CN111889133A - Preparation method of vulcanization type hydrocracking catalyst - Google Patents

Abstract

The invention belongs to the technical field of catalyst materials, and particularly relates to a preparation method of a vulcanization type hydrocracking catalyst. The preparation method comprises the steps of preparing a catalyst carrier by using a mixed molecular sieve, modifying a new functional group on the surface of the prepared carrier through a chemical bond, impregnating a VIB group element-containing compound, a VIII group element-containing compound and a sulfur-containing nonmetal compound solution, and roasting in a vacuum drying inert atmosphere to prepare the vulcanized hydrocracking catalyst, wherein pre-vulcanization treatment is not needed before use. The hydrocracking catalyst obtained by the invention has higher hydrocracking activity and diesel selectivity.

Description

A kind of preparation method of sulfurized hydrocracking catalyst

technical field

The invention belongs to the technical field of catalyst materials, and in particular relates to a preparation method of a sulfurized hydrocracking catalyst.

Background technique

The hydrocracking process is an oil refining process that converts high-boiling feedstocks into lower-boiling naphtha and diesel fractions. Compared with catalytic cracking, its raw material adaptability is high, and the yield and quality of diesel fraction are high. With the increasing social demand for clean transportation fuel oil, hydrocracking process has become one of the core processes of modern refineries. The hydrocracking catalyst is the core of the whole hydrocracking process, which usually includes a dual function center: one is an acid center, which is provided by a carrier, which basically determines the activity of the catalyst. Halogenated (chlorine or fluorine) alumina, amorphous silica-alumina, molecular sieves and other materials, since the 1970s, with the development of molecular sieve preparation technology, because of its clear structure and adjustable acidity, silica-alumina molecular sieves have gradually become an additive. The main component of acid sites in hydrocracking catalysts. The second is the metal center, which plays the role of hydrogenation/dehydrogenation in the reaction process, provides the reaction raw material for the acid center, and saturates the acid center product in time to prevent deep cracking. The metal center is generally composed of a Group VIB metal or a binary metal system of Group VIB and Group VIIIB, providing true hydrogenation/dehydrogenation activity in the sulfide form. The acid center is closely combined with the hydrogenation/dehydrogenation center, and the coordination between the two is the key to the successful operation of the hydrocracking catalyst.

In order to meet the increasing demand for clean transportation fuel oil, the hydrocracking process needs to fully utilize the high boiling point feedstock to produce more naphtha and diesel products and reduce the production of low value gaseous products (C1-C4) . At the same time, in order to reduce the cost of production and operation, industrial production expects to use a catalyst with higher activity to lower the reaction temperature. When it comes to catalyst design, it is hoped to simultaneously improve the performance of the acid center and the metal center of the catalyst: the performance of the acid center can be improved by increasing the acid strength of acidic materials (such as molecular sieves) or the amount used; while the performance of the metal center is affected by the support. The limit of the effective specific surface area that can be provided and the properties of the metal itself cannot be improved simply by increasing the amount used. Therefore, how to improve the performance of metal centers has always been a research hotspot in this field.

The performance of the acid center can be improved by increasing the acid strength or usage amount of the molecular sieve. The present invention improves the performance of the acid center by using two molecular sieves in combination. The limitation on the performance of metal centers is that the surface of inorganic oxides (such as alumina) has a large number of hydroxyl groups, and the types of hydroxyl groups can be divided into five types according to the coordination environment of the aluminum atom (Reference: Catal Rev. Sci . Eng. 17(1), 31-70, 1978). These hydroxyl groups form Al-O-M chemical bonds through condensation, which is the key reason for the strong interaction between the VIB group metals and the alumina support. In the present invention, the surface of the inorganic oxide carrier is modified, and all or part of the strong hydroxyl groups on its surface are replaced with other functional groups, so as to form a weak interaction with the VI B metal, and even directly participate in the vulcanization of the VI B metal oxide. In the process, the interaction between the transition metal and the surface of the inorganic support is essentially changed, which is beneficial to the sufficient presulfurization of the transition metal oxide, so as to exert the best hydrogenation/dehydrogenation performance in the hydrocracking reaction.

