Hydrocracking catalyst as well as preparation method and application thereof

Abstract

The invention provides a preparation method of a hydrocracking catalyst, which comprises the following steps: ball-milling and uniformly mixing a composite material and a compound containing active metal, uniformly mixing with a binder and an extrusion aid, molding, drying and roasting, the hydrocracking catalyst is obtained; the composite material is prepared from the following components in percentage by mass: 10 to 80 percent of amorphous silica-alumina, 10 to 45 percent of a Beta molecular sieve and 10 to 45 percent of a rare earth modified SSZ-13 molecular sieve, wherein the mass of the amorphous silica-alumina is 100 percent; the rare earth modified SSZ-13 molecular sieve is characterized in that the content of rare earth is 0.1 wt%-5wt% in terms of oxide by taking the mass of the rare earth modified SSZ-13 molecular sieve as 100%. The hydrocracking catalyst prepared by the method can improve the hydrocracking catalytic activity and produce more light ethylene raw materials.

Description

Technical Field

[0001] The present invention relates to the technical field of catalysts, and particularly relates to a hydrocracking catalyst, a preparation method thereof, and an application thereof. Background Art

[0002] With the accelerating transformation of the refining and chemical product structure in China, the consumption of refined oil has entered a stage of fluctuating decline from high-speed growth, while the demand for chemical products continues to grow. In particular, the market demand for basic chemical raw materials represented by olefins and aromatics has been steadily increasing. The proportion of petrochemical raw materials in the petroleum consumption structure has been gradually increasing. In the face of the rapid growth of the market demand for ethylene raw materials, how to take measures to convert oil products into ethylene raw materials has become a research hotspot in the petrochemical field. Among them, light ethylene cracking raw materials (cracked light naphtha) have the characteristics of slow coking rate and high yield of "three olefins", and are currently extremely scarce high-quality ethylene raw materials.

[0003] The hydrocracking process can process diesel and wax oil raw materials to produce reforming raw materials, ethylene raw materials and clean oil products. It has many advantages such as strong raw material adaptability, flexible processing scheme, high liquid product yield and good product quality, and has become one of the core technologies for the refining and upgrading of modern enterprises. By hydrocracking hydrotreated diesel and jet fuel to increase the production of light ethylene cracking raw materials, it can effectively support the "oil reduction and chemical increase" production adjustment of refineries. Hydrocracking catalysts are the core of hydrocracking technology, which are composed of metal active components and acidic centers. The appropriate pore structure and acid properties of the catalyst play a decisive role in regulating the fraction oil yield and product distribution, and can hydrogenate and ring-open crack heavy fraction oils during the hydrocracking reaction process, effectively converting them into light fraction oils. To meet the increasing demand for light fraction oils worldwide, the research and development of new light oil-producing hydrocracking catalysts has become the core and key of this technology.

[0004] Chinese Patent Document CN108014843B discloses a Cu-SSZ-13 / M-AlPO composite molecular sieve catalyst, which includes the following components in terms of weight percentage: a) 10-100% of CuSSZ-13 / M-AlPO composite molecular sieve; b) 0-90% of binder. It effectively solves the problems of low stability of methanol-to-olefin catalysts, low selectivity and yield of ethylene, propylene and butene in light olefins, and can be used in the industrial production of methanol-to-olefins. However, this catalyst is only applicable to the methanol reaction process and is difficult to adapt to the oil product reaction process.

[0005] Chinese patent document CN114367307A discloses a preparation method of core-shell structured M@SSZ-13@NanoBeta. Specifically, noble metals are in-situ encapsulated in the core layer of SSZ-13 zeolite to form the core layer M@SSZ-13. Take part of the above core layer samples and put them into the Beta synthesis gel. After crystallization, core-shell type M@SSZ-13@NanoBeta is formed. The pore mouths of SSZ-13 zeolite are modified by the growth of the shell layer NanoBeta zeolite, which limits the contact between sulfides and noble metals and improves the sulfur resistance of the catalyst. In the hydrogen spillover effect, the active hydrogen component can hydrogenate polycyclic aromatic hydrocarbons adsorbed on the acidic sites of the shell layer. Subsequently, the hydrogenation products are further cracked on the NanoBeta zeolite to achieve the selective hydrocracking of polycyclic aromatic hydrocarbons. However, this scheme uses noble metal encapsulation to limit the contact between sulfides and noble metals, but it is difficult to limit the influence of hydrogen sulfide gas generated during the hydrogenation process on noble metals. At the same time, using noble metals results in a high preparation cost.

[0006] Chinese patent document CN113694962B discloses a catalyst for isodewaxing of hydrocracked tail oil to produce base oil and its preparation method. First, use a ball mill to ball mill two different types of molecular sieves, then add an oxide or metal salt of Group VIII B metal elements for ball milling, and finally, the isodewaxing catalyst is prepared through kneading, extrusion, drying, and calcination. By using ball milling, the full mixing of molecular sieves is achieved, the agglomeration between molecular sieves is reduced, the surface area of the molecular sieves is increased, and then through ball milling, the metal elements chemically associate with the molecular sieves, thereby increasing the synergistic effect between the acid and metal in the catalyst, ensuring the dehydrogenation activity of the catalyst, and having high conversion rate and selectivity. Although this scheme uses the ball milling method to mix two molecular sieves with different acidic centers, there are still problems such as agglomeration between the components in the catalyst and small specific surface area of the composite material.

[0007] Chinese patent document CN116064080A provides a method for hydrocracking heavy naphtha. The method includes: in the presence of hydrogen, the heavy naphtha raw material undergoes a hydrocracking reaction under the action of a hydrocracking catalyst; the catalyst includes a carrier and metal components of Group VIB and / or Group VIII; the carrier includes modified ZSM-5 molecular sieve and alumina, and the SiO 2 / Al 2 O 3 molar ratio of the outer surface is 200 - 1000, and the SiO 2 / Al 2 O 3The molar ratio is 40 - 90, the total pyridine infrared acid amount is 0.20 - 0.55 mmol / g, and the total di-tert-butylpyridine infrared acid amount is 0.001 - 0.05 mmol / g. This method can effectively increase the content of linear hydrocarbons in light naphtha and the aromatics potential of heavy naphtha. However, the modified ZSM-5 molecular sieve used in this catalyst uses organic acids and dealumination and silicon supplementation agents during the synthesis process, which will cause environmental pollution. Summary of the Invention

[0008] The object of the present invention is to provide a preparation method of a hydrocracking catalyst, and the hydrocracking catalyst prepared by this method can improve the hydrocracking catalytic activity and produce more light ethylene raw materials.

