CN103785442B - A kind of metal nitride type hydrocracking catalyst and its preparation method and application - Google Patents

Abstract

The present invention discloses a kind of hydrocracking catalyst, and with catalyst carrier weighing scale, the content of molecular sieve is generally 2% ~ 45%, is preferably 4% ~ 15%; With catalyst weight, metal component of group VIB (the nitride weighing scale of W and/or Mo) content is generally 10%-40%, better 15%-35%, best 18%-28%, metal component of group VIII (the nitride weighing scale with Ni and/or Co) content is generally 1%-10%, better 2%-9%, preferably 4%-8%.Hydrocracking catalyst of the present invention is for the treatment of heavy hydrocarbon material, and maximum produces intermediate oil.

Description

A kind of metal nitride type hydrocracking catalyst and its preparation method and application

Technical field

The present invention relates to a kind of metal nitride type hydrocracking catalyst and its preparation method and application, this catalyst has excellent 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 race's metal to make hydrogenation component, and cracking performance provides primarily of acidic components, and acidic components can select crystal formation zeolite and/or amorphous aluminum silicide etc.Simple amorphous aluminum silicide, although selective higher, active low, operational flexibility is restricted, in most of hydrocracking catalyst all with crystal formation zeolite for acidic components, or crystal formation zeolite and amorphous aluminum silicide are acidic components jointly.

The middle oil type hydrocracking catalyst major part that commercial plant uses at present is the catalyst containing zeolite, and the zeolite component adopted mainly y-type zeolite, β zeolite and two kinds of zeolites are used in combination, and catalyst all will carry out presulfurization before reactions, metal component is made to be converted into sulphided state, to improve the serviceability of catalyst.But use the health of the higher vulcanizing agent of sulfur content not only contaminated environment, harm operating personnel, and sulfidation is numerous and diverse, needs 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 reduce hydrogen consumption, the silica/alumina molecular proportion at least 50:1 of the zeolite component in catalyst, general 100:1, even 200:1.The middle distillates oil selectivity order that variety classes zeolite is used for catalyst is: ZSM-20> β >Y type, process Arabic VGO, when control 60v% transforms, middle distillates oil selectivity 45-65v%, wherein acidic components are β zeolite, during 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 the middle distillates oil selectivity improving catalyst, be characterized in by using the dry type heat treatment method passing into inert gas being included in 676-788 DEG C of temperature water heat treatment or best 704 DEG C, obtain a kind of low acidity Y zeolite, but because this zeolitic acid is spent low, high for reaction temperature during catalytic component process feedstock oil, general more than 400 DEG C, inhibit hydrogenation reaction, the thermal cracking performance trend of zeolite strengthens, the middle distillates oil selectivity of catalyst is improved 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, embodiment 50-185 DEG C of naphtha yield improves obviously, and the use of β zeolite relatively only uses the catalyst activity of Y zeolite also high.Although this catalyst also may be used 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 dispersed in γ-Al with the use of one ₂o ₃and so on the sial on macroporous aluminium oxide matrix, the middle oil type catalyst that this patent relates to is for ensureing middle distillates oil selectivity, and activity of having to force down, makes reaction temperature higher, general more than 390 DEG C, thus result in poor adaptability to raw material.

The hydrogenation component of above-mentioned hydrocracking catalyst is the metal component of sulphided state.In hydrocracking catalyst, although hydrogenation activity and cracking activity main body are provided by two kinds of components, but in the 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 regulating in hydrocracking catalyst, the correlation of hydrogenation active component and cracking active component, is the important content improving the comprehensive serviceability of hydrocracking catalyst.

The preparation method that CN02130058.5 proposes a kind of aluminium nitride is by alchlor, under the nitrogen of the certain purity of suitable proportion and the gaseous mixture atmosphere of hydrogen, carry out multi-stage procedure temperature reaction, then cool in an inert atmosphere, passivation under certain oxygen concentration.The aluminium nitride prepared is carry out hydrodesulfurization under 250-450 DEG C, 0.2-20MPa as the application of Hydrobon catalyst.

Above-mentioned hydrocracking catalyst needs to carry out normal vulcanizing treatment before using, and active metal is converted into sulphided state, and the serviceability of catalyst needs to improve further.Transition metal nitride, as a kind of new catalytic material, not only possesses higher desulfurization, denitrification activity, and has very high selective to the cracking of heteroatomic ring, its surface nature and catalytic performance and noble metal similar.Therefore, be called " accurate noble metal " by people, be even considered to a kind of potential industrial catalyst of deep desulfuration from now on.And the application in hydrocracking is ignored, hydrocracking catalyst is a kind of bifunctional catalyst, and the raising of hydrogenating function will promote the serviceability of catalyst.