Most of the active metals in the hydrocracking catalyst are dispersed on the carrier in an oxidized state, and can be used for reactions such as hydrodesulfurization, nitrogen, hydrodearomatization and hydrocracking. Studies have shown that the activity, selectivity and stability of the unpresulfided catalyst are lower than those of the sulfurized catalyst, and the service life is shorter. The pre-sulfiding of the catalyst in the hydrogenation process is one of the important links in the application of the catalyst. Pre-sulfiding the catalyst in the oxidized state to convert the active metal components into the sulfurized state can maximize the activity of the hydrogenation catalyst. and external vulcanization.

However, no matter whether the in-vessel pre-sulfurization technology or the out-of-vessel pre-sulfurization technology is adopted, the catalyst must undergo the process of converting the active metal into the oxidized state and then from the oxidized state to the sulfurized state before practical application. The above process is relatively complicated and has many influencing factors. . In addition, due to the multiple steps to finally complete the sulfidation of the catalyst, it is easy to cause the part where the active metal can only form a strong interaction with the catalyst support and cannot be fully sulfided, thereby affecting the performance of the catalyst.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a preparation method of a sulfurized hydrocracking catalyst. The hydrocracking catalyst prepared by using the mixed molecular sieve does not need pre-sulfiding treatment before use, which can greatly shorten the start-up time, avoid safety risks, and improve the stability of the catalyst. high hydrocracking activity and diesel selectivity.

To achieve the above object, the present invention adopts the following technical solutions:

A preparation method of a sulfurized hydrocracking catalyst, which comprises the steps:

(1) After fully mixing pseudo-boehmite, amorphous silica-alumina, USY molecular sieve and beta zeolite in a certain proportion, add a certain amount of acid solution, knead for 2-60 minutes, and then extrude into strips; After drying at -200°C for 2-24 h, calcination at 400-750°C for 2-8 h to prepare the catalyst carrier;

(2) Add 0.5-20% by weight of modifying reagent to the catalyst carrier obtained in step (1), react at 5-40°C for 1-24h, then heat up to 40-100°C, and then react for 1-12h, so that the inorganic carrier can be heated for 1-24h. The surface is connected with new functional groups through chemical bonds to obtain surface-modified inorganic carriers;

(3) Disperse the VIB group element-containing compound, the VIII group element-containing compound and the sulfur-containing non-metallic compound in a solvent, impregnate the catalyst carrier obtained in step (2) for 1-12 hours, and then vacuum dry at 50-100 ° C for 6- 48 h, calcined at 200-350 °C for 2-24 h in an inert atmosphere to obtain a hydrocracking catalyst.

The weight ratio of pseudo-boehmite, amorphous silica-alumina, USY molecular sieve and beta zeolite used in step (1) is (20-80):(20-60):(1-20):(0.05-4) .

The addition amount of the acid solution used in step (1) is 0.5-10% of the total weight of pseudo-boehmite, amorphous silica-alumina and molecular sieve, and its concentration is not more than 10wt%; the acid solution, including inorganic acid or An organic acid, wherein the inorganic acid includes any one of sulfuric acid, hydrochloric acid and nitric acid, and the organic acid includes any one of formic acid, acetic acid and citric acid;

Preferably, the acid solution is a nitric acid solution, and the concentration of the acid solution is 0.5wt%-5wt%, preferably 1wt%-3wt%.

The USY molecular sieve described in step (1) has the following properties: the specific surface area is 500-800 m ² /g, the total pore volume is 0.40-0.65 cm ³ /g, and the mesopore volume is 0.05-0.35 cm ³ /g , the Si/Al molar ratio is 10~30.

The beta zeolite in step (1) is specifically: Si/Al molar ratio of 0-30, specific surface area of 360-590 m ² /g, pore volume of 0.32-0.50 cm ³ /g, and SF6 adsorption capacity of at least 28 wt % zeolite beta.

The weight ratio of USY molecular sieve and beta zeolite in step (1) is (5-20):1.