[0009] To achieve the above object, the present invention provides the following technical solutions:

[0010] A preparation method of a hydrocracking catalyst, comprising the following steps:

[0011] After ball-milling and mixing the composite material with the compound containing the active metal, it is mixed with the binder and the extrusion aid, and then formed, dried, and calcined to obtain the hydrocracking catalyst;

[0012] Based on the mass of the composite material being 100%, the composite material includes 10 wt% - 80 wt% of amorphous silica-alumina, 10 wt% - 45 wt% of Beta zeolite, and 10 wt% - 45 wt% of rare earth modified SSZ-13 zeolite;

[0013] Based on the mass of the rare earth modified SSZ-13 zeolite being 100%, the content of rare earth is 0.1 wt% - 5 wt%.

[0014] The preparation method of the hydrocracking catalyst provided by the present invention uses a hierarchical pore Beta / rare earth SSZ-13 / ASA composite material with a wide pore size range distribution and a large infrared acid amount as the carrier, in-situ ball-milling and mixing with the active metal, and mixing and forming with the binder to increase the production of light ethylene cracking raw materials while ensuring the hydrogenation activity. Among them, the Beta zeolite can be a commercial Beta-type zeolite with any crystal grain size.

[0015] Optionally, in the preparation method of the hydrocracking catalyst provided by the present invention, the silicon-aluminum ratio of the rare earth modified SSZ-13 zeolite is 20 - 100, the specific surface area is 200 - 500 m 2 / g, and the total pore volume is 0.2 - 0.5 mL / g.

[0016] Optionally, in the preparation method of the hydrocracking catalyst provided by the present invention, the ball milling rate is 200-500 rpm, preferably 250-380 rpm; the shaping is extrusion molding, and the shape after extrusion is generally cylindrical, or it can also be made into special-shaped bars such as clover or four-leaf clover shapes, etc.

[0017] Optionally, in the preparation method of the hydrocracking catalyst provided by the present invention, the active metal is selected from Group VIB metals and / or Group VIII metals; the Group VIB metals are selected from molybdenum and / or tungsten; the Group VIII metals are selected from cobalt and / or nickel.

[0018] Optionally, in the preparation method of the hydrocracking catalyst provided by the present invention, the compound containing the active metal is selected from oxides of the active metal and precursor salts of the active metal; the precursor salts of the active metal are selected from any one of carbonates, nitrates, sulfates, etc.

[0019] Optionally, in the preparation method of the hydrocracking catalyst provided by the present invention, the binder includes small-pore alumina and an acid solution, and the acid solution is selected from any one of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, citric acid, tartaric acid, oxalic acid solution, etc.;

[0020] The extrusion aid is selected from, etc.

[0021] Optionally, in the preparation method of the hydrocracking catalyst provided by the present invention, the dosages of the binder and the extrusion aid are not specifically limited, and those conventional in the industry can be used. Based on the mass of the hydrocracking catalyst being 100%, the recommended dosage of the binder in the present invention is 5%-30%; based on the mass of the carrier of the hydrocracking catalyst being 100%, the dosage of the extrusion aid is 1%-5%.

[0022] Optionally, in the preparation method of the hydrocracking catalyst provided by the present invention, the preparation of the composite material includes the following steps:

[0023] (1) Disperse Beta zeolite and rare earth-modified SSZ-13 zeolite in an acidic aluminum source solution, heat and stir to obtain a zeolite mixed slurry;

[0024] (2) While stirring, add an alkaline solution and sodium silicate to the zeolite mixed slurry to obtain a mixed material;

[0025] (3) The mixed material is separated, washed, dried, and calcined to obtain the composite material.

[0026] Optionally, in step (1) of the preparation method of the composite material provided by the present invention, with Al 2 O 3It is calculated that the concentration of the acidic aluminum source solution is 4 wt% to 9 wt%; the acidic aluminum source solution is selected from any one of aluminum chloride solution, aluminum sulfate solution, and aluminum nitrate solution;

[0027] In step (2), the alkaline solution is selected from any one of sodium hydroxide, sodium carbonate solution, and sodium bicarbonate solution, and preferably sodium hydroxide solution;

[0028] In step (1), the temperature of the heating and stirring is 60 to 100 °C, and the time is 1 to 8 h.

[0029] Optionally, in step (2) of the preparation method of the composite material provided by the present invention, the alkaline solution is added within 0.2 to 8 h under the stirring state at 60 to 100 °C. After the addition of the alkaline solution is completed, it is maintained at 60 to 100 °C for 0.5 to 8 h, and then the water glass is added within 0.5 to 10 h. After the addition of the water glass is completed, it is maintained at 60 to 100 °C for 0.5 to 8 h.

[0030] Optionally, in the preparation method of the hydrocracking catalyst provided by the present invention, the preparation of the rare earth modified SSZ-13 molecular sieve includes the following steps:

[0031] 1) Add a silicon source, an aluminum source, an alkali source, and a template agent to water and mix to form a gel, carry out hydrothermal crystallization, wash and separate to obtain a first solid;

[0032] 2) Carry out ion exchange on the first solid with a rare earth precursor solution, wash and separate to obtain a second solid;

[0033] 3) After alkali treatment of the second solid, wash and separate to obtain a third solid; carry out ammonium exchange on the third solid with an ammonium salt, and then wash, separate, dry, and calcine to obtain the rare earth modified SSZ-13 molecular sieve.

[0034] Optionally, in step 1) of the preparation method of the rare earth modified SSZ-13 molecular sieve provided by the present invention, in terms of oxides, the molar ratio of each component in the gel is (60 - 150)SiO 2 :(0.5 - 5)Al 2 O 3 :(5 - 20)Na 2 O:(3000 - 4500)H 2 O:(10 - 30) template agent;

[0035] In step 1), the temperature of the hydrothermal crystallization is 80 to 190 °C, and the time is 72 to 170 h.

[0036] Optionally, in step 2) of the preparation method of the rare earth modified SSZ-13 molecular sieve provided by the present invention, the temperature of the ion exchange is 50-120°C and the time is 1-10 h;

[0037] The concentration of the rare earth precursor solution is (0.5-7.5) g / L;

[0038] The solid-liquid ratio of the first solid to the rare earth precursor solution is 1:8-1:40;

[0039] Optionally, in step 3) of the preparation of the rare earth modified SSZ-13 molecular sieve provided by the present invention, the alkali treatment includes the following steps: at 50-120°C, soaking the second solid in an alkaline solution of 0.1 wt%-10 wt% for 1-10 h;

[0040] In step 3), the temperature of the ammonium exchange is 50-120°C and the time is 1-10 h.

