in soaking liquid prepared from 15.1g of ammonium metatungstate and 7.5g of nickel nitrate in equal volume for 12 hours, drying at 50 ℃ for 4 hours, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the hydrocracking catalyst.

The texture properties and acid properties of the catalyst are shown in table 1.

Comparative example 1

The conditions of example 1 were used, but the materials were not compounded, but prepared by direct mixing.

(1) Weighing 20g Y molecular sieve according to the adding amount of the total weight of the molecular sieve accounting for 50 wt% of the weight of the composite material, and adding the molecular sieve into a reaction kettle.

(2) Solid aluminum sulfate is prepared into 500mL of Al with the concentration of 20g₂O₃Adding a proper amount of deionized water into concentrated ammonia water to dilute into a 10 wt% dilute ammonia water solution (b), and adding a proper amount of deionized water into a concentrated water glass solution to dilute into 72mL of a 14 wt% water glass solution (c).

(3) Adding 100mL of deionized water into a reaction kettle, heating to 75 ℃, simultaneously adding the (a) and the (b), adjusting the pH value to be 8-9, gelatinizing for 30min, keeping the temperature unchanged after feeding, and aging for 30 min.

(4) After the aging is finished, adding the (c) into the aged solution, keeping the temperature unchanged, and after the feeding is finished, aging at the same temperature for 30 min.

(5) And (3) carrying out suction filtration on the aged product, and drying at 120 ℃ for 5 hours to obtain amorphous silica-alumina.

(6) Adding 20g Y molecular sieve with the addition amount of 50 wt% of the total molecular sieve into the reaction kettle, uniformly mixing with the amorphous silica-alumina prepared in the step (5), drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the composite material.

(7) And adding 4.7g of alumina sol and 2.4g of sesbania powder into the composite material, kneading, extruding into strips, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the carrier.

(8) The carrier is soaked in a soaking solution prepared from 13.4g of ammonium metatungstate and 6.7g of nickel nitrate for 12 hours in equal volume, dried at 50 ℃ for 4 hours, dried at 120 ℃ for 5 hours and roasted at 550 ℃ for 3 hours to obtain the hydrocracking catalyst.

The texture properties and acid properties of the catalyst are shown in table 1.

Comparative example 2

The conditions of example 3 were used, but the materials were not compounded, but prepared by direct mixing.

(1) According to the addition of the total weight of the molecular sieve accounting for 50 wt% of the weight of the composite material, the weight ratio of the Y molecular sieve to the beta molecular sieve is 1: 1 weigh 10g Y molecular sieves and 10g of beta molecular sieve, respectively.

(2) Solid aluminum sulfate is prepared into 500mL of Al with the concentration of 20g₂O₃Adding a proper amount of deionized water into concentrated ammonia water to dilute into a 10 wt% dilute ammonia water solution (b), and adding a proper amount of deionized water into a concentrated water glass solution to dilute into 72mL of a 14 wt% water glass solution (c).

(3) Adding 100mL of deionized water into a reaction kettle, heating to 75 ℃, simultaneously adding the (a) and the (b), adjusting the pH value to be 8-9, gelatinizing for 30min, keeping the temperature unchanged after feeding, and aging for 30 min.

(4) After the aging is finished, adding the (c) into the aged solution, keeping the temperature unchanged, and after the feeding is finished, aging at the same temperature for 30 min.

(5) And (3) carrying out suction filtration on the aged product, and drying at 120 ℃ for 5 hours to obtain amorphous silica-alumina.

(6) According to the weight ratio of 1: 1, uniformly mixing the Y molecular sieve and the beta molecular sieve which account for 50 wt% of the total weight of the composite material with the amorphous silica-alumina prepared in the step (5), drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the composite material.

(7) And adding 4.7g of alumina sol and 2.4g of sesbania powder into the composite material, kneading, extruding into strips, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the carrier.

