CN103055923B - Preparation method of hydrocracking catalyst - Google Patents

Abstract

The invention discloses a preparation method of a hydrocracking catalyst. The method comprises the steps of preparing an acidic mixed solution A containing hydrogenation reactive metals and silicon, preparing a sodium metaaluminate alkaline solution B, and then adding the acidic mixed solution A, the alkaline solution B and CO2 to a reaction tank filled with clear water in parallel to prepare gel; and then adding turbid liquid of a Y type molecular sieve, mixing the substances uniformly, filtering, drying and forming the mixture, and then washing, drying and roasting the product, thus preparing the hydrocracking catalyst. The method has the beneficial effects that a clean preparation method is adopted, so not only can the catalyst be easily formed and the strength of the catalyst be improved, but also the pore volume and specific surface area of the catalyst can be increased and the dispersity of metals in the catalyst can be improved, thus the catalyst has higher hydrocracking activity, middle oil selectivity and stability; and the catalyst prepared by the method can be used for a single-section hydrocracking process of a non-refining section or a one-section serial hydrocracking process of a refining section.

Description

A kind of preparation method of hydrocracking catalyst

Technical field

The present invention relates to a kind of preparation method of hydrocracking catalyst for the treatment of of heavy hydrocarbon class, the particularly preparation method of high activity medium oil type hydrocracking catalyst.

Background technology

At present, worldwide petroleum resources are not enough, and crude quality is deteriorated year by year, intermediate oil demand increases, petroleum chemicals upgrading and environmental regulation are more and more strict, all greatly facilitate heavy oil lighting, and form the very strong driving force of accelerated development hydrogen addition technology.The main feature of hydrocracking technology is that adaptability to raw material is strong, products scheme, object product selectivity are high, good product quality and added value is high, directly can produce multiple high-quality oil product (as gasoline, jet fuel, diesel oil, lube base wet goods) and high-quality industrial chemicals (as the production such as benzene,toluene,xylene, ethene raw material).

Hydrocracking is carried out at elevated pressures, and hydrocarbon molecules and hydrogen carry out at catalyst surface the conversion process that cracking and hydrogenation reaction generate lighter molecule, and the hydrogenation reaction of hydrodesulfurization, denitrogenation and unsaturated hydrocarbons also occurs simultaneously.The cracking reaction of hydro carbons in hydrocracking process is carried out on the acid centre of catalyst, follows carbon ion reaction mechanism, with the generation of hydro carbons isomerization reaction while hydrogenation, cracking reaction.Hydrocracking catalyst is made up of hydrogenation component and acidic components, and both add as required by a certain percentage, makes hydrogenation and cracking performance reach balance, and its effect is the abundant hydrogenation of hydrocarbon mixture, cracking and isomerization orientation reaction.Therefore, the catalyst of distillate hydrocracking process need should possess stronger hydrogenation sites and have moderate acid centre again.

The single stage process flow process reduced investment of hydrocracking, simple to operate, and also air speed is large, and unconverted oil can Appropriate application.But to the anti-nitrogen performance of catalyst, hydrocracking performance all requires very high.The hydrocracking catalyst that single-stage hydrocracking technical process uses uses when not having prerefining to protect.Generally react to directly contacting with hydrocracking catalyst when 1000 ~ 2000 μ g/g when feed nitrogen content is high, this just requires that hydrocracking catalyst has the poisoning ability of good anti-nitride, namely there is good hydrocracking under the condition that reactant nitrogen content is higher active, also will have the performance delaying carbon deposit preferably and generate simultaneously.

Bulk phase catalyst refers to that the loaded catalyst be dispersed on carrier with active constituent is relative, not with inactive carrier for carrier.Catalyst major part is made up of active component, and the content of active constituent is generally unrestricted, sometimes also claims body catalyst.Compared with load hydrogenation catalyst, body phase hydrogenation catalyst activated centre density wants high a lot, has that superelevation is desulphurizing activated, denitrogenation and an arene saturating activity.

The petroleum refining industry of 21st century must follow the strategy of sustainable development, the principle that must pay attention to economic benefit, protection of the environment simultaneously and economize on resources.Therefore, adopt the preparation method of non-environmental-pollution to produce bulk phase catalyst and become more important.Existing coprecipitation method Kaolinite Preparation of Catalyst technology, uses NH mostly ₃h ₂o is as precipitating reagent, and this is by producing a large amount of waste water containing ammonia, nitrogen, to environment.

