阅读说明：本技术 一种加氢裂化催化剂及其制备方法和应用 (Hydrocracking catalyst, and preparation method and application thereof ) 是由 王会刚 杨占林 姜虹 刘奕 丁思佳 王继锋 于 2019-10-28 设计创作，主要内容包括：本发明公开一种加氢裂化催化剂的制备方法,包括如下内容：(1)将含铝有机骨架材料与酸性组分混合、成型、干燥；(2)用配置好的金属溶液浸渍步骤(1)干燥后的物料；经干燥、焙烧后制得最终的加氢裂化催化剂。所述方法制备的催化剂优化了加氢中心的活性和催化剂的酸性,从而促进重质馏分油的加氢和裂化过程,满足生产优质石油产品和改善尾油产品性质的需求。(The invention discloses a preparation method of a hydrocracking catalyst, which comprises the following steps: (1) mixing an aluminum-containing organic framework material with an acidic component, molding and drying; (2) dipping the dried material in the step (1) by using a prepared metal solution; and drying and roasting to obtain the final hydrocracking catalyst. The catalyst prepared by the method optimizes the activity of a hydrogenation center and the acidity of the catalyst, thereby promoting the hydrogenation and cracking processes of heavy distillate oil, and meeting the requirements of producing high-quality petroleum products and improving the properties of tail oil products.)

1. A preparation method of a hydrocracking catalyst is characterized by comprising the following steps: the method comprises the following steps:

(1) mixing an aluminum-containing organic framework material with an acidic component, molding and drying;

(2) dipping the dried material in the step (1) by using a prepared metal solution; after drying and roasting

To prepare the final hydrocracking catalyst.

2. The method of claim 1, wherein: the aluminum-containing organic framework material has the following properties: the specific surface area after activation is 800-1500 m²The pore volume is 0.60-1.20 mL/g, and the proportion of 1-10 nm pore channels is>90%。

3. The method of claim 2, wherein: the aluminum-containing organic framework material has the following properties: the specific surface area after activation is 900-1300 m²The pore volume is 0.75-1.15 mL/g, and the proportion of 1-10 nm pore channels is>95%。

4. The method of claim 1, wherein: the aluminum-containing organic framework material in the step (1) is an aluminum-containing organic framework material modified by an auxiliary agent, and the auxiliary agent is one or more of fluorine, silicon, phosphorus, titanium, zirconium, boron and the like.

5. The method of claim 4, wherein: the auxiliary agent is zirconium or titanium, and accounts for 0.1-6% of the mass content of the aluminum oxide corresponding to the aluminum-containing organic framework compound in terms of simple substance.

6. The method of claim 4, wherein: the auxiliary agent is one or more of sulfate, sulfite, persulfate and organic sulfide, and is loaded on the aluminum-containing organic framework material through the impregnation process, and the drying treatment is carried out after the impregnation, wherein the drying temperature is 60-140 ℃, and the drying time is 1-24 h.

7. The method of claim 1, wherein: the acidic component in step (1) is one or more of hydrocracking catalysts including but not limited to Y-type molecular sieves, beta molecular sieves, ZSM-5 molecular sieves, SAPO molecular sieves, amorphous silica-alumina and the like.

8. The method of claim 7, wherein: the acid component is a Y-type molecular sieve, and the properties of the Y-type molecular sieve are as follows: the specific surface area is 500m²/g～800m²The total pore volume is 0.30-0.75 mL, the molar ratio of silicon to aluminum is 6-40, and the infrared acid content is 0.35-0.80 mmol/g.

9. The method of claim 1, wherein: adding an extrusion aid, a bonding agent and/or a peptizing agent in the forming process of the step (1), wherein the bonding agent comprises inorganic oxide, such as one or a combination of silicon oxide, magnesium oxide, titanium oxide, aluminum oxide and zirconium oxide, and the bonding agent accounts for 2-12% of the weight of the aluminum oxide component.

