CN103785446A - High-activity hydrocracking catalyst and preparation method thereof - Google Patents
High-activity hydrocracking catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a preparation method of a hydrocracking catalyst. The method of the present invention includes the following steps: (1) preparing a catalyst carrier containing a molecular sieve and an inorganic refractory oxide; (2) preparing a dipping solution containing a VIB group metallic compound, a VIII group metallic compound and a hydrazine derivative, (3)dipping the catalyst carrier obtained in the step (1) in the dipping solution obtained in the step (2), and then drying the carrier; and (4) activating the materials obtained in the step (3) by using hydrogen, so as to obtain the hydrocracking catalyst used for the hydrocracking reaction after the activation. The hydrocracking catalyst provided by the invention has high activity, and the preparation method is simple, can be used for the treatment of heavy hydrocarbon materials and can produce middle distillates by the maximum amount.
Description
Technical field
The present invention relates to a kind of high-activity hydrocracking catalyst and preparation method thereof, this catalyst has good hydrocracking performance, and active high, middle distillates oil selectivity is high.
Background technology
Hydrocracking catalyst is a kind of bifunctional catalyst, there is Hydrogenation and cracking performance, non-noble metal hydrocracking catalyst generally selects VI B and VIII family metal to make hydrogenation component, and cracking performance is mainly provided by acidic components, and acidic components can be selected crystal formation zeolite and/or amorphous aluminum silicide etc.Simple with amorphous aluminum silicide, although selectively higher, active low, operational flexibility is restricted, and in most of hydrocracking catalysts, all take crystal formation zeolite as acidic components, or crystal formation zeolite and amorphous aluminum silicide are acidic components jointly.
The middle oil type hydrocracking catalyst major part using at present on commercial plant is the catalyst that contains zeolite, and the zeolite component adopting is mainly that y-type zeolite, β zeolite and two kinds of zeolites mix use, and catalyst all will carry out presulfurization before reaction, make metal component be converted into sulphided state, to improve the serviceability of catalyst.But use not only contaminated environment, harm operating personnel's the health of vulcanizing agent that sulfur content is higher, and sulfidation is numerous and diverse, need to drop into a lot of manpower and materials.
US4820402 discloses a kind of hydrocracking catalyst, has used β zeolite, and this patent is thought, in order to improve middle distillates oil selectivity and to reduce hydrogen consumption, at least 50:1 of silica/alumina molecular proportion of the zeolite component in catalyst, general 100:1, even 200:1.Variety classes zeolite for the middle distillates oil selectivity order of catalyst is: ZSM-20> β >Y type, process Arabic VGO, in the situation that controlling 60v% conversion, middle distillates oil selectivity 45-65v%, wherein acidic components are β zeolite, when conversion ratio 60v%, the catalyst middle distillates oil selectivity that this patent relates to is no more than 70v%.
US4894142 discloses a kind of hydrocracking catalyst, object is to improve the middle distillates oil selectivity of catalyst, be characterized in being included in by use the dry type heat treatment method that passes into inert gas of 676-788 ℃ of temperature hydrothermal treatment consists or best 704 ℃, obtain a kind of low acidity Y zeolite, but because this zeolitic acid is spent low, while processing feedstock oil for catalytic component, reaction temperature is high, generally more than 400 ℃, suppress hydrogenation reaction, the thermal cracking performance trend of zeolite strengthens, make the middle distillates oil selectivity of catalyst improve not obvious, middle distillates oil selectivity is no more than 70%.
US5447623 discloses hydrocracking catalyst and the technique thereof of a kind of compound β zeolite and Y zeolite, but this catalyst is mainly used in light oil type hydrogen cracking catalyst, example embodies 50-185 ℃ of naphtha yield and improves obviously, and the use of β zeolite is relatively only used the catalyst activity of Y zeolite also high.Although this catalyst also can be for middle oil type hydrocracking catalyst, due to the characteristic of used β zeolite, in middle oil type catalyst, the content range of β zeolite is generally limited between 2.5w%-10w%, and generally must be used in conjunction with one and be dispersed in γ-Al
2o
3and so on the sial on macroporous aluminium oxide matrix, the middle oil type catalyst that this patent relates to, for guaranteeing middle distillates oil selectivity, has to force down activity, makes reaction temperature higher, general more than 390 ℃, thereby has caused poor adaptability to raw material.