[0041] Optionally, in the preparation process of the rare earth modified SSZ-13 molecular sieve provided by the present invention, the silicon source is selected from one or more of silica sol, solid silica gel and fumed silica; preferably silica sol or solid silica gel;

[0042] The aluminum source is selected from any one of aluminum hydroxide, pseudo-boehmite, aluminum isopropoxide and aluminum sulfate; preferably aluminum hydroxide or pseudo-boehmite;

[0043] The template agent is selected from any one of N,N,N-trimethyl-adamantylammonium, N,N,N-trimethyl-adamantylammonium iodide and tetraethylammonium hydroxide; preferably N,N,N-trimethyl-adamantylammonium or N,N,N-trimethyl-adamantylammonium iodide;

[0044] The rare earth precursor is selected from soluble rare earth chlorides or nitrates; preferably any one of lanthanum chloride, cerium chloride, lanthanum nitrate and cerium nitrate, etc.;

[0045] The alkali source is selected from any one of sodium hydroxide, sodium carbonate, sodium bicarbonate, etc.

[0046] The ammonium salt is selected from any one of ammonium sulfate, ammonium chloride, etc.

[0047] The present invention also provides a hydrocracking catalyst prepared by the above preparation method of the hydrocracking catalyst. Based on the mass of the hydrocracking catalyst being 100%, in terms of oxides, the content of the active metal is 15 wt%-35 wt%; preferably, the content of the Group VIB metal is 10 wt%-28 wt%; the content of the Group VIII metal is 1 wt%-12 wt%.

[0048] Optionally, the specific surface area of the hydrocracking catalyst provided by the present invention is 280-310 m 2 / g, the pore volume is 0.27-0.40 mL / g, the pore diameter is 7.8-10.2 nm, and the acid amount is 350-383 μmol / g.

[0049] The present invention also provides an application of a hydrocracking catalyst prepared by the preparation method of the above-mentioned hydrocracking catalyst in the preparation of light ethylene cracking raw materials by diesel hydrocracking or jet fuel hydrocracking; preferably, the conditions of the hydrocracking are as follows: the temperature is 285-345 °C, the pressure is 6-16 MPa, the hydrogen-oil volume ratio is 500-1500:1, and the liquid hourly space velocity is 0.6-1.8 h -1 .

[0050] Compared with the prior art, the present invention has the following advantages:

[0051] The preparation method of the hydrocracking catalyst provided by the present invention utilizes the pore structure and acidity of the composite material, and ball-mills and mixes the composite material with a compound containing an active metal to achieve high dispersion of the active metal in the composite material, significantly improving the hydrocracking catalytic activity and the yield of light ethylene raw materials; in addition, this method omits the processes of carrier drying, calcination, impregnation, etc. in the conventional catalyst preparation process, shortening the preparation process, saving energy and reducing consumption. Specific Embodiments

[0052] The present invention will be specifically described below through examples. It is necessary to point out here that the following examples are only used to further illustrate the present invention and cannot be construed as limiting the protection scope of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention according to the above content of the present invention.

[0053] For those not specifying specific experimental steps or conditions in the examples, the operations or conditions of the conventional experimental steps described in the literature in the art can be followed. For reagents or instruments not indicating the manufacturer, they are all conventional reagent products that can be obtained through commercial purchase.

[0054] Source of raw materials:

[0055] Sodium hydroxide, analytical pure, Beijing Chemical Plant;

[0056] Aluminum sulfate, industrial grade, Research Institute of Shandong Aluminum Industry Company;

[0057] Sodium silicate, industrial grade, Beijing Hongxing Sodium Silicate Factory;

[0058] Ammonium metatungstate, industrial grade, Merck reagent, WO 3 Content 85%;

[0059] ZSM-35 molecular sieve, innochem, silica-alumina ratio 19;

[0060] Tartaric acid, innochem, purity ≥ 99%;

[0061] Citric acid, innochem, purity 99%;

[0062] Beta molecular sieve, industrial product, Research Institute of Shandong Aluminum Industry Company;

[0063] Ammonium sulfate, innochem, purity 99%;

[0064] Lanthanum chloride, innochem, purity 99%;

[0065] Nickel basic carbonate, industrial product, Merck reagent, NiO2 content 40%;

[0066] Ammonia water, Innochem, purity 25.0 - 30.0%

[0067] Tetraethylammonium hydroxide, innochem, AR 25% aqueous solution

[0068] Sodium carbonate, Fisher

[0069] Sodium bicarbonate, innochem, purity 99%;

[0070] Cerium nitrate, Innochem, 99.5% - Ce

[0071] N,N,N-Trimethyl-adamantanammonium, Tci, purity 98%.

[0072] Analysis and testing methods: The specific surface area and pore volume were measured using an ASAP2020M specific surface area and porosity analyzer produced by Micromeritics. The specific surface area was calculated according to the BET method; the pore volume and pore diameter were calculated by the BJH method.

[0073] Pyridine-infrared spectroscopy (Py-IR)

[0074] Take about 10 mg of the sample to be tested and press it into a self-supporting tablet, fix it in an infrared cell, desorb for 2 hours at a vacuum of 0.01 Pa and a temperature of 400 °C to purify the surface, cool to room temperature, and measure the background infrared spectrum of the sample. After adsorbing pyridine at room temperature, equilibrate for 0.5 hour, then program the temperature to 200 °C and 350 °C for vacuum (0.01 Pa) desorption for 2 hours, and then cool to room temperature respectively to measure the spectra. Use the integrated intensities of the infrared bands at 1450 cm -1 and 1540 cm -1 to determine the amounts of Brønsted acid and Lewis acid, and use the integrated extinction coefficients given by Emeis for quantitative calculation of the acid amounts.

[0075] Example 1

[0076] This example provides a hydrocracking catalyst, and its preparation method includes the following steps:

[0077] Rare earth modified SSZ-13 molecular sieve

[0078] 1) Add 120 g of 30% silica sol, 0.8 g of aluminum hydroxide, 16.8 g of sodium hydroxide, and 25.9 g of N,N,N-trimethyl-adamantylammonium (template agent) to 685.7 g of water and mix to form a gel. Then, hydrothermally crystallize at 130 °C for 150 h, wash and filter to obtain the first solid;

[0079] Calculated as oxides (the template agent is not calculated as an oxide), the molar ratio of each component in the gel is 60SiO 2 : 0.5Al 2 O 3 : 20Na 2 O: 4300H 2 O: 12 template agent;

[0080] 2) Take 100 g of the first solid and mix it with 1 L of a lanthanum chloride solution containing 2.2 g according to a solid-liquid ratio of 1:11. Perform ion exchange under stirring conditions at 110 °C for 1 h, then wash and filter to obtain the second solid;

[0081] 3) Add the obtained second solid to 1000 mL of a 5 wt% sodium hydroxide solution, soak and treat at 80 °C for 3 h, then wash and filter; add the obtained third solid to a 2 mol / L ammonium sulfate solution, perform ammonium exchange at 90 °C for 4 h, wash, filter, dry at 120 °C, and calcine at 500 °C to obtain the rare earth modified SSZ-13 molecular sieve. After testing, the silica-alumina ratio of this rare earth modified SSZ-13 molecular sieve is 96, the specific surface area is 200 m 2 / g, and the total pore volume is 0.43 mL / g. The lanthanum oxide content is 1.1 wt%.