10. The method of claim 1, wherein: in the step (2), the metal is selected from metals in families VIB and/or VIII, and the metal is loaded on the carrier by an impregnation method and is impregnated in equal volume or excessively impregnated.

11. The method of claim 1, wherein: the drying conditions in the step (2): the temperature is 70-150 ℃, and the drying time is 1-20 h; the roasting condition is as follows: the temperature is 250-600 ℃, and the time is 0.5-10 h.

12. The method of claim 1, wherein: in the step (2), the roasting is carried out in at least two stages: the first stage is as follows: roasting in inert gas at 250-450 deg.c for 0.5-5 hr; and a second stage: in the air atmosphere, the roasting temperature is 430-600 ℃, and the roasting time is 0.5-5 h.

13. The method of claim 12, wherein: in the step (2), the roasting is carried out in at least two stages: the first stage is as follows: in inert gas, the roasting temperature is 270-430 ℃, and the roasting time is h-4 h; suitable inert gases are nitrogen or argon; and a second stage: in the air atmosphere, the roasting temperature is 450-580 ℃, and the roasting time is 1-3 h.

14. The method of claim 1, wherein: in the step (2), the catalyst is roasted until the carbon content in the catalyst is 0.3-1.6% of the weight of the final hydrocracking catalyst, and preferably 0.4-1.5%.

15. A catalyst prepared by the process of any one of claims 1 to 14, wherein: based on the weight of the final hydrocracking catalyst, the content of the acidic component Y-type molecular sieve is 30-60%, the content of the alumina is 10-65%, the content of the VIB group metal oxide is 10-35%, and the content of the VIII group metal oxide is 3-10%.

16. The catalyst of claim 15, wherein: the specific surface area of the catalyst is 150-380 m²The volume of pores is 0.23-0.65 mL/g, the average pore diameter is 5-15 nm, and the total infrared acid amount is 0.40-0.75 mmol/g.

17. The catalyst of claim 15, wherein: the carbon content in the catalyst is 0.3-1.6 wt%, preferably 0.4-1.5 wt% of the hydrocracking catalyst.

18. The catalyst of claim 15, which is used in hydrocracking reaction using wax oil as raw material, and the reaction conditions are as follows: 10 MPa-20 Mpa, reaction temperature 350-450 ℃, feeding volume airspeed 1.0-2.0 h-1, hydrogen-oil volume ratio 500: 1-2000: 1.

Technical Field

The invention relates to a hydrocracking catalyst, a preparation method and application thereof, in particular to a high-activity hydrocracking catalyst suitable for heavy raw oil and a preparation method and application thereof.

Background

Hydrocracking technology is an important technical means for deep secondary processing of heavy oil, and is also an important way for efficiently producing clean oil products and high-quality chemical raw materials. Since hydrocracking has the characteristics of strong raw material applicability, flexible scheme for regulating and controlling product distribution, high target product selectivity, good product added value and the like, hydrocracking has become one of the most important processing technologies in the fields of modern oil refining and petrochemical industry, and is widely applied in China at present. Along with the increasing trend of crude oil heaviness in the world, the contents of sulfur and heavy metals in the crude oil are obviously increased, and particularly, the import quantity of the high-sulfur crude oil is greatly increased by mainly depending on imported crude oil in China. Meanwhile, the national requirements on environmental protection are more and more strict, and a stricter environmental protection law is issued in succession. In addition, the national requirements for the processing technology of heavy oil and the quality of corresponding petroleum products are becoming stricter, and the market demands for clean fuel oil and chemical raw materials are increasing. Therefore, it is a very urgent task to further improve the hydrocracking technology level to meet environmental and market demands.