The amorphous silica-alumina described in step (1) has the following properties after being calcined at 530 °C for 6 h in an air atmosphere: the specific surface area is 350-600 m ² /g; the pore volume is 0.6-1.8 cm ³ /g, preferably 1.0 ~1.4 cm ³ /g; SiO ₂ content is 20-80% by weight.

After the pseudo-boehmite described in step (1) is calcined at 530 °C for 6 h in an air atmosphere, the alumina obtained has the following properties: the specific surface is 150-400 m ² /g, preferably 200-350 m ² /g; the pore volume is 0.3-0.8 cm ³ /g, preferably 0.40-0.65 cm ³ /g; in terms of weight fraction, the Na element content is less than or equal to 0.1%.

The size and shape of the shaped body in step (1) are preferably similar to conventional hydrocracking commercial catalysts, and more preferably made into an extrudate with a diameter of 1.5-3.5 nm and a length of 3-12 nm and a cross-section of a circle or clover.

The modification reagent in step (2) contains two or more functional groups, one of which must be able to react with the surface of the inorganic carrier, which is selected from hydroxyl, carboxyl, amino, acid anhydride, and halogen substituents (such as -Cl, -Br, -I, etc.), siloxy group, phosphoric acid group, metaphosphoric acid group or phosphite group, preferably the functional group is siloxy; the other functional group needs to be able to interact with the VIB group metal element or VIIB group The oxide or salt reaction of the metal element is selected from any one of hydroxyl, carboxyl, amino, mercapto, amide or halogen substituents, preferably the functional group is mercapto.

In step (3), the compound containing Group VIII element is preferably a nickel salt, and the nickel salt includes but is not limited to one or more of nickel nitrate, nickel acetate, and basic nickel carbonate.

In step (3), the compound containing the VIB group element is preferably a sulfur-containing tungsten salt, and the sulfur-containing tungsten salt includes but is not limited to ammonium trithiotungstate, ammonium tetrathiotungstate, ammonium dodecathiotungstate and One or more of ammonium tridecylthiotungstate.

The sulfur-containing non-metallic compound in step (3) includes, but is not limited to, one or more of ammonium sulfide, thiourea, and ammonium thiosulfate.

The solvent in step (3) is not particularly limited, as long as the operation of impregnation and loading can be achieved. These solvents can be dissolved, or dissolved by adjusting pH, or those solvents that can form colloids or form colloids by adjusting pH , which can be a single solvent or a mixed solvent.

The mass ratio of the VIB group element-containing compound, the VIII group element-containing compound, and the sulfur-containing non-metallic compound described in step (3) is (1-600):(1-50):(0.3-500).

Step (3) calcination includes one or more of nitrogen, argon and helium, and the pressure is 0-5MPa.

A significant advantage of the present invention is that the present invention modifies functional groups on the surface of the inorganic support through chemical bonds, while the low amount of beta zeolite relative to Y zeolite helps reduce the formation of undesired heavy polynuclear aromatic by-products that may reduce stability, The stability of the catalyst is improved, and the obtained catalyst has a higher diesel liquid yield. Moreover, the above-mentioned catalyst start-up process does not require vulcanization or activation, which can greatly shorten the start-up time and avoid safety risks, and has a good application prospect.

Detailed ways

In order to make the content of the present invention easier to understand, the technical solutions of the present invention will be further described below with reference to specific embodiments, but the present invention is not limited thereto.

The used USY molecular sieve has the following properties: the specific surface area is 600 m ² /g, the total pore volume is 0.48 cm ³ /g, the mesopore volume is 0.15 cm ³ /g, and the Si/Al molar ratio is 22.

After calcination at 530 ℃ for 6 h in air atmosphere, the used amorphous silicon-alumina has a specific surface area of 382 m ² /g, a pore volume of 1.22 cm ³ /g, and a SiO ₂ content of 35%.

The used pseudo-boehmite was calcined at 530 ℃ for 6 h, and the alumina obtained had a specific surface of 235 m ² /g, a pore volume of 0.63 cm ³ /g, and a Na content of less than 0.08%.