The hydrogenation component of above-mentioned hydrocracking catalyst is the metal component of sulphided state, needs to carry out normal vulcanizing treatment before use, and the serviceability of catalyst needs further to improve.In hydrocracking catalyst, although provided by two kinds of components in hydrogenation activity and cracking activity main body, but in catalyst, the effect of two kinds of components is not well-separated, but the interactional coordinated effect that influences each other, hydrocracking reaction is the reaction that raw material has been worked in coordination with on two kinds of activated centres.How to regulate in hydrocracking catalyst, the correlation of hydrogenation activity component and cracking activity component, is the important content that improves hydrocracking catalyst Integrated using performance.
Summary of the invention
The object of the present invention is to provide a kind of new type hydrocracking catalyst and preparation method thereof, hydrocracking catalyst activity of the present invention is high, and preparation method is simple, and for the treatment of heavy hydrocarbon material, maximum is produced intermediate oil.
The preparation method of hydrocracking catalyst of the present invention comprises following process:
(1) catalyst carrier that preparation contains molecular sieve and inorganic refractory oxide;
(2) dipping solution that preparation contains VI B family metallic compound, VIII family metallic compound and hydrazine derivative;
(3) catalyst carrier of the dipping solution impregnation steps (1) of step (2) preparation, then dry;
(4) material that step (3) obtains carries out hydrogen activation, obtains the hydrocracking catalyst for hydrocracking reaction after activation.
In hydrocracking catalyst preparation method of the present invention, in step (1), molecular sieve is generally one or more in Y molecular sieve, beta-molecular sieve, ZSM-5 molecular sieve, SAPO-11 molecular sieve, modenite, ZSM-22 molecular sieve, ZSM-23 molecular screen and mesopore molecular sieve, is preferably Y molecular sieve and/or beta-molecular sieve.Required molecular sieve can carry out suitable modification, as hydrothermal treatment consists modification, acid treatment modification etc.Inorganic refractory oxide is generally aluminium oxide, silica, silica-alumina (being amorphous aluminum silicide), silica-alumina and is scattered in one or more in aluminium oxide (being dispersed in the amorphous aluminum silicide in aluminium oxide) wherein, aluminium oxide, magnesia, zirconia, boron oxide and titanium dioxide that silica is covered with paint, lacquer, colour wash, etc., is preferably amorphous aluminum silicide and/or alumina component.
In hydrocracking catalyst preparation method of the present invention, the preparation of catalyst carrier can adopt the method for this area routine in step (1), as required material is obtained to catalyst carrier in steps such as the required ratio mixing of the final composition of catalyst, moulding, dry, roastings.Dry being generally is dried 4-12 hour at 80-150 ℃, and roasting is roasting 2-6 hour at 400-600 ℃.
In hydrocracking catalyst preparation method of the present invention, step (2) ZhongⅥ B family metallic compound is the soluble compound containing W and/or Mo, and VIII family metallic compound is the soluble compound containing Ni and/or Co.
In hydrocracking catalyst preparation method of the present invention, in step (2), hydrazine derivative can use any hydrazine derivative, preferably uses dialkyl group hydrazine, particularly dimethyl hydrazine NH
2n (CH
3)
2.By it, the weight concentration in maceration extract is 25%-45% to the addition of hydrazine derivative.
In hydrocracking catalyst preparation method of the present invention, the dipping in step (3) is saturated dipping or excess solution dipping, and dipping can once carry out, and also can repeatedly flood.Drying process after dipping is dry 4-12 hour at 80-150 ℃.
In hydrocracking catalyst preparation method of the present invention, hydrogen activation process and the condition of step (4) are: under nitrogen atmosphere, take heating rate as 2-10 ℃/min rises to 300-500 ℃ from room temperature, then take heating rate as 0.5-2 ℃/min, be warming up to 600-750 ℃, and at intensification outlet temperature constant temperature 2-4 hour.Hydrogen purity is wherein greater than 95%(volume), hydrogen gas space velocity is 50-1000h
-1, pressure can be normal pressure to 1MPa, be preferably normal pressure.