For hydrocracking technology, the heart is the hydrocracking catalyst. The catalyst belongs to a bifunctional catalyst, and has a cracking function and a hydrogenation function at the same time. The cracking activity in the catalyst is mainly provided by various molecular sieves, while the hydrogenation activity is mainly provided by metals of groups VI B and VIII in the element cycle. The hydrocracking raw material is subjected to hydrogenation reaction in a hydrogenation active center, and then transferred to a strong acid center of a molecular sieve to carry out cracking reaction and isomerization reaction to different degrees. In order to convert the raw oil to a greater extent and produce oil products and chemical raw materials meeting the market demand, the efficient hydrocracking catalyst needs to have a hydrogenation center and a cracking center which are matched in reaction rate. The research directions of the prior art are more prone to the improvement and the improvement of the cracking function, and the improvement range of the hydrogenation performance is small. Therefore, how to effectively and synchronously improve the hydrogenation performance and the cracking performance of the catalyst is an important means for promoting the progress of the hydrocracking technology.

CN102451743A discloses a preparation method of a hydrocracking catalyst. The catalyst is prepared by mixing, molding and drying a molecular sieve, amorphous silica-alumina and alumina to be used as a carrier, then impregnating with VIII group and VIB group metal solutions, and drying and roasting. The preparation process simplifies the preparation process, weakens the interaction between the metal and the carrier, but has lower overall catalytic activity and still needs to be improved.

US6174429 discloses a hydrocracking catalyst, which adopts an acidified amorphous aluminum-containing matrix and a Y-type molecular sieve with the framework silicon-aluminum oxide molar ratio of about 20 to prepare a carrier, and then loads 0.1-30 wt% of at least one VIII group metal component, 1-40 wt% of at least one VIB group metal component and 1-40 wt% of at least one VII A group element. In the preparation process, the acidified amorphous aluminum-containing matrix is adopted to improve the performance of the catalyst, and although the catalyst shows better catalytic activity and stability, the yield of heavy naphtha and aviation kerosene in corresponding products is low.

CN109304214A discloses a hydrocracking catalyst, the carrier used is mainly formed by mixing modified graphene and aluminum hydroxide dry glue powder, then dipping VIB group and/or VIII group metal elements, mixing with a molecular sieve for molding, and roasting to prepare the hydrocracking catalyst. Although the catalyst improves the yield of light oil products, the application of the catalyst is limited by the complicated preparation process.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a hydrocracking catalyst and a preparation method thereof. The catalyst prepared by the method optimizes the activity of a hydrogenation center and the acidity of the catalyst, thereby promoting the hydrogenation and cracking processes of heavy distillate oil, and meeting the requirements of producing high-quality petroleum products and improving the properties of tail oil products.

The preparation method of the hydrocracking catalyst comprises the following steps:

(1) mixing an aluminum-containing organic framework material with an acidic component, molding and drying;

(2) dipping the dried material in the step (1) by using a prepared metal solution; after drying and roasting

To prepare the final hydrocracking catalyst.

The above method, step (1) of the aluminum-containing organic framework material can be commercially available or prepared according to the prior art. Preferred aluminum-containing organic framework materials have the following properties: after activation (treatment at 200 ℃ for 6 hours), the specific surface area is 800-1500 m²Preferably 900 to 1300 m/g²The pore volume is 0.60-1.20 mL/g, preferably 0.75-1.15 mL/g, and the proportion of pore channels with the diameter of 1-10 nm is>90%, preferably>95%。

In the method, the aluminum-containing organic framework material in the step (1) is preferably an aluminum-containing organic framework material modified by an auxiliary agent, the auxiliary agent can be one or more of fluorine, silicon, phosphorus, titanium, zirconium, boron and the like, preferably zirconium or titanium, and the auxiliary agent accounts for 0.1-6%, preferably 0.3-5% of the content of alumina corresponding to the aluminum-containing organic framework compound in terms of a simple substance. The auxiliary agent is derived from compounds of inorganic salts, organic esters and other types, preferably contains sulfur element, and can be sulfate, sulfite, persulfate, organic sulfide and the like. The auxiliary agent is loaded on the aluminum-containing organic framework material through an impregnation process, and equal-volume impregnation, excess impregnation, step-by-step impregnation and co-impregnation can be adopted, and equal-volume co-impregnation is preferable. And drying after the impregnation, wherein the drying temperature is 60-140 ℃, preferably 80-130 ℃, and the drying time is 1-24 h, preferably 6-18 h.