Summary of the invention

The object of the present invention is to provide a kind of metal nitride type hydrocracking catalyst and its preparation method and application, hydrocracking catalyst of the present invention is for the treatment of heavy hydrocarbon material, and maximum produces intermediate oil.

In hydrocracking catalyst of the present invention, with catalyst carrier weighing scale, the content of molecular sieve is generally 2% ~ 45%, is preferably 4% ~ 15%; With catalyst weight, metal component of group VIB (W and/or Mo) is generally 10%-40% in the content of nitride, is better 15%-35%, best 18%-28%, metal component of group VIII (Ni and/or Co) is generally 1%-10% in the content of nitride, is better 2%-9%, preferably 4%-8%.

The preparation method of metal nitride type hydrocracking catalyst of the present invention comprises following process:

(1) preparation contains the catalyst carrier of molecular sieve and inorganic refractory oxide;

(2) dipping solution of preparation containing VI B race metallic compound, VIII race's metallic compound;

(3) add hydrazine derivative in the dipping solution that step (2) is prepared, carry out ultrasonic wave dispersion, then the catalyst carrier of impregnation steps (1), 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, if hydrazine derivative can use any can with tungsten react become tungsten nitride hydrazine derivative as this nitrogenous source.Preferably use dialkyl group hydrazine, be in particular dimethyl hydrazine NH ₂n (CH ₃) ₂.The addition of hydrazine derivative is 25%-45% by its weight concentration in maceration extract.Required hydrazine derivative is added in the dipping solution containing VI B race metallic compound and VIII race's metallic compound, carry out ultrasonic wave dispersion, hyperacoustic frequency is 10-40KHz, power is 0.1-500W/L, the time of ultrasonic disperse is 0.5-10 hour, frequency preferably can be adopted to be 15-25KHz, and power is 80-200W/L, and the time of ultrasonic disperse is 2-6 hour.

In hydrocracking catalyst preparation method of the present invention, 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 the modification be suitable for, as hydrothermal treatment consists modification, acid treatment modification etc.One or more in inorganic refractory oxide is generally aluminium oxide, silica, silica-alumina (i.e. amorphous aluminum silicide), silica-alumina are scattered in aluminium oxide (being namely dispersed in the amorphous aluminum silicide in aluminium oxide) wherein, silica is covered with paint, lacquer, colour wash, etc. aluminium oxide, magnesia, zirconia, boron oxide and titanium dioxide, are 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, obtains catalyst carrier as required material finally formed the steps such as the mixing of required ratio, shaping, dry, roasting in catalyst.Drying is generally dry 4-12 hour at 80-150 DEG C, and roasting is roasting 2-6 hour at 400-600 DEG C.

In hydrocracking catalyst preparation method of the present invention, the dipping in step (3) is saturated dipping or excess solution impregnation, and be preferably excess solution impregnation, dipping can once carry out, and also can repeatedly flood.Drying process after dipping is dry 4-12 hour at 80-150 DEG C.The all or part of time of dipping process adopts ultrasonic wave dispersion dipping, hyperacoustic frequency is 10-40KHz, power is 0.1-500W/L, the time of ultrasonic disperse dipping is 10% ~ 100% of total dipping, frequency preferably can be adopted to be 15-25KHz, power is 80-200W/L, and the time of ultrasonic disperse dipping is 50% ~ 90% of total dip time.

In hydrocracking catalyst preparation method of the present invention, VI B race metallic compound is the soluble compound containing W and/or Mo, and VIII race's metallic compound is the soluble compound containing Ni and/or Co.Drying process after dipping is dry 4-12 hour at 80-150 DEG C.Dipping solution take water as solvent, can add ammonia etc. in right amount and promote that compound dissolves.

In hydrocracking catalyst preparation method of the present invention, Hydrogen activation process and the condition of step (4) are: under a hydrogen atmosphere, be that 2-10 DEG C/min rises to 300-500 DEG C from room temperature with heating rate, then be 0.5-2 DEG C/min with heating rate, be warming up to 600-750 DEG C, 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.