A hydrocracking catalyst preparation, adopts above method to be prepared, and with catalyst carrier weighing scale, the content of molecular sieve is generally 2%～45%, is preferably 4%～15%; In catalyst weight, metal component of group VIB (weighing scale of W and/or Mo) content is generally 10%-40%, is better 15%-35%, preferably 18%-28%, metal component of group VIII (with the weighing scale of Ni and/or Co) content is generally 1%-10%, is better 2%-9%, preferably 4%-8%.Inorganic refractory oxide is surplus.The initial feed of various components can be the material source of this area routine.In preparation method, the consumption of various material raw materials can be determined by the composition in final catalyst.
Hydrocracking catalyst prepared by the inventive method, for the hydrocracking process take vacuum distillate as raw material inceasing output of jet fuel and diesel oil, reaction pressure is preferably in 6-20MPa, hydrogen to oil volume ratio 500:1-2000:1, raw material volume space velocity 0.5-2.0hr
-1, reaction temperature 350-410 ℃.Feedstock oil, before carrying out hydrocracking, carries out hydrofinishing, and organic nitrogen content is wherein reduced to below 50ug/g, is preferably below 20ug/g.
In hydrocracking catalyst preparation process of the present invention, introduce the nitrogen-containing compound matching with active metal component, and common hydrocracking catalyst sulfidation is cancelled, adopt hydrogen reducing mode to carry out activation processing to the catalyst of metal-containing compound and nitrogen component.This preparation method can make active metal component have desirable Hydrogenation on the one hand, and active metal component has produced certain effect to the acid centre of molecular sieve on the other hand.Show by analysis, the B acid site of active metal and molecular sieve interacts, significantly improved the acid strength on zeolite and distributed, strong acid is reduced, middle intensity acid increases, acid site number increases to some extent, and L acid site number reduces relatively, can reduce like this fine melt function, increase the activity that moderate strength acid amount is conducive to improve catalyst, reduce reaction temperature, and improve the selective of intermediate oil (kerosene and diesel oil).Hydrocracking catalyst of the present invention can obviously improve the nitrogen resistance of catalyst simultaneously, and in the time using identical acidic components, the resistance to nitrogen ability of catalyst of the present invention obviously improves.
The specific embodiment
Hydrocracking catalyst prepared by the inventive method is applicable to hydrocracking process, be particularly suitable for treatment of heavy hydrocarbon material, the boiling range of heavy hydrocarbon material is generally within the scope of 250-600 ℃, and preferably, within the scope of 300-550 ℃, wherein cut more than 70w% is more than 350 ℃.There is the feedstock oil of These characteristics as gas oil, vacuum distillate, de-pitch prill oil, catalytic cracking recycle oil, shale oil, coal tar wet goods.Reaction condition generally under hydrogen existence condition, reaction pressure 5-20MPa, hydrogen to oil volume ratio 100:1-5000:1, raw material volume space velocity 0.1-5.0hr
-1, reaction temperature 350-450 ℃.Hydrocracking process generally comprises the hydrofinishing of leading portion, be used for removing the most S of feedstock oil, N, and the saturated severity that reduces the operation of hydrocracking section of polycyclic aromatic hydrocarbon, but this catalyst can reduce the severity of refining stage operation, embodies good effect in the time of high nitrogen-containing.
Following embodiment has illustrated the present invention, but does not limit its scope.Under hydrogen atmosphere, reduction activation is to carry out under normal pressure.
Comparative example 1
By 25.3 grams of Y sieves (butt 95wt%), 71.4 grams of amorphous aluminum silicide (SiO
2content 50wt%, pore volume 0.85ml/g, specific area 370m
2/ g, butt 70wt%), 122.9 grams of macroporous aluminium oxides (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) put into roller mixed grind, add water, be rolled into paste, extrusion, extrudes bar and is dried 4 hours at 110 ℃, then 550 ℃ of roastings 4 hours, obtain carrier T-1, character is in table 1.