In the above method, the acidic component in step (1) is an acidic component commonly used in hydrocracking catalysts, and includes but is not limited to one or more of Y-type molecular sieve, beta molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve, amorphous silica-alumina, etc., preferably Y-type molecular sieve, and the properties of the Y-type molecular sieve are as follows: the specific surface area is 500m²/g～800m²The total pore volume is 0.30-0.75 mL, the molar ratio of silicon to aluminum is 6-40, and the infrared acid content is 0.35-0.80 mmol/g. The molecular sieve used can be subjected to appropriate post-treatment according to the requirements of specific applications.

In the method, the extrusion aid, the adhesive and the peptizing agent can be added in the forming process of the step (1). Suitable binder materials include inorganic oxides such as one of silica, magnesia, titania, alumina and zirconia or combinations thereof. The binder is present in an amount of 2% to 12%, preferably 4% to 10% by weight of the alumina component. Suitable peptizing agents are various organic acids, inorganic acids and organic acids capable of ionizing H^＋The peptizing agent used is one or more of the above substances. The catalyst precursor with different shapes can be obtained through the forming process, and is preferably in the shape of a strip (clover, cylindrical strip and the like), and can be made into different sizes according to the requirements. The drying temperature is 60-150 ℃, preferably 70-140 ℃, and the drying time is 1-24 h, preferably 6-12 h.

In the method, the metal in the step (2) is selected from group VIB and/or group VIII metals, and can be selected from compounds such as salts, oxides or acids, and can be one or more of the metals. The metal is loaded onto the support by impregnation, mainly by isovolumetric impregnation, excess impregnation and stepwise impregnation, co-impregnation, preferably isovolumetric co-impregnation. Drying after the completion of the impregnation, wherein the drying conditions are as follows: the temperature is 70-150 ℃, preferably 90-140 ℃, and the drying time is 1-20 h, preferably 5-15 h.

The above method, the drying conditions in step (2): the temperature is 70-150 ℃, preferably 90-140 ℃, and the drying time is 1-20 h, preferably 5-15 h; the roasting condition is as follows: the temperature is 250-600 ℃, preferably 270-580 ℃, and the time is 0.5-10 h, preferably 1-7 h.

In the method, the roasting in the step (2) is divided into at least two stages: the first stage is as follows: in inert gas, the roasting temperature is 250-450 ℃, preferably 270-430 ℃, and the roasting time is 0.5-5 h, preferably 1-4 h; suitable inert gases are preferably nitrogen or argon; and a second stage: in the air atmosphere, the roasting temperature is 430-600 ℃, preferably 450-580 ℃, and the roasting time is 0.5-5 h, preferably 1-3 h.

In the method, the carbon content in the catalyst in the step (2) is 0.3-1.6%, preferably 0.4-1.5% of the weight of the final hydrocracking catalyst.

In the method, an auxiliary agent can be introduced in the forming process in the step (1) or the dipping process in the step (2), the auxiliary agent can be one or more of fluorine, silicon, phosphorus, titanium, zirconium, boron and the like, preferably zirconium or titanium, and the auxiliary agent accounts for 0.1-6%, preferably 0.3-5% of the content of alumina corresponding to the aluminum-containing organic framework compound in terms of a simple substance.

The catalyst prepared by the method has the advantages that the weight of the final hydrocracking catalyst is taken as the standard, the content of the acidic component, preferably Y-type molecular sieve, is 30-60%, the content of alumina is 10-65%, the content of VIB group metal oxide is 10-35%, and the content of VIII group metal oxide is 3-10%.