[0082] Composite material:

[0083] (1) Weigh the Beta molecular sieve with a silica-alumina ratio of 50 and the above-prepared rare earth modified SSZ-13 molecular sieve according to a mass ratio of 1:1:1 for amorphous silica-alumina, Beta molecular sieve, and rare earth modified SSZ-13 molecular sieve. Disperse them in an aluminum sulfate solution with an alumina concentration of 7 wt%, heat to 90 °C, and stir constantly at a constant temperature for 2 h to obtain a slurry of the molecular sieve mixture;

[0084] (2) While maintaining at 60 °C with stirring, add a 10 wt% sodium hydroxide solution to the slurry of the above molecular sieve mixture (taking 0.5 h). After the addition of the dilute ammonia water solution is completed, maintain at 70 °C for 1 h; then continue to add 21.4 g of a 28 wt% sodium silicate solution while maintaining at 70 °C with stirring (taking 0.8 h). After the addition of the sodium silicate solution is completed, maintain at 70 °C for 2 h to obtain a mixed material;

[0085] (3) Filter, wash, dry the mixed material at 100 °C for 3 hours, and calcine at 500 °C for 5 hours to obtain a composite material.

[0086] Hydrocracking catalyst:

[0087] (1) Weigh 40 g of the above composite material, 17.5 g of molybdenum oxide, and 6.3 g of nickel basic carbonate, place them in a ball mill, mix and ball mill at a rate of 400 r / min for 3 h, then uniformly mix with 10 g of small-pore alumina and 2.5 g of talc powder, add 2.5 g of concentrated nitric acid (68 wt%) solution, extrude into pellets, dry at 100 °C for 3 h, and calcine at 500 °C for 4 h to obtain a hydrocracking catalyst.

[0088] Example 2

[0089] This example provides a hydrocracking catalyst, and its preparation method includes the following steps:

[0090] Rare earth modified SSZ-13 molecular sieve

[0091] 1) Add 60 solid silica gel, 1.6 g of aluminum hydroxide, 4.2 g of sodium hydroxide, and 32.4 g of N,N,N-trimethyl-adamantyl ammonium iodide to 755.3 g of water and mix to form a gel. Then, carry out hydrothermal crystallization at 160 °C for 100 h, wash and filter to obtain a first solid;

[0092] Calculated as oxides (the template agent is not calculated as an oxide), the molar ratio of each component in the gel is 100SiO 2 : 1Al 2 O 3 : 5Na 2 O: 4400H 2 O: 15 template agent;

[0093] 2) Take 100 g of the above first solid and mix it with 1000 mL of a cerium chloride solution containing 0.8 g according to a solid-liquid ratio of 1:9, carry out ion exchange at 100 °C with stirring for 3 h, wash and filter to obtain a second solid;

[0094] (3) The obtained second solid was added to 1000 mL of 3 wt% sodium hydroxide solution and soaked at 50 °C for 9 h, followed by washing and filtration; the obtained third solid was added to 2 mol / L ammonium sulfate solution and subjected to ammonium exchange at 110 °C for 2 h, followed by washing, filtration, drying at 110 °C, and calcination at 600 °C to obtain rare earth modified SSZ-13 zeolite. After detection, the silicon-aluminum ratio of the rare earth modified SSZ-13 zeolite was 75, the specific surface area was 300 m 2 / g, the total pore volume was 0.35 mL / g, and the cerium oxide content was 0.5 wt%.

[0095] Composite material:

[0096] (1) According to the mass ratio of amorphous silica-alumina, Beta zeolite and rare earth modified SSZ-13 zeolite being 16:9:9, Beta zeolite with a silicon-aluminum ratio of 45 and the above-prepared rare earth modified SSZ-13 zeolite were weighed and dispersed in an aluminum sulfate solution with a concentration of 5 wt% calculated based on Al 2 O 3 . The mixture was heated to 80 °C and stirred at a constant temperature for 1 h to obtain a slurry of the zeolite mixture;

[0097] (2) While maintaining 80 °C and stirring, 10 wt% dilute ammonia water solution was added to the slurry of the zeolite mixture (within 0.2 h). After the addition of the dilute ammonia water solution was completed, it was maintained at 80 °C for 1 h; then, while still maintaining 80 °C and stirring, 28.6 g of 28 wt% water glass solution was added (within 0.5 h). After the addition of the water glass solution was completed, it was maintained at 80 °C for 7 h to obtain a mixed material;

[0098] (3) The mixed material was filtered, washed, dried at 110 °C for 5 h, and calcined at 550 °C for 5 h to obtain the composite material.

[0099] Hydrocracking catalyst:

[0100] (1) Weigh 30 g of the above composite material, 17.5 g of molybdenum oxide and 6.3 g of basic nickel carbonate, place them in a ball mill and mix and ball mill at a rate of 350 r / min for 3 h. Then, after uniformly mixing with 20 g of small pore alumina and 2.5 g of talc powder, 2.5 g of concentrated nitric acid (68 wt%) solution was added, extruded into pellets, dried at 100 °C for 3 h, and calcined at 500 °C for 4 h to obtain the hydrocracking catalyst.