The beta zeolite used has the following properties: a beta zeolite with a Si/Al molar ratio of 25, a specific surface area of 470 m ² /g, a pore volume of 0.39 cm ³ /g, and an SF6 adsorption capacity of 30% by weight.

Example 1:

Weigh 200 g of pseudo-boehmite (on a dry basis, all the following raw materials, unless otherwise specified, all weights are on a dry basis), 170 g of amorphous silica-alumina, 25 g of USY molecular sieve, and 5 g of beta zeolite. After the solid powder was fully mixed, the pre-prepared dilute nitric acid solution was added to it, kneaded for 15 minutes, extruded through a 3.0mm orifice plate, dried at 140°C for 12 hours, and then calcined at 560°C for 4 hours in an air atmosphere to obtain a catalyst carrier. S1.

Example 2:

5.6g of 3-aminopropyltriethoxysilane was weighed and added to 100mL of 95% ethanol solution, and stirred at room temperature for 20min to fully dissolve it. Then, 40 g of the carrier S1 prepared in Example 1 was added to the above solution, the reaction vessel was purged with nitrogen and maintained at a slight positive pressure in nitrogen atmosphere, left to react at room temperature for 12 hours, heated to 60°C, and then reacted for 4 hours. After the reaction, the excess ethanol solution was poured out, and the obtained solid particles were washed three times with absolute ethanol at room temperature, then pre-dried at room temperature for 4 h in an air atmosphere, and then placed in a vacuum drying box to fully dry at 70 °C to obtain a surface-modified carrier. Z1.

Example 3:

Take 19.1 g of ammonium tetrathiotungstate, 7.8 g of nickel nitrate and 7.8 g of ammonium thiosulfate, add 26 mL of deionized water, stir until completely dissolved to obtain a mixed aqueous solution, then impregnate and support 40.0 g of catalyst carrier Z1, and then vacuum at 60 °C After drying for 12 h, calcined at 315 °C for 3 h in nitrogen atmosphere to obtain hydrocracking catalyst C1.

Example 4:

Weigh 200 g of pseudo-boehmite (on a dry basis, all the following raw materials, unless otherwise specified, all weights are on a dry basis), 170 g of amorphous silica-alumina, 26.25 g of USY molecular sieve, and 3.75 g of beta zeolite. After the solid powder was fully mixed, the pre-prepared dilute nitric acid solution was added to it, kneaded for 15 minutes, extruded through a 3.0 mm orifice plate, dried at 140 °C for 12 h, and then calcined at 560 °C for 4 h in an air atmosphere to obtain the catalyst. Carrier S2; then weigh 5.6 g of 3-aminopropyltriethoxysilane and add it to 100 mL of 95% ethanol solution, and stir at room temperature for 20 min to fully dissolve it. Then, 40 g of the prepared carrier S2 was added to the above solution, the reaction vessel was purged with nitrogen and maintained at a slight positive pressure in nitrogen atmosphere. After the reaction, the excess ethanol solution was poured out, and the obtained solid particles were washed three times with absolute ethanol at room temperature, then pre-dried at room temperature for 4 h in an air atmosphere, and then placed in a vacuum drying box to fully dry at 70 °C to obtain a surface-modified carrier. Z2; finally take 19.1 g ammonium tetrathiotungstate, 7.8 g nickel nitrate and 7.8 g ammonium thiosulfate, add 26 mL deionized water, stir until completely dissolved to obtain a mixed aqueous solution, and then impregnate and support 40.0 g catalyst carrier Z2, then It was vacuum dried at 60°C for 12 h, and calcined at 315°C for 3 h in a nitrogen atmosphere to obtain hydrocracking catalyst C2.