In the catalyst, the specific surface area of the hydrocracking catalyst is 150-380 m²The volume of pores is 0.23-0.65 mL/g, the average pore diameter is 5-15 nm, and the total infrared acid amount is 0.40-0.75 mmol/g.

In the catalyst, the carbon content in the catalyst is 0.3-1.6%, preferably 0.4-1.5% of the weight of the hydrocracking catalyst.

The catalyst is used for hydrocracking reaction taking wax oil as a raw material, and the reaction conditions are as follows: 10 MPa-20 Mpa, reaction temperature 350-450 ℃, feeding volume airspeed 1.0-2.0 h-1, hydrogen-oil volume ratio 500: 1-2000: 1.

Compared with the prior art, the hydrocracking catalyst and the preparation method thereof have the following advantages:

(1) in the catalyst prepared by the method, because the alumina component precursor aluminum-containing organic framework material has the advantages of high adsorption, high specific surface area and the like, the alumina component contains more hydrogenation active metals, the metal component on the acidic material and the metal component on the alumina are matched with each other, the hydrogenation performance and the cracking performance are matched with each other, and the performance of the catalyst is obviously improved;

(2) the proper carbon content in the alumina component of the two-stage roasting and/or hydrocracking catalyst can obviously improve the dispersion degree of active metals in the alumina component and improve the cracking effect.

Detailed Description

The hydrocracking catalyst is prepared through rolling, forming and drying the organic skeleton matter containing Al and molecular sieve in the presence of peptizing agent or adhesive to obtain composite carrier, soaking in active metal, drying, regulating and roasting to obtain the final catalyst.

The active metals described therein are exemplified by the tungsten-nickel system. The aluminium-containing organic framework compounds used in the examples were prepared as follows: adding terephthalic acid into an aluminum nitrate nonahydrate aqueous solution, stirring for 30min, transferring to a high-pressure reaction kettle, and crystallizing for 72h at 220 ℃. After crystallization is finished, centrifugal separation is carried out to obtain a solid; and repeatedly washing and drying the N, N-dimethyl amide and ethanol to obtain the aluminum-containing organic framework compound.

The preparation process of the modified aluminum-containing organic framework compound in the examples is as follows: dipping into solution containing soluble assistant to synthesize aluminum-containing organic frame compound, drying.

The Y-type molecular sieve adopted in the embodiment is preferably a modified Y-type molecular sieve after high-temperature steam treatment and acid washing treatment, and the high-temperature steam treatment conditions are as follows: the gauge pressure is controlled to be 0.1MPa to 0.2MPa, the temperature is controlled to be 500 ℃ to 600 ℃, and the treatment time is 1h to 3 h. And washing the molecular sieve sample by using an inorganic acid or organic acid solution.

And mixing the modified Y molecular sieve and the modified aluminum-containing organic framework compound in a kneading machine or a rolling machine for 10-80 min. And slowly adding the adhesive and/or the peptizing agent into the mixed powder, mixing or rolling for 10-30 min, and making the carrier into various shapes such as spheres, tablets or strips according to different requirements. Preferably in the form of strips (clover, cylindrical strips, etc.) and can be made in different sizes as required. Drying to obtain the catalyst carrier.

The catalyst carrier is impregnated with a solution containing an active metal component and then dried. The catalyst is preferably obtained by calcination in two stages. The first stage is as follows: in inert gas, the roasting temperature is 250-450 ℃, preferably 270-430 ℃, and the roasting time is 0.5-5 h, preferably 1-4 h; suitable inert gases are preferably nitrogen or argon. And a second stage: in the air atmosphere, the roasting temperature is 430-600 ℃, preferably 450-580 ℃, and the roasting time is 0.5-5 h, preferably 1-3 h.