Carrier floods 2 hours by the maceration extract room temperature of tungstenic and nickel (ammonium metatungstate and nickel nitrate), and 120 ℃ are dried 4 hours, 500 ℃ of roastings 4 hours, obtain catalyst B J-1, and catalyst property is in table 2.Catalyst uses the common vulcanizing treatment of row of advancing, sulfidation for hydrogen sulfide containing hydrogen 230 ℃ of constant temperature 8 hours, 280 ℃ of constant temperature 8 hours, 320 ℃ of constant temperature 8 hours.
Embodiment 1
Prepare dimethyl hydrazine NH
2n (CH
3)
2and the maceration extract of tungsten and nickel, dimethyl hydrazine NH in maceration extract
2n (CH
3)
2weight concentration is 30%, the carrier T-1 of comparative example 1 is flooded 2 hours with the maceration extract preparing, be dried 4 hours at 120 ℃, then reduction activation under hydrogen atmosphere, reduction activation program, for to rise to 450 ℃ with 5 ℃/min from room temperature, take heating rate as 2 ℃/min, rises to 700 ℃ from 450 ℃, and 700 ℃ of constant temperature 2 hours, be prepared into catalyst C-1 of the present invention.
Comparative example 2
By 14.7 grams of beta-molecular sieves (butt 95wt%), 151.4 grams of amorphous aluminum silicide (SiO
2content 50wt%, pore volume 0.85ml/g, specific area 370m
2/ g, butt 70wt%), 57.1 grams of macroporous aluminium oxides (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) put into roller mixed grind, add water, be rolled into paste, extrusion, extrudes bar and is dried 4 hours at 110 ℃, then 550 ℃ of roastings 4 hours, obtain carrier T-2, character is in table 1.
Carrier floods 2 hours by the maceration extract room temperature of tungstenic and nickel, and 120 ℃ are dried 4 hours, 500 ℃ of roastings 4 hours, obtain catalyst B J-2, and catalyst property is in table 2.Catalyst uses the common vulcanizing treatment of row of advancing, sulfidation for hydrogen sulfide containing hydrogen 230 ℃ of constant temperature 8 hours, 280 ℃ of constant temperature 8 hours, 320 ℃ of constant temperature 8 hours.
Embodiment 2
Prepare dimethyl hydrazine NH
2n (CH
3)
2and the maceration extract of tungsten and nickel, dimethyl hydrazine NH in maceration extract
2n (CH
3)
2weight concentration is the 40% carrier T-2 by the comparative example 2 maceration extract dipping preparing 2 hours, be dried 6 hours at 100 ℃, then under hydrogen atmosphere, carry out hydrogen activation, first rise to 350 ℃ with 10 ℃/min from room temperature, take heating rate as 1 ℃/min, rise to 600 ℃ from 350 ℃, and 600 ℃ of constant temperature 4 hours, prepare catalyst C-2.
Comparative example 3
By 8.4 grams of Y molecular sieves (butt 95wt%), 85.7 grams of amorphous aluminum silicide (SiO
2content 50wt%, pore volume 0.85ml/g, specific area 370m
2/ g, butt 70wt%), 131.42 grams of macroporous aluminium oxides (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) put into roller mixed grind, add water, be rolled into paste, extrusion, extrudes bar and is dried 4 hours at 110 ℃, then 550 ℃ of roastings 4 hours, obtain carrier T-3, character is in table 1.
Carrier floods 2 hours by the maceration extract room temperature of tungstenic and nickel, and 120 ℃ are dried 4 hours, and 500 ℃ of roastings of temperature programming 4 hours, obtain catalyst B J-3, and catalyst property is in table 2.Catalyst uses the common vulcanizing treatment of row of advancing, sulfidation for hydrogen sulfide containing hydrogen 230 ℃ of constant temperature 8 hours, 280 ℃ of constant temperature 8 hours, 320 ℃ of constant temperature 8 hours.
Embodiment 3
Prepare dimethyl hydrazine NH
2n (CH
3)
2and the maceration extract of tungsten and nickel, dimethyl hydrazine NH in maceration extract
2n (CH
3)
2weight concentration is 40%, the carrier T-3 of comparative example 3 is flooded 2 hours with the maceration extract preparing, be dried 6 hours at 110 ℃, then under hydrogen atmosphere, carry out activation processing, first rise to 450 ℃ with 8 ℃/min from room temperature, take heating rate as 1 ℃/min, rise to 650 ℃ from 450 ℃, and 650 ℃ of constant temperature 4 hours, prepare catalyst C-3.