Example 5:

Weigh 200 g of pseudo-boehmite (on a dry basis, all the following raw materials, unless otherwise specified, all weights are on a dry basis), 170 g of amorphous silica-alumina, 26.67 g of USY molecular sieve, and 3.33 g of beta zeolite. After the solid powder was thoroughly mixed, the pre-prepared dilute nitric acid solution was added to it, kneaded for 15 minutes, extruded through a 3.0 mm orifice plate, dried at 140 °C for 12 h, and then calcined at 560 °C for 4 h in an air atmosphere to obtain the catalyst. Carrier S3; then weigh 5.6g of 3-aminopropyltriethoxysilane and add it to 100mL of 95% ethanol solution, stir at room temperature for 20min to fully dissolve it. Then, 40 g of the prepared carrier S3 was added to the above solution, the reaction vessel was purged with nitrogen and maintained at a slight positive pressure in nitrogen atmosphere. After the reaction, the excess ethanol solution was poured out, and the obtained solid particles were washed three times with absolute ethanol at room temperature, then pre-dried at room temperature for 4 h in an air atmosphere, and then placed in a vacuum drying box to fully dry at 70 °C to obtain a surface-modified carrier. Z3; finally, 19.1 g of ammonium tetrathiotungstate, 7.8 g of nickel nitrate and 7.8 g of ammonium thiosulfate were taken, added to 26 mL of deionized water, stirred until completely dissolved to obtain a mixed aqueous solution, and then impregnated and supported 40.0 g of catalyst carrier Z3, and then Vacuum-drying at 60 °C for 12 h, and calcined at 315 °C for 3 h in a nitrogen atmosphere to obtain hydrocracking catalyst C3.

Example 6:

Weigh 200 g of pseudo-boehmite (dry basis, all the following raw materials, unless otherwise specified, all weights are on a dry basis), 170 g of amorphous silica-alumina, 27.27 g of USY molecular sieve, and 2.73 g of beta zeolite. After the solid powder was thoroughly mixed, the pre-prepared dilute nitric acid solution was added to it, kneaded for 15 minutes, extruded through a 3.0 mm orifice plate, dried at 140 °C for 12 h, and then calcined at 560 °C for 4 h in an air atmosphere to obtain the catalyst. Carrier S4; then weigh 5.6 g of 3-aminopropyltriethoxysilane and add it to 100 mL of 95% ethanol solution, and stir at room temperature for 20 min to fully dissolve it. Then, 40 g of the prepared carrier S4 was added to the above solution, the reaction vessel was purged with nitrogen and maintained at a slight positive pressure in nitrogen atmosphere. After the reaction, the excess ethanol solution was poured out, and the obtained solid particles were washed three times with absolute ethanol at room temperature, then pre-dried at room temperature for 4 h in an air atmosphere, and then placed in a vacuum drying box to fully dry at 70 °C to obtain a surface-modified carrier. Z4; finally take 19.1 g of ammonium tetrathiotungstate, 7.8 g of nickel nitrate and 7.8 g of ammonium thiosulfate, add 26 mL of deionized water, stir until completely dissolved to obtain a mixed aqueous solution, and then impregnate and support 40.0 g of catalyst carrier Z4, and then Vacuum drying at 60 °C for 12 h, and calcination at 315 °C for 3 h in a nitrogen atmosphere to obtain hydrocracking catalyst C4.

Example 7:

Weigh 200 g of pseudo-boehmite (on a dry basis, unless otherwise specified, all the weights of the following raw materials are on a dry basis), 170 g of amorphous silica-alumina, 28.12 g of USY molecular sieve, and 1.88 g of beta zeolite. After the solid powder was thoroughly mixed, the pre-prepared dilute nitric acid solution was added to it, kneaded for 15 minutes, extruded through a 3.0 mm orifice plate, dried at 140 °C for 12 h, and then calcined at 560 °C for 4 h in an air atmosphere to obtain the catalyst. Carrier S5; then weigh 5.6 g of 3-aminopropyltriethoxysilane and add it to 100 mL of 95% ethanol solution, and stir at room temperature for 20 min to fully dissolve it. Then, 40 g of the prepared carrier S5 was added to the above solution, and the reaction vessel was purged with nitrogen and maintained at a slight positive pressure in nitrogen atmosphere. After the reaction, the excess ethanol solution was poured out, and the obtained solid particles were washed three times with absolute ethanol at room temperature, then pre-dried at room temperature for 4 h in an air atmosphere, and then placed in a vacuum drying box to fully dry at 70 °C to obtain a surface-modified carrier. Z5; finally take 19.1 g of ammonium tetrathiotungstate, 7.8 g of nickel nitrate and 7.8 g of ammonium thiosulfate, add 26 mL of deionized water, stir until completely dissolved to obtain a mixed aqueous solution, and then impregnate and support 40.0 g of catalyst carrier Z5, and then It was vacuum-dried at 60 °C for 12 h, and calcined at 315 °C for 3 h in a nitrogen atmosphere to obtain hydrocracking catalyst C5.