The physicochemical properties of the Y-type molecular sieves used in the examples are as follows: specific surface area of 635m²Per g, pore volume of 0.54cm³The infrared acid content was 0.67 mmol/g. The physicochemical properties of the inorganic alumina powder used in the comparative example were as follows: the pore volume is 0.57cm³Per g, specific surface area 438 m²/g。

The specific surface area and the pore volume of the catalyst obtained after roasting are measured by adopting a low-temperature liquid nitrogen physical adsorption method, the molar ratio of silicon oxide to aluminum oxide is measured by adopting a chemical method, and the infrared acid content is measured by adopting a pyridine infrared spectrometry method.

The technical features of the present invention are further described below by way of examples, but the present invention should not be construed as being limited to only these examples. The percentage of the material is weight percentage.

Preparation of aluminum-containing organic framework compound:

example 1

2800g of aluminum nitrate nonahydrate is added into 9600mL of water, and the mixture is stirred at room temperature until the aluminum nitrate nonahydrate is completely dissolved; 622g of terephthalic acid is weighed and slowly added into the aluminum nitrate solution, the mixture is stirred for 30min, the solution is transferred to a stainless steel reaction kettle, and crystallization is carried out for 72h at 220 ℃. After crystallization, centrifugal separation is carried out to obtain solid; and repeatedly washing the mixture by using N, N-dimethyl amide and ethanol, and drying the mixture at 80 ℃ to obtain the aluminum-containing organic framework compound.

The structural parameters of the prepared aluminum-containing organic framework compound are as follows: after activation (treatment at 200 ℃ for 6 hours) the specific surface area was 1050m²The pore volume is 0.89mL/g, and the proportion of the pore channel with the diameter of 1nm to 10nm is 97 percent.

Modification of aluminum-containing organic framework compound:

example 2

500G of aluminum-containing organic framework compound is weighed, isovolumetric impregnation is carried out by using a solution containing 1.05G of zirconium sulfate tetrahydrate, and drying is carried out for 16h at 80 ℃ to obtain modified powder G-1.

Example 3

500G of aluminum-containing organic framework compound is weighed, isovolumetric impregnation is carried out by using a solution containing 8.40G of zirconium sulfate tetrahydrate, and drying is carried out for 12h at 100 ℃ to obtain modified powder G-2.

Example 4

500G of aluminum-containing organic framework compound is weighed, isovolumetric impregnation is carried out by using a solution containing 17.5G of zirconium sulfate tetrahydrate, and drying is carried out for 8 hours at 130 ℃ to obtain modified powder G-3.

Preparation of catalyst carrier:

example 5

Calculated on the weight of the final hydrocracking catalyst: 47% of Y-type molecular sieve, 7% of nickel oxide, 30% of tungsten oxide and the balance of aluminum oxide and auxiliary agent. The preparation raw materials are selected from a modified Y molecular sieve and a modified aluminum-containing organic framework material G-1.

The catalyst was prepared as follows: mixing the modified Y-type molecular sieve, the G-1 modified aluminum-containing organic framework powder and sesbania powder, adding 2.3wt% of nitric acid solution for peptization, mixing and rolling for 20min, and extruding into 1.7mm clover strips. Drying at 120 deg.C for 4h to obtain the carrier. The solution was immersed in an equal volume of W, Ni containing metal for 4h and then dried at 120 ℃ for 6 h. Roasting at 400 ℃ for 4h in a nitrogen atmosphere; then, the air atmosphere is switched, and the catalyst C-1 is obtained after roasting for 2h at 530 ℃.

Example 6

Calculated on the weight of the final hydrocracking catalyst: 47% of Y-type molecular sieve, 7% of nickel oxide, 30% of tungsten oxide and the balance of aluminum oxide and auxiliary agent. The preparation raw materials are selected from modified Y molecular sieve and modified aluminum-containing organic framework powder G-2. The catalyst formation, impregnation, drying and calcination steps were the same as in example 5 to give the final catalyst C-2.