Hydrocracking catalyst disclosed in US 3954671, hydrogenation conversion catalyst disclosed in US 4313817, the hydrocracking catalyst of nitrogen-resistant type fecund intermediate oil disclosed in CN1253988A, heavy hydrocarbons hydrocraking catalyst disclosed in CN1253989A, these catalyst are that glue legal system is standby altogether in employing, alkaline precipitating agent used is all Ammonia, though can obtain for the treatment of the comparatively ideal hydrocracking catalyst of heavy hydrocarbon fecund intermediate oil performance, the too not effective control measures of ammonia nitrogen pollution on the environment.CN101239324A discloses a kind of glue legal system altogether for the method for high activity, medium oil type hydrocracking catalyst, and precipitating reagent adopts alkalescent ammoniac compounds, still there is the problem of ammonia and nitrogen pollution.

Adopt sodium metaaluminate aqueous slkali to be the method that hydrogenation catalyst prepared by precipitating reagent disclosed in CN101172261A, precipitation is mainly from meta-aluminic acid radical ion and hydroxide ion, easily larger deposit seed is formed like this in precipitation process, the bad adhesion of catalyst feed, cause the specific area of catalyst and intensity to decline to some extent simultaneously, can have an impact to the serviceability of catalyst.

Existing coprecipitation method Kaolinite Preparation of Catalyst technology, adopts sodium metaaluminate to do aluminium source and precipitating reagent, avoid producing ammonia, polluted by nitrogen in catalyst preparation process, but catalyst feed adhesivity is poor.The caking property of precipitated metal thing can be increased in body phase method metalliferous material containing suitable heteroion, contribute to metalliferous material extruded moulding.If sodium metaaluminate instead of the solvable inorganic aluminates such as aluminium chloride, aluminum nitrate, aluminum sulfate and does aluminium source, a large amount of NO will be reduced ₃ ^-, Cl ^-, SO ₄ ^2-deng heteroion, the composite oxides precursor peptization of preparation is poor, metalliferous material difficult forming.Coprecipitation method Kaolinite Preparation of Catalyst also has a difficult point to be that the metal mixture grain size difference that obtains of different aluminium sources and precipitating reagent is large and then have considerable influence to the specific area of catalyst, intensity.In order to decreasing pollution, how to solve the problem adopting sodium metaaluminate replacement ammoniacal liquor to do the materials from bonding difference of the body phase clean method for preparing generation of precipitating reagent.How to allow Ni prepared by coprecipitation method _xw _yo _zcomposite oxides and Al ₂o ₃the mixture crystal grain homoepitaxial of precursor, catalyst has the scattered feature of bigger serface, good pore structure, active metal, improves the Hydrogenation of catalyst.

Summary of the invention

For the deficiencies in the prior art, the invention provides a kind of preparation method of hydrocracking catalyst, particularly adopt clean method for preparing, the method not only can make catalyst easily shaping, improve the intensity of catalyst, the pore volume of catalyst, specific area can also be increased, improve the metal dispersity in catalyst, make catalyst have higher hydrogenation cracking activity, middle distillates oil selectivity and stability.Catalyst of the present invention can be used for the single-stage hydrocracking technique without refining stage, also can be used for the one-stage serial hydrocracking technique having refining stage.

The preparation method of hydrocracking catalyst of the present invention, described hydrocracking catalyst comprises amorphous aluminum silicide, Y zeolite, hydrogenation active metals component, wherein hydrogenation active metals component is group VIB metal and group VIII metal, preparation process is as follows: preparation contains the acidic mixed solution A of hydrogenation active metals and silicon, preparation sodium metaaluminate alkaline solution B, then acidic mixed solution A, alkaline solution B and gas CO ₂and stream add water purification is housed retort in plastic, plastic pH value controls 6.5 ~ 8.5; Then the suspension adding Y zeolite mixes, and the mixture of gained filters, the filter cake drying obtained, then obtains hydrocracking catalyst through shaping, washing, drying, roasting.

In the inventive method, acidic mixed solution A, alkaline solution B and gas CO ₂and flow in plastic process that to control gelling temperature be 40 ~ 70 DEG C.CO used ₂the volumetric concentration of gas is 30% ~ 60%, adds CO ₂al in the total amount of gas and alkaline solution B ₂o ₃mol ratio be 2 ~ 8, control gelation time at 0.5 ~ 3.0 hour.