Embodiment 4
The present embodiment has been introduced the catalyst prepared by the present invention and the activity rating result of comparative example catalyst.On fixed bed hydrogenation experimental rig, evaluate.
Appreciation condition is: reaction stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, raw material volume space velocity 1.0h
-1, use vacuum distillate (VGO) as feedstock oil, feedstock oil character is listed in table 3.The catalyst of preparing in above-mentioned each example is evaluated under above-mentioned process conditions, and the evaluation result obtaining is listed in table 4.
As can be seen from Table 4, catalyst of the present invention is in the situation that refined oil nitrogen content obviously improves, and reaction temperature is low, and activity is higher, and product property is better.
the physico-chemical property of table 1 catalyst carrier
| Numbering | T-1 | T-2 | T-3 |
| Molecular sieve, wt% | 12.0 | 7.0 | 4.0 |
| Amorphous aluminum silicide, wt% | 25.0 | 53.0 | 30.0 |
| Macroporous aluminium oxide, wt% | 43.0 | 20.0 | 46.0 |
| Adhesive, wt% | 20.0 | 20.0 | 20.0 |
table 2 catalyst composition and character
| Numbering | BJ-1 | C-1 | BJ-2 | C-2 | BJ-3 | C-3 |
| W，wt% | 15.1 | 15.6 | 18.0 | 18.5 | 20.4 | 20.8 |
| Ni，wt% | 3.4 | 3.6 | 5.73 | 5.81 | 6.2 | 6.4 |
| Pore volume, ml/g | 0.56 | 0.54 | 0.53 | 0.56 | 0.55 | 0.57 |
| Specific area, m 2/g | 324 | 228 | 279 | 296 | 281 | 301 |
table 3 feedstock oil main character
| Feedstock oil | Vacuum distillate |
| Density (20 ℃), kg/m 3 | 920.6 |
| Boiling range, ℃ | ? |
| ? IBP/10% | 328/413 |
| ? 30%/50% | 450/471 |
| ? 70%/90% | 493/522 |
| ? 95%/EBP | 534/545 |
| Nitrogen, μ g/g | 1575 |
| Carbon, wt% | 85.25 |
| Hydrogen, wt% | 11.96 |
| Carbon residue, wt% | 0.35 |
table 4 catalyst comparative evaluation of the present invention result
| Catalyst | BJ-1 | BJ-2 | BJ-3 | C-1 | C-2 | C-3 |
| Refined oil nitrogen content, μ g/g | 3 | 5 | 8 | 28 | 30 | 35 |
| Reaction temperature, ℃ | 383 | 390 | 393 | 373 | 374 | 378 |
| Product yield and character | ? | ? | ? | ? | ||
| Heavy naphtha | ? | ? | ? | ? | ||
| Yield, wt% | 9 | 8.9 | 10.7 | 8.9 | 8.8 | 10.1 |
| Virtue is dived, wt% | 61.9 | 62.8 | 60.8 | 62.8 | 62.5 | 60.6 |
| Jet fuel | ? | ? | ? | ? | ||
| Yield, wt% | 25.3 | 23.8 | 24.6 | 25.6 | 24.8 | 25 |
| Smoke point, mm | 24 | 23 | 22 | 22 | 24 | 23 |
| Aromatic hydrocarbons, v% | 8.9 | 10 | 12.4 | 12.4 | 8.6 | 10.7 |
| Diesel oil | ? | ? | ? | ? | ||
| Yield, wt% | 36.5 | 35.9 | 33.6 | 36.1 | 37.9 | 33 |
| Cetane number | 58.2 | 56.4 | 55.5 | 55.5 | 60.5 | 60.9 |
| Tail oil | ? | ? | ? | ? | ||
| Yield, wt% | 24.2 | 28.5 | 28.6 | 24.3 | 25.1 | 28.9 |
| BMCI value | 9.8 | 10 | 11 | 9.7 | 9.9 | 11.4 |
| Chemical hydrogen consumption, wt% | 2.21 | 2.18 | 2.26 | 2.26 | 2.34 | 2.23 |
| Middle distillates oil selectivity, wt% | 81.5 | 83.5 | 81.5 | 81.5 | 83.7 | 81.6 |
Claims (13)
1. a preparation method for hydrocracking catalyst, is characterized in that: comprise following process:
(1) catalyst carrier that preparation contains molecular sieve and inorganic refractory oxide;
(2) dipping solution that preparation contains VI B family metallic compound, VIII family metallic compound and hydrazine derivative;
(3) catalyst carrier of the dipping solution impregnation steps (1) of step (2) preparation, then dry;
(4) material that step (3) obtains carries out hydrogen activation, obtains the hydrocracking catalyst for hydrocracking reaction after activation.