Example 7

Calculated on the weight of the final hydrocracking catalyst: 47% of Y-type molecular sieve, 7% of nickel oxide, 30% of tungsten oxide and the balance of aluminum oxide and auxiliary agent. The preparation raw materials are selected from modified Y molecular sieve and modified aluminum-containing organic framework powder G-3. The catalyst formation, impregnation, drying and calcination steps were the same as in example 5 to give the final catalyst C-3.

Example 8

Calculated on the weight of the final hydrocracking catalyst: 32% of Y-type molecular sieve, 7% of nickel oxide, 30% of tungsten oxide and the balance of aluminum oxide and auxiliary agent. The preparation raw materials are selected from a modified Y molecular sieve and a modified aluminum-containing organic framework material G-2.

The catalyst molding, impregnation and drying steps were performed simultaneously in example 5, and the calcination was carried out in nitrogen at 420 ℃ for 3 h; then, the air atmosphere is switched, and the mixture is roasted for 2 hours at the temperature of 550 ℃ to obtain the final catalyst C-4.

Example 9

Calculated on the weight of the final hydrocracking catalyst: 55% of Y-type molecular sieve, 7% of nickel oxide, 30% of tungsten oxide and the balance of aluminum oxide and auxiliary agent. The preparation raw materials are selected from a modified Y molecular sieve and a modified aluminum-containing organic framework material G-2.

The catalyst molding, impregnation and drying steps were performed simultaneously in example 5, and the calcination was carried out at 410 ℃ for 3.5h in nitrogen; then, the air atmosphere is switched, and the mixture is roasted for 1.8h at 480 ℃ to obtain the final catalyst C-5.

Example 10

Calculated on the weight of the final hydrocracking catalyst: 47% of Y-type molecular sieve, 7% of nickel oxide, 30% of tungsten oxide and the balance of aluminum oxide and auxiliary agent. The preparation raw materials are selected from a modified Y molecular sieve and a modified aluminum-containing organic framework material G-2.

The catalyst is molded, impregnated and dried simultaneously in the step of example 5, and is roasted for 5 hours at 395 ℃ in a nitrogen atmosphere; then, the air atmosphere is switched, and the catalyst C-6 is obtained after roasting for 3.5h at 550 ℃.

Example 11

Calculated on the weight of the final hydrocracking catalyst: 47% of Y-type molecular sieve, 7% of nickel oxide, 30% of tungsten oxide and the balance of aluminum oxide and auxiliary agent. The preparation raw materials are selected from a modified Y molecular sieve and a modified aluminum-containing organic framework material G-2.

The catalyst molding, impregnation and drying steps were performed simultaneously in example 5, and the calcination was carried out at 400 ℃ for 4 hours in a nitrogen atmosphere; then, the air atmosphere is switched, and the catalyst C-7 is obtained after roasting for 5 hours at 460 ℃.

Example 12

The hydrocracking catalyst is prepared by mixing the raw materials and the composition ratio in the example 6 to prepare a catalyst carrier, loading a hydrogenation metal component by adopting an impregnation method, drying, and directly roasting at 550 ℃ for 5 hours in an air atmosphere to obtain the catalyst with the number of C-8.

Example 13

The hydrocracking catalyst is prepared by mixing the raw materials and the composition ratio in the example 6 to prepare a catalyst carrier, loading a hydrogenation metal component by adopting an impregnation method, drying, and directly roasting at 510 ℃ for 2 hours in an air atmosphere to obtain the catalyst, wherein the number of the catalyst is C-9.

Example 14

Calculated on the weight of the final hydrocracking catalyst: 47% of Y-type molecular sieve, 7% of nickel oxide, 30% of tungsten oxide and the balance of aluminum oxide and auxiliary agent. The preparation raw materials are selected from modified Y molecular sieve and unmodified aluminum-containing organic framework material.