[0101] Example 3

[0102] This example provides a hydrocracking catalyst, and its preparation method includes the following steps:

[0103] Rare earth modified SSZ-13 zeolite

[0104] 1) 200 g of 30% silica sol, 1.9 g of pseudo-boehmite (containing 70% alumina), 12.6 g of sodium hydroxide, and 38.9 g of N,N,N-trimethyl-adamantylammonium were added to 556.4 g of water and mixed to form a gel. Then, hydrothermal crystallization was carried out at 140 °C for 120 h, followed by washing and filtration to obtain a first solid;

[0105] Calculated as oxides (the template agent is not calculated as an oxide), the molar ratio of each component in the gel is 100SiO 2 : 1.3Al 2 O 3 : 15Na 2 O: 3900H 2 O: 18 template agent;

[0106] 2) 100 g of the first solid was mixed with 800 mL of a lanthanum nitrate solution containing 5.8 g at a solid-liquid ratio of 1:12, and ion exchange was carried out under stirring conditions at 60 °C for 9 h. After washing and filtration, a second solid was obtained;

[0107] 3) The obtained second solid was added to 1000 mL of an 8 wt% sodium hydroxide solution and soaked at 60 °C for 7 h. After washing and filtration, the obtained third solid was added to a 2 mol / L ammonium sulfate solution, and ammonium exchange was carried out at 100 °C for 3 h. After washing, filtration, drying at 110 °C, and calcination at 550 °C, a rare earth-modified SSZ-13 molecular sieve was obtained. After testing, the silicon-aluminum ratio of the rare earth-modified SSZ-13 molecular sieve was 60, the specific surface area was 400 m 2 / g, the total pore volume was 0.22 mL / g, and the lanthanum oxide content was 2.5 wt%.

[0108] Composite material:

[0109] (1) According to the mass ratio of amorphous silica-alumina, Beta molecular sieve to rare earth-modified SSZ-13 molecular sieve of 4:6:5, a Beta molecular sieve with a silicon-aluminum ratio of 55 and the above-prepared rare earth-modified SSZ-13 molecular sieve were weighed and dispersed in an aluminum nitrate solution with a concentration of 5 wt% calculated as Al 2 O 3 and heated to 90 °C, and stirred at a constant temperature for 2 h to obtain a slurry of the molecular sieve mixture;

[0110] (2) While maintaining 80 °C and stirring, a 12 wt% sodium hydroxide solution was added to the slurry of the above molecular sieve mixture (for 1 h). After the addition of the dilute ammonia water solution was completed, it was maintained at 90 °C for 7 h; then, while continuing to maintain 90 °C and stirring, 28.6 g of a 28 wt% water glass solution was added (for 0.5 h). After the addition of the water glass solution was completed, it was maintained at 90 °C for 6 h to obtain a mixed material;

[0111] (3) Filter, wash the mixed materials, dry them at 120 °C for 2 hours, and calcine them at 550 °C for 3 hours to obtain the composite material.

[0112] Hydrocracking catalyst:

[0113] (1) Weigh 40 g of the above composite material, 17.5 g of molybdenum oxide, and 6.3 g of basic nickel carbonate, place them in a ball mill, mix and ball mill at a rate of 300 r / min for 3 h, then uniformly mix with 10 g of small-pore alumina and 2.5 g of carboxymethyl cellulose, add 2.5 g of concentrated nitric acid (68 wt%) solution, extrude into pellets, dry at 100 °C for 3 h, and calcine at 500 °C for 4 h to obtain the hydrocracking catalyst.

[0114] Example 4

[0115] This example provides a hydrocracking catalyst, and its preparation method includes the following steps:

[0116] Rare earth modified SSZ-13 molecular sieve

[0117] 1) Add 240 g of silica sol, 6.9 g of aluminum sulfate, 18.2 g of sodium carbonate, and 31.2 g of tetraethylammonium hydroxide to 643.9 g of water and mix to form a gel, then hydrothermally crystallize at 100 °C for 150 h, wash and filter to obtain the first solid;

[0118] Calculated as oxides (the template agent is not calculated as an oxide), the molar ratio of each component in the gel is 120SiO 2 : 2Al 2 O 3 : 17Na 2 O: 3600H 2 O: 21 template agent;

[0119] 2) Take 100 g of the above first solid and 2000 mL of a solution containing 8.5 g of cerium nitrate, carry out ion exchange at a solid-liquid ratio of 1:16 under stirring conditions at 80 °C for 7 h, wash and filter to obtain the second solid;

[0120] 3) Add the obtained second solid to 1000 mL of 10 wt% sodium hydroxide solution, soak and treat at 70 °C for 5 h, wash and filter, add the obtained third solid to 2 mol / L ammonium sulfate solution, carry out ammonium exchange at 80 °C for 5 h, wash, filter, dry at 115 °C, and calcine at 650 °C to obtain the rare earth modified SSZ-13 molecular sieve. After testing, the silica-alumina ratio of the rare earth modified SSZ-13 molecular sieve is 55, the specific surface area is 350 m 2 / g, the total pore volume is 0.25 mL / g, and the cerium oxide content is 4.1 wt%.

[0121] Composite material:

[0122] (1) According to the mass ratio of amorphous silica-alumina, Beta zeolite and rare earth modified SSZ-13 zeolite being 12:7:6, weigh Beta zeolite with a silica-alumina ratio of 50 and the above-prepared rare earth modified SSZ-13 zeolite, disperse them in an aluminum sulfate solution with a concentration of 8 wt% calculated based on Al 2 O 3 , heat to 60 °C, and stir at a constant temperature for 7 h to obtain a slurry of the molecular sieve mixture;

[0123] (2) While maintaining 90 °C and stirring, add a 6 wt% dilute ammonia water solution to the slurry of the above molecular sieve mixture (it takes 5 h). After the addition of the dilute ammonia water solution is completed, maintain at 100 °C for 5 h; then continue to add 28.6 g of a water glass solution with a concentration of 28 wt% at 100 °C and under stirring (it takes 3 h). After the addition of the water glass solution is completed, maintain at 100 °C for 5 h to obtain a mixed material;

[0124] (3) Filter, wash, dry at 110 °C for 6 hours, and calcine at 550 °C for 3 hours for the mixed material to obtain a composite material.

[0125] Hydrocracking catalyst:

[0126] (1) Weigh 30 g of the above composite material, 17.5 g of molybdenum oxide and 6.3 g of nickel basic carbonate, place them in a ball mill and mix and ball mill at a speed of 500 r / min for 3 h. Then, after uniformly mixing with 20 g of small pore alumina and 2.5 g of sawdust powder, add 2.5 g of concentrated nitric acid (68 wt%) solution, extrude into pellets, dry at 100 °C for 3 h, and calcine at 500 °C for 4 h to obtain a hydrocracking catalyst.