Comparative Example 1:

Weigh 200 g of pseudo-boehmite (dry basis, all the following raw materials unless otherwise specified, all weights are on a dry basis), 170 g of amorphous silica-alumina, and 30 g of USY molecular sieve, and thoroughly mix these three solid powders Then, the pre-prepared dilute nitric acid solution was added to it, kneaded for 15 minutes, extruded through a 3.0 mm orifice plate, dried at 140 °C for 12 h, and then calcined at 560 °C for 4 h in an air atmosphere to obtain a catalyst carrier S0; then weighed Take 5.6g of 3-aminopropyltriethoxysilane and add it to 100mL of 95% ethanol solution, stir at room temperature for 20min to make it fully dissolved. Then, 40 g of the prepared carrier SO was added to the above solution, the reaction vessel was purged with nitrogen and maintained at a slight positive pressure in nitrogen atmosphere, left to react at room temperature for 12 hours, heated to 60°C, and then reacted for 4 hours. After the reaction, the excess ethanol solution was poured out, and the obtained solid particles were washed three times with absolute ethanol at room temperature, then pre-dried at room temperature for 4 h in an air atmosphere, and then placed in a vacuum drying box to fully dry at 70 °C to obtain a surface-modified carrier. Z0; finally, 19.1 g of ammonium tetrathiotungstate, 7.8 g of nickel nitrate and 7.8 g of ammonium thiosulfate were taken, added to 26 mL of deionized water, stirred until completely dissolved to obtain a mixed aqueous solution, and then impregnated and supported 40.0 g of catalyst carrier Z0, and then Vacuum-drying at 60 °C for 12 h, and calcined at 315 °C for 3 h in a nitrogen atmosphere to obtain the hydrocracking catalyst C0.

Application Example 1: Wax Oil Hydrocracking Reaction

The hydrocracking reaction conditions are: hydrogen pressure 15.2 MPa, hydrogen oil volume ratio 700:1, and space velocity 4.0 h ^-1 . The modified catalyst C0-C5 is used directly. The hydrocracking cycle oil was used as the reaction raw material, the density of which was 0.855 g/ml, the nitrogen content was 1.1 ppmw, the sulfur content was 19 ppmw, and the distillation range distribution was shown in Table 1 below.

Table 1

The hydrocracking reaction unit adopts a one-pass hydrogenation process. The unit is mainly composed of gas feed, liquid feed, hydrogenation reaction, gas-liquid separation and product collection. It is equipped with a single reactor filled with hydrocracking catalyst, which is heated by a 5-stage electric furnace. The reaction effluent enters the high pressure separator and the low pressure separation tank for gas-liquid separation. The high-fraction hydrogen-rich gas is liquid-separated by the separation tank, and the jacketed water is used to cool down and cool down and corresponding technical measures are used to make the ammonium salt crystallize and settle and prevent the downstream pipeline and equipment from being blocked. The low pressure tail gas after the pressure control valve is metered with a gas flow meter and consists of on-line chromatographic analysis. Offline analysis of distillation range for liquid products. The catalyst test results are shown in Table 2 below.

Table 2 Catalyst test results

The catalyst test results show that, compared with the catalyst C0 without the addition of zeolite beta, the activities of catalysts C1~C5 prepared by adding the amount of zeolite beta with different USY: β mass ratios are improved, and the product selectivity occurs. The naphtha selectivity of catalysts C1~C2 increased by about 1-3 percentage points, and the diesel selectivity of catalysts C4-C5 was increased by 1-2 percentage points, indicating that by adding β zeolite with different USY:β mass ratios The amount helps to reduce the formation of undesired heavy polynuclear aromatic by-products that can reduce stability, helps to improve the stability of the catalyst, and indeed helps to improve the performance of the catalyst for addition/dehydrogenation.