Hydrocracking catalyst prepared by the inventive method, for vacuum distillate be raw material inceasing output of jet fuel and diesel oil hydrocracking process in, reaction pressure preferably at 6-20MPa, hydrogen to oil volume ratio 500:1-2000:1, raw material volume air speed 0.5-2.0hr ^-1, reaction temperature 350-410 DEG C.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 hydrazine derivative matched with active metal component, by suitable process, nitrogen and active metal are formed the nitride metal state of bonding state to a certain degree, show by analyzing, in catalyst prepared by the inventive method, there is metal nitride, and common for hydrocracking catalyst sulfidation is cancelled, adopt the catalyst of hydrogen reducing mode to metal-containing compound and nitrogen component to carry out activation process, make metallic compound be converted into nitride metal state.The nitrogenize state of active metal component has desirable Hydrogenation on the one hand, and the acid centre of nitrogenize state to molecular sieve of active metal component creates certain effect on the other hand.Show by analysis, the B acid site of active metal nitrogenize state and molecular sieve interacts, significantly improve the acid strength distribution on zeolite, strong acid is reduced, middle intensity acid increases, acid site number increases to some extent, and L acid site number reduces relatively, can reduce fine melt function like this, increase the activity that moderate strength acid amount is conducive to improving catalyst, reduce reaction temperature, and improve the selective of intermediate oil (kerosene and diesel oil).Hydrocracking catalyst of the present invention can significantly improve the nitrogen resistance of catalyst simultaneously, and when using identical acidic components, the resistance to nitrogen ability of catalyst of the present invention significantly improves.In addition, method for preparing catalyst of the present invention has the interaction between suitable active metal component and carrier, ensures the stability of active constituent loading on the one hand, makes catalyst cracking performance and Hydrogenation play better synergy on the other hand.Ultrasonic wave dispersion and ultrasonic wave is adopted to flood the interaction that can promote further between active component and hydrazine derivative in the preparation method of catalyst of the present invention.

Detailed description of the invention

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 DEG C, and preferably within the scope of 300-550 DEG C, wherein the cut of more than 70w% is more than 350 DEG C.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 air speed 0.1-5.0hr ^-1, reaction temperature 350-450 DEG C.Hydrocracking process generally comprises the hydrofinishing of leading portion, for removing most S, N in feedstock oil, and the saturated severity reducing the operation of hydrocracking section of polycyclic aromatic hydrocarbon, but this catalyst can reduce the severity of refining stage operation, embodies good effect when high nitrogen-containing.

Following embodiment describes the present invention, but does not limit its scope.Under hydrogen atmosphere, reduction activation is 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, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier T-1, character is in table 1.

The dipping solution room temperature immersion of carrier tungstenic and nickel (ammonium metatungstate and nickel nitrate, lower with) 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 hours, obtain catalyst B J-1, catalyst property was in table 2.Catalyst uses the common vulcanizing treatment of row of advancing, and sulfidation is with hydrogen sulfide containing hydrogen 230 DEG C of constant temperature 8 hours, 280 DEG C of constant temperature 8 hours, 320 DEG C of constant temperature 8 hours.

Embodiment 1

With the dipping solution of comparative example 1, add dimethyl hydrazine NH ₂n (CH ₃) ₂its weight concentration in dipping solution is made to be 25%-45%, employing frequency is 18KHz, power is that the ultrasonic echography of 100W/L disperses 1 hour, at room temperature carrier T-1 is flooded, dip time is 2 hours, adopts frequency to be 18KHz while dipping, and power is the ultrasonic echography dispersion of 100W/L, then in 120 DEG C of dryings 4 hours, then reduction activation in a hydrogen atmosphere.Reduction activation program, for rise to 450 DEG C with 5 DEG C/min from room temperature, is 2 DEG C/min with heating rate, rises to 500 DEG C from 450 DEG C, and 500 DEG C of constant temperature 2 hours, is prepared into catalyst C-1 of the present invention.

Through XRD analysis (under nitrogen protection condition), can find out that there is in catalyst of the present invention the characteristic diffraction peak of tungsten nitride and nickel oxide, define the nitrogenize state of active metal.

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, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier T-2, character is in table 1.

The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 hours, obtain catalyst B J-2, catalyst property was in table 2.Catalyst uses the common vulcanizing treatment of row of advancing, and sulfidation is with hydrogen sulfide containing hydrogen 230 DEG C of constant temperature 8 hours, 280 DEG C of constant temperature 8 hours, 320 DEG C of constant temperature 8 hours.