[0127] Example 5

[0128] This example provides a hydrocracking catalyst, and its preparation method includes the following steps:

[0129] Rare earth modified SSZ-13 zeolite

[0130] 1) Add 85 g of fumed silica, 4.7 g of pseudo-boehmite, 20.4 g of sodium bicarbonate, and 54.0 g of N,N,N-trimethyl-adamantyl ammonium iodide to 687 g of water and mix to form a gel. Then, hydrothermally crystallize at 80 °C for 165 h, wash and filter to obtain a first solid;

[0131] Based on oxides (the template agent is not counted as an oxide), the molar ratio of each component in the gel is 145SiO 2 : 3Al 2 O 3 : 12Na 2 O: 3400H 2O: 25 template agent;

[0132] 2) Take 100 g of the above-mentioned first solid and 3000 mL of a solution containing 10.6 g of cerium nitrate, and perform ion exchange at a solid-liquid ratio of 1:25 under stirring conditions at 90 °C for 5 h. After washing and filtering, a second solid is obtained;

[0133] 3) Add the obtained second solid to 1000 mL of 1 wt% sodium hydroxide solution, soak it at 100 °C for 3 h, wash and filter it; add the obtained third solid to 2 mol / L ammonium sulfate solution, perform ammonium exchange at 70 °C for 7 h, wash, filter, dry at 120 °C, and calcine at 500 °C to obtain a rare-earth modified SSZ-13 molecular sieve. After testing, the silicon-aluminum ratio of the rare-earth modified SSZ-13 molecular sieve is 45, the specific surface area is 450 m 2 / g, the total pore volume is 0.32 mL / g, and the cerium oxide content is 5.0 wt%.

[0134] Composite material:

[0135] (1) Weigh amorphous silica-alumina, Beta zeolite and the above-prepared rare-earth modified SSZ-13 molecular sieve according to a mass ratio of 2:9:2. Disperse the Beta zeolite with a silicon-aluminum ratio of 50 and the above-prepared rare-earth modified SSZ-13 molecular sieve in an aluminum chloride solution with a concentration of 5 wt% calculated based on Al 2 O 3 and heat it to 70 °C, and stir it at a constant temperature for 3 h to obtain a slurry of the molecular sieve mixture;

[0136] (2) While maintaining 100 °C and stirring, add a 13 wt% sodium hydroxide solution to the slurry of the above molecular sieve mixture (it takes 6 h). After the addition of the dilute ammonia water solution is completed, maintain it at 100 °C for 3 h; then continue to add 28.6 g of a 28 wt% water glass solution while maintaining 100 °C and stirring (it takes 8 h). After the addition of the water glass solution is completed, maintain it at 100 °C for 1 h to obtain a mixed material;

[0137] (3) Filter, wash, dry the mixed material at 120 °C for 2 h, and calcine it at 500 °C for 5 h to obtain a composite material.

[0138] Hydrocracking catalyst:

[0139] (1) Weigh 20 g of the above composite material, 11.6 g of molybdenum oxide and 4.2 g of basic nickel carbonate, place them in a ball mill and mix and ball mill at a speed of 400 r / min for 3 h. Then, uniformly mix them with 30 g of small-pore alumina and 2.5 g of talc powder, add 2.5 g of concentrated nitric acid (68 wt%) solution, extrude into pellets, dry at 100 °C for 3 h, and calcine at 500 °C for 4 h to obtain a hydrocracking catalyst.

[0140] Example 6

[0141] This example provides a hydrocracking catalyst, and its preparation method includes the following steps:

[0142] Rare earth modified SSZ-13 molecular sieve

[0143] 1) Add 81 g of solid silica gel, 20.6 g of aluminum isopropoxide, 8.4 g of sodium hydroxide, and 62.7 g of N,N,N-trimethyl-adamantylammonium to 541.8 g of water and mix to form a gel. Then, hydrothermally crystallize at 190 °C for 75 h, wash and filter to obtain the first solid;

[0144] Calculated as oxides (template agent is not calculated as oxides), the molar ratio of each component in the gel is 135SiO 2 : 5Al 2 O 3 : 10Na 2 O: 3100H 2 O: 29 template agent;

[0145] 2) Take 100 g of the above first solid and 4000 mL of a lanthanum nitrate solution containing 11 g, and perform ion exchange at a solid-liquid ratio of 1:40 under stirring conditions at 100 °C for 2 h. After washing and filtering, obtain the second solid;

[0146] 3) Add the obtained second solid to 1000 mL of 0.5 wt% sodium hydroxide solution, soak and treat at 120 °C for 1 h, wash and filter; add the obtained third solid to 2 mol / L ammonium sulfate solution, perform ammonium exchange at 50 °C for 9 h, wash, filter, dry at 120 °C, and calcine at 500 °C to obtain the rare earth modified SSZ-13 molecular sieve. After detection, the silicon-aluminum ratio of the rare earth modified SSZ-13 molecular sieve is 25, the specific surface area is 500 m 2 / g, the total pore volume is 0.46 mL / g, and the lanthanum oxide content is 5 wt%.

[0147] Composite material:

[0148] (1) Weigh Beta molecular sieve with a silicon-aluminum ratio of 50 and the above-prepared rare earth modified SSZ-13 molecular sieve according to the mass ratio of amorphous silica-alumina, Beta molecular sieve and rare earth modified SSZ-13 molecular sieve being 8:1:12, disperse them in an aluminum sulfate solution with a concentration of 5 wt% calculated as Al 2 O 3 and heat to 80 °C, stir at a constant temperature for 1 h to obtain a slurry of the molecular sieve mixture;

[0149] (2) While maintaining at 70 °C and with stirring, add a 9 wt% sodium aluminate solution to the slurry of the above molecular sieve mixture (over 3 h). After the addition of the dilute ammonia water solution is complete, maintain at 60 °C for 1 h; then continue to add 28.6 g of a 28 wt% water glass solution while maintaining at 60 °C and with stirring (over 2.5 h). After the addition of the water glass solution is complete, maintain at 60 °C for 1 h to obtain a mixed material;

[0150] (3) Filter, wash, dry the mixed material at 100 °C for 8 h, and calcine at 650 °C for 2 h to obtain a composite material.

[0151] Hydrocracking catalyst:

[0152] (1) Weigh 40 g of the above composite material, 17.5 g of molybdenum oxide, and 6.3 g of nickel basic carbonate, place them in a ball mill, mix and ball mill at a rate of 250 r / min for 3 h, then uniformly mix with 10 g of small-pore alumina and 2.5 g of talc powder, add 2.5 g of concentrated nitric acid (68 wt%) solution, extrude into pellets, dry at 100 °C for 3 h, and calcine at 500 °C for 4 h to obtain a hydrocracking catalyst.