2. method according to claim 1, is characterized in that: in step (1), molecular sieve is generally one or more in Y molecular sieve, beta-molecular sieve, ZSM-5 molecular sieve, SAPO-11 molecular sieve, modenite, ZSM-22 molecular sieve, ZSM-23 molecular screen and mesopore molecular sieve.
3. method according to claim 1, is characterized in that: in step (1), inorganic refractory oxide is one or more in aluminium oxide, silica, silica-alumina, magnesia, zirconia, boron oxide and titanium dioxide.
4. method according to claim 1, is characterized in that: step (2) ZhongⅥ B family metallic compound is the soluble compound containing W and/or Mo, and VIII family metallic compound is the soluble compound containing Ni and/or Co.
5. method according to claim 1, is characterized in that: in step (2), hydrazine derivative is dialkyl group hydrazine.
6. method according to claim 1 or 5, is characterized in that: in step (2), hydrazine derivative is dimethyl hydrazine NH
2n (CH
3)
2, by it, the weight concentration in maceration extract is 25%-45% to the addition of hydrazine derivative.
7. method according to claim 1, is characterized in that: the dipping in step (3) is saturated dipping or excess solution dipping, floods for one or many, and the drying process after dipping is dry 4-12 hour at 80-150 ℃.
8. method according to claim 1, it is characterized in that: hydrogen activation process and the condition of step (4) are: under nitrogen atmosphere, take heating rate as 2-10 ℃/min rises to 300-500 ℃ from room temperature, then take heating rate as 0.5-2 ℃/min, be warming up to 600-750 ℃, and at intensification outlet temperature constant temperature 2-4 hour.
9. method according to claim 8, is characterized in that: hydrogen purity is greater than 95%(volume), hydrogen gas space velocity is 50-1000h
-1, pressure is that normal pressure is to 1MPa.
10. a hydrocracking catalyst preparation, is characterized in that: described in employing claim 1-9, method is prepared, and with catalyst carrier weighing scale, the content of molecular sieve is 2%～45%; With the weighing scale of catalyst, metal component of group VIB content is 10%-40%; Metal component of group VIII content is 1%-10%.
11. catalyst according to claim 10, is characterized in that: the content of molecular sieve is 4%～15%; Metal component of group VIB content is 15%-35%, and metal component of group VIII content is 2%-9%.
The catalyst that described in 12. claims 1 prepared by method is at the hydrocracking process for take vacuum distillate as raw material inceasing output of jet fuel and diesel oil, reaction pressure 6-20MPa, hydrogen to oil volume ratio 500:1-2000:1, raw material volume space velocity 0.5-2.0hr
-1, reaction temperature 350-410 ℃.
13. application according to claim 12, is characterized in that: feedstock oil, before carrying out hydrocracking, carries out hydrofinishing, and organic nitrogen content is wherein reduced to below 50 ug/g.
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| WO2020119754A1 (en) * | 2018-12-13 | 2020-06-18 | 中国石油化工股份有限公司 | Hydrocracking catalyst, preparation method therefor and application thereof |
| RU2776810C1 (en) * | 2018-12-13 | 2022-07-26 | Чайна Петролиум энд Кемикал Корпорейшн | Hydrocracking catalyst, method for its preparation and its application |
| CN117654606A (en) * | 2024-01-31 | 2024-03-08 | 山东昊瑞环保科技有限公司 | Hydrocracking catalyst and preparation method thereof |
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| WO2020119754A1 (en) * | 2018-12-13 | 2020-06-18 | 中国石油化工股份有限公司 | Hydrocracking catalyst, preparation method therefor and application thereof |
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