In hydrocracking catalyst of the present invention, with the weight of catalyst for benchmark, the content of group vib metal oxide is 10wt% ~ 50wt%, preferably 20wt% ~ 30wt%, and the content of group VIII metal oxide is 1wt% ~ 20wt%, preferably 5wt% ~ 15wt%, preferably 4wt% ~ 8wt%, the content of Y zeolite is 10wt% ~ 40wt%, preferably 20wt% ~ 30wt%, the content of amorphous aluminum silicide is 30wt% ~ 60wt%, preferably 30wt% ~ 40wt%.

In hydrocracking catalyst of the present invention, also can contain adjuvant component, described adjuvant component is IVB race metal, and the content of IVB family metal oxide in hydrocracking catalyst is 1 ~ 10wt%.Described IVB race metal is preferably Ti and/or Zr.In hydrocracking catalyst preparation process of the present invention, preparing in acid solution A process the compound added containing adjuvant component, i.e. titanium source and/or zirconium source.

In hydrocracking catalyst of the present invention, Y zeolite used can adopt all Y zeolites that can be used in hydrocracking catalyst in prior art, such as: Y zeolite disclosed in CN1253988A, CN1508228A, CN101450319A.The molecular sieve that in the present invention, preferred CN 96119840.0 reports is raw material, it is 650 ~ 800 DEG C in temperature, pressure is that normal pressure is to 0.3MPa, time is that to carry out hydrothermal treatment consists in the condition and range of 20 ~ 30 hours deep sealumination modified, a small amount of ammonia can be contained in water vapour during hydrothermal treatment consists, ammonia dividing potential drop is 50 ~ 3000Pa(absolute pressure), then be 0.5 ~ 10.0mol/L in acid concentration, time is 0.5 ~ 20.0 hour, temperature is 30 ~ 80 DEG C, acid consumption and the ratio of molecular sieve be 1:1 ~ 20:1 condition and range in carry out acid treatment, use inorganic acid is hydrochloric acid, sulfuric acid or nitric acid etc., the Y zeolite being applicable to the present invention's use is obtained after hydrothermal treatment consists and acid treatment, its character is as follows: the pore volume that bore dia is greater than 1.7nm accounts for more than 45% of total pore volume, specific area is 750 ~ 900m ²/ g, cell parameter at 2.423nm ~ 2.545nm, relative crystallinity 95% ~ 110%, SiO ₂/ Al ₂o ₃mol ratio is 7 ~ 60.The existing high degree of crystallinity of this molecular sieve, have again low cell parameter, the secondary pore of molecular sieve is many, is conducive to the diffusion velocity improving raw material and product, reduces the second pyrolysis of product; Large specific area, less acid site number, the intermediate oil being also more conducive to improving hydrocracking catalyst is selective; High silica alumina ratio, major part is the acid centre of moderate strength, and the acid site degree that is evenly distributed is high, makes this molecular sieve have very strong nitrogen resistance and broken ring ability preferably.The above-mentioned characteristic of this molecular sieve can make catalyst have the poisoning ability of good anti-nitride when the raw material that directly contact impurity content is high, the stability that good hydrocracking activity is become reconciled.

In hydrocracking catalyst preparation method of the present invention, described washing can adopt conventional method to carry out, such as adopt deionized water washing 2 ~ 5 times, drying condition before shaping is as follows: drying 2 ~ 10 hours at 100 ~ 150 DEG C, drying condition after shaping is as follows: at 100 ~ 150 DEG C dry 2 ~ 10 hours, and described roasting condition is roasting 3 ~ 10 hours at 450 ~ 650 DEG C.

Hydrocracking catalyst of the present invention adopts coprecipitation method preparation, and acidic components and active metal component coprecipitation get off, and metal loading is unrestricted, and metal dispersion is good.And the present invention is not with the NH that coprecipitation method is conventional _3.h ₂o is precipitating reagent, avoids a large amount of ammonia and nitrogen pollutions.

Present invention employs sodium metaaluminate is aluminium source, adopts containing hydrogenation active metals, silicon, the acidic mixed solution preferably containing adjuvant component, sodium metaaluminate alkaline solution and CO ₂the preparation method of gas co-precipitation, to make in plastic thing, except being formed except precipitation of hydroxide, to define CO after reaction ₃ ^2-or HCO ₃ ^-, after adding heteroion, precipitated metal thing caking property strengthens, and makes catalyst easily shaping, improves the intensity of catalyst, simultaneously CO ₃ ^2-or HCO ₃ ^-can remove during ion roasting, pollution-free and without the need to washing, avoid and use NH ₃h ₂o, as precipitating reagent, produces a large amount of waste water containing ammonia, nitrogen.And the Ni generated _xw _yo _zthe mixture homogeneous grain size of composite oxides and amorphous aluminum silicide precursor, improves the physico-chemical property of catalyst, has larger specific area and pore volume, reasonably pore structure.Simultaneously in roasting process, release a certain amount of carbon dioxide, under the percussion of gas, not only improve the pore structure of catalyst, but also make more metal active position be exposed to the surface of catalyst, improve the utilization rate of active metal.The inventive method is pollution-free in preparation process, catalyst easy-formation, there is larger specific area and pore volume, reasonably pore size distribution, originally intensive active metal decentralization can be improved, fully expose the high hydrogenation sites of Ni-W, make containing heteroatomic labyrinth hydrocarbon molecule have more multimachine can close to Ni-W high activity center effective hydrogenation, more easily imurity-removal.