(8) The carrier is soaked in a soaking solution prepared from 13.4g of ammonium metatungstate and 6.7g of nickel nitrate for 12 hours in equal volume, dried at 50 ℃ for 4 hours, dried at 120 ℃ for 5 hours and roasted at 550 ℃ for 3 hours to obtain the hydrocracking catalyst.

The texture properties and acid properties of the catalyst are shown in table 1.

Comparative example 3

The conditions of example 5 were used, but the materials were not compounded, but prepared by direct mixing.

(1) Weighing 20g of beta molecular sieve according to the adding amount of the total weight of the molecular sieve accounting for 50 wt% of the weight of the composite material, and adding the beta molecular sieve into a reaction kettle.

(2) Solid aluminum sulfate is prepared into 500mL of Al with the concentration of 20g₂O₃Adding a proper amount of deionized water into concentrated ammonia water to dilute into a 10 wt% dilute ammonia water solution (b), and adding a proper amount of deionized water into a concentrated water glass solution to dilute into 72mL of a 14 wt% water glass solution (c).

(3) Adding 100mL of deionized water into a reaction kettle, heating to 75 ℃, simultaneously adding the (a) and the (b), adjusting the pH value to be 8-9, gelatinizing for 30min, keeping the temperature unchanged after feeding, and aging for 30 min.

(4) After the aging is finished, adding the (c) into the aged solution, keeping the temperature unchanged, and after the feeding is finished, aging at the same temperature for 30 min.

(5) And (3) carrying out suction filtration on the aged product, and drying at 120 ℃ for 5 hours to obtain amorphous silica-alumina.

(6) And (3) according to the addition amount of the total weight of the molecular sieve accounting for 50 wt% of the weight of the composite material, adding 20g of beta molecular sieve into a reaction kettle, uniformly mixing with the amorphous silica-alumina prepared in the step (5), drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the composite material.

(7) And adding 4.7g of alumina sol and 2.4g of sesbania powder into the composite material, kneading, extruding into strips, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the carrier.

(8) The carrier is soaked in a soaking solution prepared from 13.4g of ammonium metatungstate and 6.7g of nickel nitrate for 12 hours in equal volume, dried at 50 ℃ for 4 hours, dried at 120 ℃ for 5 hours and roasted at 550 ℃ for 3 hours to obtain the hydrocracking catalyst.

The texture properties and acid properties of the catalyst are shown in table 1.

TABLE 1 catalyst texture Properties of Y/beta/ASA-containing composites

The data in table 1 show that the catalyst containing the Y/beta/ASA composite material has the characteristics of large specific surface area, large pore volume, wide pore size distribution range and large infrared acid amount, has the advantages of strong raw material adaptability, good cracking activity, high product yield, good product quality and the like, and is suitable for the technological process of producing different target products by hydrocracking reaction.

The performance of the catalyst is evaluated by a small hydrocracking evaluation device with the volume of 10mL, a series process is adopted, and CS-containing materials are adopted before evaluation₂The properties and reaction conditions of the raw oil used for the evaluation of the catalyst performance, which was presulfided with 3 wt% cyclohexane, are shown in tables 2 and 3, respectively, and the results of the evaluation of the catalyst reactions are shown in table 4.

TABLE 2 Properties of the feed oils

Raw oil	Harbin catalytic cracking diesel oil
		Density (20 ℃ C.), g/cm3	0.8405
Sulfur,. mu.g/g	1220
		Nitrogen,. mu.g/g	1042
Distillation range, deg.C
		IBP	179.6
10％	229.7
		50％	270.8
90％	322.6
		95％	337.7
EBP	354.0

TABLE 3 reaction Process conditions

H2Partial pressure, MPa	6.25
		Volume ratio of hydrogen to oil	500
Liquid hourly volume space velocity, h-1	1
		Temperature, C	380

TABLE 4 catalyst reaction evaluation results

As can be seen from the evaluation results of the catalysts in Table 4, the hydrocracking catalyst containing the Y/beta/ASA composite prepared by compounding has higher reactivity than the catalyst prepared by mixing.