[0153] Comparative Example 1

[0154] This comparative example provides a hydrocracking catalyst, and its preparation method includes the following steps:

[0155] Preparation of SSZ-13 molecular sieve

[0156] 1) Add 120 g of 30% silica sol, 0.8 g of aluminum hydroxide, 16.8 g of sodium hydroxide, and 25.9 g of N,N,N-trimethyl-adamantylammonium (template agent) to 685.7 g of water and mix to form a gel. Then, hydrothermally crystallize at 130 °C for 150 h, wash and filter to obtain a first solid;

[0157] In terms of oxides (the template agent is not counted as an oxide), the molar ratio of each component in the gel is 60SiO 2 : 0.5Al 2 O 3 : 20Na 2 O: 4300H 2 O: 12 template agent;

[0158] 2) Take 100 g of the first solid and add it to 1000 mL of a 5 wt% sodium hydroxide solution. Soak and treat at 80 °C for 3 h, then wash and filter; add the obtained third solid to a 2 mol / L ammonium sulfate solution, perform ammonium exchange at 90 °C for 4 h, wash, filter, dry at 120 °C, and calcine at 500 °C to obtain SSZ-13 molecular sieve. The silicon-aluminum ratio of the SSZ-13 molecular sieve is 96, and the specific surface area is 510 m 2 / g, and the total pore volume is 0.33 mL / g.

[0159] Composite material:

[0160] (1) According to the mass ratio of amorphous silica-alumina, Beta zeolite and SSZ-13 zeolite being 1:1:1, weigh Beta zeolite with a silica-alumina ratio of 50 and the above-prepared rare earth-modified SSZ-13 zeolite, disperse them in an aluminum sulfate solution with an alumina concentration of 7 wt%, heat to 90 °C, and stir at a constant temperature for 2 h to obtain a slurry of the zeolite mixture;

[0161] (2) While maintaining 60 °C and stirring, add a 10 wt% sodium hydroxide solution to the slurry of the above zeolite mixture (it takes 0.5 h). After the addition of the dilute ammonia water solution is completed, maintain at 70 °C for 1 h; then continue to add 21.4 g of a water glass solution with a concentration of 28 wt% at 70 °C and under stirring (it takes 0.8 h). After the addition of the water glass solution is completed, maintain at 70 °C for 2 h to obtain a mixed material;

[0162] (3) Filter, wash, dry at 100 °C for 3 hours, and calcine at 500 °C for 5 hours for the mixed material to obtain the composite material.

[0163] Hydrocracking catalyst:

[0164] (1) Weigh 40 g of the above composite material, 0.22 g of lanthanum chloride, 17.5 g of molybdenum oxide and 6.3 g of basic nickel carbonate, place them in a ball mill and mix and ball mill at a speed of 400 r / min for 3 h, then uniformly mix with 10 g of small-pore alumina and 2.5 g of talc powder, add 2.5 g of concentrated nitric acid (68 wt%) solution, extrude into pellets, dry at 100 °C for 3 h, and calcine at 500 °C for 4 h to obtain the hydrocracking catalyst.

[0165] Comparative Example 2

[0166] This comparative example provides a hydrocracking catalyst, and its preparation method includes the following steps:

[0167] Rare earth-modified SSZ-13 zeolite

[0168] 1) Add 120 g of 30% silica sol, 0.8 g of aluminum hydroxide, 16.8 g of sodium hydroxide and 25.9 g of N,N,N-trimethyl-adamantylammonium (template agent) to 685.7 g of water and mix to form a gel, then hydrothermally crystallize at 130 °C for 150 h, wash and filter to obtain the first solid;

[0169] Calculated as oxides (the template agent is not calculated as oxides), the molar ratio of each component in the gel is 60SiO 2 : 0.5Al 2 O 3: 20Na 2 O: 4300H 2 O: 12 template agent;

[0170] 2) Take 100 g of the first solid and mix it with 1 L of a lanthanum chloride solution containing 2.2 g at a solid-liquid ratio of 1:11. Conduct ion exchange for 1 h under stirring conditions at 110 °C, and then wash and filter to obtain the second solid;

[0171] 3) Add the obtained second solid to 1000 mL of 5 wt% sodium hydroxide solution, soak and treat it at 80 °C for 3 h, then wash and filter; add the obtained third solid to 2 mol / L ammonium sulfate solution, conduct ammonium exchange at 90 °C for 4 h, wash, filter, dry at 120 °C, and calcine at 500 °C to obtain the rare earth modified SSZ-13 molecular sieve. After testing, the silica-alumina ratio of this rare earth modified SSZ-13 molecular sieve is 96, the specific surface area is 200 m 2 / g, and the total pore volume is 0.43 mL / g. The lanthanum oxide content is 1.1 wt%.

[0172] Composite material:

[0173] (1) Weigh the Beta molecular sieve with a silica-alumina ratio of 50 and the above-prepared rare earth modified SSZ-13 molecular sieve according to the mass ratio of amorphous silica-alumina, Beta molecular sieve to rare earth modified SSZ-13 molecular sieve being 10:2:13, disperse them in an aluminum sulfate solution with an alumina concentration of 7 wt%, heat to 90 °C, and stir constantly at a constant temperature for 2 h to obtain a slurry of the molecular sieve mixture;

[0174] (2) While maintaining 60 °C and stirring, add 10 wt% sodium hydroxide solution to the slurry of the above molecular sieve mixture (it takes 0.5 h). After the addition of the dilute ammonia water solution is completed, maintain it at 70 °C for 1 h; then continue to maintain at 70 °C and stir, and add 21.4 g of a water glass solution with a concentration of 28 wt% (it takes 0.8 h). After the addition of the water glass solution is completed, maintain it at 70 °C for 2 h to obtain a mixed material;

[0175] (3) Filter, wash, dry the mixed material at 100 °C for 3 h, and calcine at 500 °C for 5 h to obtain the composite material.

[0176] Hydrocracking catalyst:

[0177] (1) Weigh 40 g of the above composite material, 17.5 g of molybdenum oxide, and 6.3 g of basic nickel carbonate, place them in a ball mill and mix and ball mill at a speed of 400 r / min for 3 h, then uniformly mix them with 10 g of small pore alumina and 2.5 g of talc powder, add 2.5 g of concentrated nitric acid (68 wt%) solution, extrude into pellets, dry at 100 °C for 3 h, and calcine at 500 °C for 4 h to obtain the hydrocracking catalyst.

[0178] Comparative Example 3

[0179] This comparative example provides a hydrocracking catalyst, and its preparation method comprises the following steps:

[0180] Rare earth modified SSZ-13 molecular sieve: same as Example 1.

[0181] Composite material: Same as Example 1.