The catalyst was prepared as follows: mixing the modified Y-type molecular sieve, unmodified aluminum-containing organic framework powder and sesbania powder, adding 2.3wt% of nitric acid solution for peptization, mixing and rolling for 20min, and extruding into 1.7mm clover strips. Drying at 120 deg.C for 4h to obtain the carrier. The solution was immersed in an equal volume of W, Ni containing metal for 4h and then dried at 120 ℃ for 6 h. Roasting at 400 ℃ for 4h in a nitrogen atmosphere; then, the air atmosphere is switched, and the catalyst C-10 is obtained after roasting for 2h at 530 ℃.

Example 15

The hydrocracking catalyst used the same feedstock and composition as in example 14, and the catalyst was prepared according to the following procedure: mixing the modified Y-type molecular sieve, unmodified aluminum-containing organic framework powder and sesbania powder, adding 2.3wt% of nitric acid solution for peptization, adding the same amount of zirconium sulfate tetrahydrate solution as in example 6, mixing and rolling for 20min, and extruding into 1.7mm clover strips. Drying at 120 deg.C for 4h to obtain the carrier. The solution was immersed in an equal volume of W, Ni containing metal for 4h and then dried at 120 ℃ for 6 h. Roasting at 400 ℃ for 4h in a nitrogen atmosphere; then, the air atmosphere is switched, and the catalyst C-11 is obtained after roasting for 2h at 530 ℃.

Example 16

The hydrocracking catalyst used the same feedstock and composition as in example 14, and the catalyst was prepared according to the following procedure: mixing the modified Y-type molecular sieve, the unmodified aluminum-containing organic framework powder and sesbania powder, adding 2.3wt% of nitric acid solution for peptization, and then adding a zirconium nitrate pentahydrate solution to ensure that the zirconium content in the catalyst is the same as that in example 6. Then mixing and rolling for 20min, and extruding into 1.7mm clover strips. Drying at 120 deg.C for 4h to obtain the carrier. The solution was immersed in an equal volume of W, Ni containing metal for 4h and then dried at 120 ℃ for 6 h. Roasting at 400 ℃ for 4h in a nitrogen atmosphere; then, the air atmosphere is switched, and the catalyst C-12 is obtained after roasting for 2h at 530 ℃.

Comparative example 1

The alumina raw material adopts inorganic alumina powder, is not modified and is mixed according to the composition proportion in the embodiment 6 to prepare a catalyst carrier, the hydrogenation metal component is loaded by adopting an impregnation method, and the catalyst DC-1 is obtained by roasting for 2h at 530 ℃.

Comparative example 2

The alumina raw material adopts inorganic alumina powder, is treated according to the modification method in the embodiment 3, is mixed according to the composition proportion in the embodiment 6 to prepare a catalyst carrier, adopts an impregnation method to load hydrogenation metal components, and is roasted for 2 hours at 530 ℃ to obtain the catalyst DC-2.

Example 17

The catalytic activity of the catalyst and the contrast agent prepared by the invention is evaluated by adopting a 200mL small fixed bed hydrocracking test device, and the catalyst is vulcanized before the evaluation is started. The basic properties of the vacuum distillate oil used as the feed oil are shown in Table 1. Evaluation conditions used: the total reaction pressure is 14.3Mpa, the volume ratio of hydrogen to oil is controlled at 1200:1, and the liquid hourly volume space velocity is 1.6h^-1. The evaluation raw oil passes through a hydrofining reactor, and the organic nitrogen in the crude oil discharged from the refining reactor is controlled to be below 20 mu g/g. The performance of the catalysts obtained in examples and the performance of the catalysts obtained in comparative examples were evaluated in comparison under the same reaction conditions, and the evaluation results are shown in table 3.

TABLE 1 Properties of the stock oils

The physicochemical properties of this catalyst in the above examples are shown in Table 2:

TABLE 2 physicochemical Properties of the catalyst

TABLE 3 evaluation results of catalytic Properties of the catalysts