Claims (10)

1. a preparation method of sulfide type hydrocracking catalyst, is characterized in that: may further comprise the steps: (1) After fully mixing pseudo-boehmite, amorphous silica-alumina, USY molecular sieve and beta zeolite in a certain proportion, add a certain amount of acid solution, knead for 2-60 minutes, and then extrude into strips; the obtained shaped body is dried and roasted , the catalyst carrier is prepared; (2) Add a modification reagent to the catalyst carrier obtained in step (1), react at 5-40°C for 1-24h, then heat up to 40-100°C, and react for 1-12h, so as to connect new functional groups on the surface of the carrier through chemical bonds, A surface-modified catalyst carrier is obtained; (3) Disperse the VIB group element-containing compound, the VIII group element-containing compound and the sulfur-containing non-metallic compound in a solvent, impregnate the catalyst carrier obtained in step (2) for 1-12 hours, then vacuum dry and calcine in an inert atmosphere , to obtain a hydrocracking catalyst. 2. The preparation method of a sulfurized hydrocracking catalyst according to claim 1, characterized in that: the weight of pseudo-boehmite, amorphous silica-alumina, USY molecular sieve and beta zeolite used in step (1) The ratio is (20-80):(20-60):(1-20):(0.05-4). 3. the preparation method of a kind of sulfide type hydrocracking catalyst according to claim 1, is characterized in that: the add-on of acid solution used in step (1) is pseudo-boehmite, amorphous silica-alumina, USY molecular sieve and 0.5-10% of the total weight of beta zeolite, and its concentration is no more than 10wt%; the acid solution includes inorganic acid or organic acid, wherein the inorganic acid includes any one of sulfuric acid, hydrochloric acid and nitric acid, and the organic acid includes Any of formic acid, acetic acid and citric acid. 4 . The preparation method of a sulfurized hydrocracking catalyst according to claim 1 , wherein the drying and roasting described in step (1) is, after drying at 100-200° C. for 2-24 h, at 400° C. -750 ℃ calcination for 2-8 h. 5 . The preparation method of a sulfurized hydrocracking catalyst according to claim 1 , wherein the modification reagent in step (2) contains two or more functional groups, and one of the functional groups needs to be capable of It reacts with the surface of the inorganic carrier, which is selected from any one of hydroxyl, carboxyl, amino, acid anhydride, halogen substituent, siloxy, phosphoric acid, metaphosphoric or phosphorous; the other functional group needs to be able to interact with VIB The oxide or salt reaction of a Group metal element or a Group VIIB metal element is selected from any one of a hydroxyl group, a carboxyl group, an amino group, a mercapto group, an amide group or a halogen substituent. 6 . The preparation method of a sulfurized hydrocracking catalyst according to claim 1 , wherein the modification reagent added in the step (2) is 0.5-20% of the weight of the catalyst carrier obtained in the step (1). 7 . . 7 . The method for preparing a sulfurized hydrocracking catalyst according to claim 1 , wherein: the compound containing group VIII elements in step (3) includes but is not limited to nickel salts; the compound containing group VIB elements The compound includes sulfur-containing tungsten salt; the sulfur-containing non-metallic compound includes one or more of ammonium sulfide, thiourea, and ammonium thiosulfate. 8 . The method for preparing a sulfurized hydrocracking catalyst according to claim 1 , wherein: the compound containing Group VIB element, the compound containing Group VIII element and the non-metallic sulfur containing described in step (3) The mass ratio of the compounds is (1-600):(1-50):(0.3-500). 9 . The preparation method of a sulfurized hydrocracking catalyst according to claim 1 , wherein the inert atmosphere in step (3) comprises one or more of nitrogen, argon and helium, and the pressure 0-5MPa. 10 . The preparation method of a sulfurized hydrocracking catalyst according to claim 1 , wherein the vacuum drying in step (3) is: vacuum drying at 50-100° C. for 6-48 h, and the inert The roasting in the atmosphere is specifically roasting at 200-350 °C for 2-24 h.