Embodiment 2

With the dipping solution of comparative example 1, add dimethyl hydrazine NH ₂n (CH ₃) ₂its weight concentration in dipping solution is made to be 35%, employing frequency is 25KHz, power is that the ultrasonic echography of 150W/L disperses 5 hours, at room temperature carrier T-2 is flooded, dip time is 4 hours, frequency is adopted to be 25KHz while dipping, power is the ultrasonic echography dispersion of 150W/L, ultrasonic echography stops ultrasonic wave after disperseing 2 hours, continue dipping 2 hours, 100 DEG C of dryings 6 hours, then Hydrogen activation is carried out in a hydrogen atmosphere, first 350 DEG C are risen to 10 DEG C/min from room temperature, be 1 DEG C/min with heating rate, 600 DEG C are risen to from 350 DEG C, and 600 DEG C of constant temperature 4 hours, prepare nitrogenize transition-metal 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, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier T-3, character is in table 1.

The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, temperature programming 500 DEG C of roastings 4 hours, obtain catalyst B J-3, catalyst property is in table 2.Catalyst uses the common vulcanizing treatment of row of advancing, and sulfidation is with hydrogen sulfide containing hydrogen 230 DEG C of constant temperature 8 hours, 280 DEG C of constant temperature 8 hours, 320 DEG C of constant temperature 8 hours.

Embodiment 3

With the dipping solution of comparative example 1, add dimethyl hydrazine NH ₂n (CH ₃) ₂its weight concentration in dipping solution is made to be 45%, employing frequency is 35KHz, power is that the ultrasonic echography of 10W/L disperses 7 hours, at room temperature carrier T-3 is flooded, dip time is 4 hours, dipping adopts frequency to be 35KHz simultaneously, power is the ultrasonic echography dispersion of 10W/L, 110 DEG C of dryings 6 hours, then activation process is carried out in a hydrogen atmosphere, first 450 DEG C are risen to 8 DEG C/min from room temperature, be 1 DEG C/min with heating rate, 650 DEG C are risen to from 450 DEG C, and 650 DEG C of constant temperature 4 hours, prepare nitrogenize transition-metal catalyst C-3.

Embodiment 4

This embodiment describes the Activity evaluation of catalyst and the comparative example catalyst prepared by the present invention.Fixed bed hydrogenation experimental rig is evaluated.

Appreciation condition is: reaction stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, raw material volume air speed 1.0h ^-1, use vacuum distillate (VGO) as feedstock oil, feedstock oil character lists in table 3.Evaluated under above-mentioned process conditions by the catalyst prepared in above-mentioned each example, the evaluation result obtained lists in table 4.

As can be seen from Table 4, catalyst of the present invention activity when refined oil nitrogen content significantly improves 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	BJ-2	BJ-3	C-1	C-2	C-3
							WO 3，wt%	16.58	22.82	23.27	-	-	-
W 2N，wt%	-	-	-	15.88	25.16	23.18
							NiO，wt%	4.36	5.73	5.81	-	-	-
Ni 3N 2，wt%	-	-	-	4.21	5.54	6.55
							Pore volume, mL/g	0.56	0.53	0.55	0.53	0.54	0.57
Specific area, m 2/g	324	279	281	329	294	298

table 3 feedstock oil main character

Feedstock oil	Vacuum distillate
		Density (20 DEG C), kg/m 3	920.6
Boiling range, DEG C
		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 COMPARATIVE CATALYST's evaluation result of the present invention

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, DEG C	383	390	393	370	371	375
							Product yield and character
Heavy naphtha
							Yield, wt%	9	8.9	10.7	7.9	7.8	9.1
Virtue is dived, wt%	61.9	62.8	60.8	63	62.9	61.3
							Jet fuel
Yield, wt%	25.3	23.8	24.6	25.8	25.1	25.4
							Smoke point, mm	24	23	22	24	26	25
Aromatic hydrocarbons, v%	8.9	10	12.4	12.1	8.2	10.1
							Diesel oil
Yield, wt%	36.5	35.9	33.6	36.5	38.3	33.8
							Cetane number	58.2	56.4	55.5	55.9	61.5	61.9
Tail oil
							Yield, wt%	24.2	28.5	28.6	24.2	24.8	29.2
BMCI value	9.8	10	11	9.5	9.6	11.1
							Chemical hydrogen consumption, wt%	2.21	2.18	2.26	2.28	2.38	2.29
Middle distillates oil selectivity, wt%	81.5	83.5	81.5	82.2	84.3	83.6

Claims (14)

1. a preparation method for metal nitride type hydrocracking catalyst, is characterized in that: comprise following process:

(1) preparation contains the catalyst carrier of molecular sieve and inorganic refractory oxide;

(2) dipping solution of preparation containing VI B race metallic compound, VIII race's metallic compound;

(3) hydrazine derivative is added in the dipping solution that step (2) is prepared, carry out ultrasonic wave dispersion, then the catalyst carrier of impregnation steps (1), then dry, described hydrazine derivative is dialkyl group hydrazine, and the addition of hydrazine derivative is 25%-45% by its weight concentration in maceration extract;

(4) material that step (3) obtains carries out Hydrogen activation, obtains the hydrocracking catalyst for hydrocracking reaction after activation;

With catalyst carrier weighing scale, the content of molecular sieve is 2% ~ 45%; With catalyst weight, metal component of group VIB in the content of nitride for 10%-40%, metal component of group VIII in the content of nitride for 1%-10%.

2. the preparation method of catalyst according to claim 1, it is characterized in that: with catalyst carrier weighing scale, the content of molecular sieve is 4% ~ 15%; With the weighing scale of catalyst, metal component of group VIB in the content of nitride for 15%-35%, metal component of group VIII in the content of nitride for 2%-9%.

3. the preparation method of catalyst according to claim 1, is characterized in that: the condition of ultrasonic wave dispersion is ultrasonic frequency is 10-40KHz, and power is 0.1-500W/L, and the time of ultrasonic disperse is 0.5-10 hour.

4. the preparation method of catalyst according to claim 3, is characterized in that: hydrazine derivative is dimethyl hydrazine NH ₂n (CH ₃) ₂, ultrasonic frequency is 15-25KHz, and power is 80-200W/L, and the time of ultrasonic disperse is 2-6 hour.

5. the preparation method of catalyst according to claim 1, it is characterized in that: molecular sieve is 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 inorganic refractory oxide is one or more in aluminium oxide, silica, silica-alumina, magnesia, zirconia, boron oxide and titanium dioxide.

6. the preparation method of catalyst according to claim 1, it is characterized in that: the preparation of catalyst carrier comprises material and finally forms required ratio mixing, shaping, dry, calcination steps in catalyst, drying is dry 4-12 hour at 80-150 DEG C, and roasting is roasting 2-6 hour at 400-600 DEG C.

7. the preparation method of catalyst according to claim 1, it is characterized in that: the dipping in step (3) is saturated dipping or excess solution impregnation, dipping once carries out or repeatedly floods, and the drying process after dipping is dry 4-12 hour at 80-150 DEG C.

8. the preparation method of catalyst according to claim 7, it is characterized in that: all or part of time of dipping process adopts ultrasonic wave dispersion dipping, hyperacoustic frequency is 10-40KHz, and power is 0.1-500W/L, and the time of ultrasonic disperse dipping is 10% ~ 100% of total dipping.

9. the preparation method of catalyst according to claim 8, it is characterized in that: frequency is 15-25KHz, power is 80-200W/L, and the time of ultrasonic disperse dipping is 50% ~ 90% of total dip time.

10. the preparation method of catalyst according to claim 1, it is characterized in that: VI B race metallic compound is the soluble compound containing W and/or Mo, VIII race's metallic compound is the soluble compound containing Ni and/or Co, and the drying process after dipping is dry 4-12 hour at 80-150 DEG C.

The preparation method of 11. catalyst according to claim 1, it is characterized in that: Hydrogen activation process and the condition of step (4) are: under a hydrogen atmosphere, be that 2-10 DEG C/min rises to 300-500 DEG C from room temperature with heating rate, then be 0.5-2 DEG C/min with heating rate, be warming up to 600-750 DEG C, and at intensification outlet temperature constant temperature 2-4 hour.

12. according to the preparation method of catalyst described in claim 11, and it is characterized in that: hydrogen volume purity is greater than 95%, hydrogen gas space velocity is 50-1000h ^-1, pressure is that normal pressure is to 1MPa.

The application of the catalyst that described in 13. claims 1 prepared by method in the hydrocracking process taking vacuum distillate as raw material inceasing output of jet fuel and diesel oil, it is characterized in that: reaction pressure 6-20MPa, hydrogen to oil volume ratio 500:1-2000:1, raw material volume air speed 0.5-2.0hr ^-1, reaction temperature 350-410 DEG C.

14. application according to claim 13, is characterized in that: feedstock oil, before carrying out hydrocracking, carries out hydrofinishing, and organic nitrogen content is wherein reduced to 50 below μ g/g.