[0182] Hydrocracking catalyst:

[0183] Weigh 40g of the composite material, mix it evenly with 10g of small pore alumina and 2.5g of sesbania powder, then add 2.5g of concentrated nitric acid (68wt%), extrude it into strips, dry it at 120℃ for 3h, and calcine it at 540℃ for 4h to obtain a catalyst carrier;

[0184] Weigh 17.5 g of molybdenum oxide and 6.3 g of basic nickel carbonate, mix them, add 2.5 g of phosphoric acid solution, prepare an equal volume of impregnation solution according to the water absorption rate of the carrier, impregnate the above catalyst carrier with an equal volume, dry at 100° C. for 3 h, calcine at 500° C. for 4 h, and hydrocracking catalyst.

[0185] Comparative Example 4

[0186] This comparative example provides a hydrocracking catalyst, and its preparation method comprises the following steps:

[0187] 40 g of USY molecular sieve, 17.5 g of molybdenum oxide and 6.3 g of basic nickel carbonate were mixed, placed in a ball mill and mixed and ball-milled at a rate of 400 r / min for 3 h, then evenly mixed with 10 g of small-pore alumina and 2.5 g of sesbania powder, and 2.5 g of concentrated nitric acid (68 wt%) solution was added, extruded into strips, dried at 100 ° C for 3 h, and calcined at 500 ° C for 4 h to obtain a hydrocracking catalyst.

[0188] The hydrocracking catalysts prepared in the above-mentioned embodiments and comparative examples were tested according to the above-mentioned methods, and the specific test results are shown in Table 1 below.

[0189] Table 1 Test results

[0190]

[0191] The hydrocracking catalysts prepared in the examples and comparative examples were used to evaluate the hydrocracking of kerosene in a 200 mL fixed bed hydrogenation unit. The catalyst loading was 100 mL, and kerosene containing 2% carbon disulfide was used for sulfurization. The hydrocracking conditions were: reaction pressure 12 MPa, hydrogen to oil volume ratio 800:1, cracking stage liquid hourly space velocity 1.5 h -1, the reaction temperature was 340 °C. The main properties of the feedstock oil are listed in Table 2, and the evaluation results are listed in Table 3.

[0192] Table 2 Feedstock properties

[0193]

[0194] Table 3 Evaluation results

[0195]

[0196] As can be seen from the data in the above table, the sum of the light naphtha yield and the non-naphtha yield in each example is higher than that in each comparative example, indicating that the hydrocracking catalyst obtained by the preparation method of the hydrocracking catalyst provided by the present invention produces more ethylene cracking feedstock, and the light naphtha yield as high-quality cracking feedstock is also higher than that in the comparative example.

[0197] Of course, the present invention may also have many other embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and deformations according to the present invention, but these corresponding changes and deformations should all fall within the protection scope of the claims of the present invention.

Claims

1. A preparation method of a hydrocracking catalyst, characterized in that, it comprises the following steps: After ball-milling and mixing the composite material with the compound containing the active metal, it is mixed with the binder and the extrusion aid, and then formed, dried, and calcined to obtain the hydrocracking catalyst; Based on the mass of the composite material being 100%, the composite material comprises 10 wt% - 80 wt% of amorphous silica-alumina, 10 wt% - 45 wt% of Beta zeolite, and 10 wt% - 45 wt% of rare earth modified SSZ-13 zeolite; Based on the mass of the rare earth modified SSZ-13 zeolite being 100%, calculated as oxides, the content of rare earth is 0.1 wt% - 5 wt%.

2. The preparation method of the hydrocracking catalyst according to claim 1, characterized in that, The silica-alumina ratio of the rare earth modified SSZ-13 molecular sieve is 20 to 100, the specific surface area is 200 to 500 m 2 / g, and the total pore volume is 0.2 to 0.5 mL / g.

3. The preparation method of the hydrocracking catalyst according to claim 1, characterized in that, the active metal is selected from Group VIB metals and / or Group VIII metals; the Group VIB metals are selected from molybdenum and / or tungsten; the Group VIII metals are selected from cobalt and / or nickel.

4. The preparation method of the hydrocracking catalyst according to claim 1, characterized in that, the preparation of the composite material comprises the following steps: (1) Disperse Beta zeolite and rare earth modified SSZ-13 zeolite in an acidic aluminum source solution, heat and stir to obtain a zeolite mixed slurry; (2) Under stirring, add an alkaline solution and sodium silicate to the zeolite mixed slurry to obtain a mixed material; (3) The mixed material is separated, washed, dried, and calcined to obtain the composite material.

5. The preparation method of the hydrocracking catalyst according to claim 4, characterized in that, In step (2), under stirring at 60 - 100 °C, the alkaline solution is added within 0.2 - 8 h. After the addition of the alkaline solution is completed, it is maintained at 60 - 100 °C for 0.5 - 8 h, and then sodium silicate is added within 0.5 - 10 h. After the addition of sodium silicate is completed, it is maintained at 60 - 100 °C for 0.5 - 8 h.

6. The preparation method of the hydrocracking catalyst according to claim 1, characterized in that, the preparation of the rare earth modified SSZ-13 zeolite comprises the following steps: 1) Add a silicon source, an aluminum source, an alkali source, and a template agent to water and mix to form a gel, carry out hydrothermal crystallization, and after washing and separation, obtain a first solid; 2) Carry out ion exchange on the first solid with a rare earth precursor solution, and after washing and separation, obtain a second solid; 3) After alkali treatment of the second solid, and after washing and separation, obtain a third solid; The third solid is subjected to ammonium exchange with an ammonium salt, and after washing, separation, drying, and calcination, obtain the rare earth modified SSZ-13 zeolite.

7. The preparation method of the hydrocracking catalyst according to claim 6, characterized in that, In step 1), in terms of oxides, the molar ratio of each component in the gel is (60-150)SiO 2 :(0.5-5)Al 2 O 3 :(5-20)Na 2 O:(3000-4500)H 2 O:(10-30) templating agent; In step 1), the temperature of the hydrothermal crystallization is 80 - 190 °C, and the time is 72 - 170 h.

8. A hydrocracking catalyst, characterized in that, Prepared by the preparation method of the hydrocracking catalyst according to any one of claims 1-7, based on the mass of the hydrocracking catalyst being 100%, calculated as oxides, the content of the active metal is 15%-35%.

9. The hydrocracking catalyst according to claim 8, characterized in that The specific surface area of the hydrocracking catalyst is 280-310 m 2 / g, the pore volume is 0.27-0.40 mL / g, the pore diameter is 7.8-10.2 nm, and the acid amount is 350-383 μmol / g.

10. Application of the hydrocracking catalyst prepared by the preparation method of the hydrocracking catalyst according to any one of claims 1-7 in the preparation of light ethylene cracking raw materials by diesel hydrocracking or jet fuel hydrocracking.

Images