Catalyst of the present invention has bigger serface, large pore volume, reasonably pore size distribution, and a large amount of active metal comes out equably, and acid centre can be made fully to contact with hydrogenation sites.The preferred Y zeolite of the present invention is applicable to oil in fecund, improves activity, is conducive to anti-nitrogen, be dispersed in the homogeneous system of amorphous silicon aluminium carrier and active metal formation, active metal and acid function can be made to play one's part to the full, thus hydrocracking catalyst is reached both there is high hydrogenation cracking activity, there is again high middle distillates oil selectivity, also there is the serviceability that stronger resistance to nitrogen ability etc. is good simultaneously.

Catalyst of the present invention is used for, in single-stage hydrocracking technical process, having liquid yield high, the advantages such as good product quality.

Detailed description of the invention

In hydrocracking catalyst of the present invention, hydrogenation active metals component is group vib metal and group VIII metal, and group vib metal is preferably W and/or Mo, group VIII metal Co and/or Ni.Auxiliary agent is IVB race metal, is preferably Ti and/or Zr.Contain hydrogenation active metals, silicon in preparation, preferably contain in the process of acidic mixed solution A of auxiliary agent, hydrogenation active metals and auxiliary agent can adopt water soluble compound soluble in water formulated, such as tungsten source can adopt one or more in ammonium metatungstate, sodium tungstate, molybdenum source can adopt molybdenum trioxide, ammonium molybdate, cobalt source can adopt cobalt nitrate, nickel source can adopt in nickel nitrate, nickel chloride, basic nickel carbonate one or more, silicon source can adopt in Ludox, sodium metasilicate one or more.Titanium source can adopt in Titanium Nitrate, titanium sulfate, titanium chloride etc. one or more, zirconium source can adopt in zirconium nitrate, zirconium chloride, zirconium oxychloride etc. one or more.Containing Al in described sodium metaaluminate alkaline solution B ₂o ₃concentration is 10 ~ 40g/L solution.

The heavy charge scope that catalyst prepared by the inventive method is suitable for is very wide, they comprise vacuum gas oil (VGO), coker gas oil, deasphalted oil, thermal cracking gas oil, catalytic gas oil, the various hydrocarbon ils of catalytic cracking circulation wet goods, also can combinationally use, raw material is the hydro carbons of 250 ~ 550 DEG C usually containing boiling point, and nitrogen content can at 50 ~ 2500 μ g/g.

The catalyst prepared of the inventive method preferably at single hop once by carrying out under hydrocracking condition.Reaction temperature is 300 ~ 500 DEG C, is more preferably 350 ~ 450 DEG C; Pressure is 6 ~ 20MPa, is more preferably 13 ~ 17MPa; During liquid, volume space velocity is 0.5 ~ 3 hr ^-1, preferably 0.8 ~ 1.5 hr ^-1; Hydrogen to oil volume ratio is 400 ~ 2000:1, preferably 800 ~ 1500:1.

The solution of the present invention and effect is further illustrated below by embodiment.Wt% is mass fraction, and v% is volume fraction.In the present invention, the specific area of product and pore structure adopt low temperature liquid nitrogen determination of adsorption method, and intensity adopts side pressure method to measure.

Embodiment 1

Concrete preparation process is as follows:

(1) acid solution A is prepared: configuration is the nickel chloride solution 200 milliliters of 140g/l containing NiO, containing WO ₃the ammonium metatungstate of 85g/l 1000 milliliters, containing ZrO ₂140g/l zirconyl chloride solution 150 milliliters, and be mixed in the container of 5 liters, add 800 milliliters of water purification dilutions.Preparation is containing SiO ₂rare water glass solution of 75g/l 550 milliliters, adds in mixing salt solution above under agitation;

(2) alkaline solution B is configured: configuration is containing Al ₂o ₃concentration is 27g/l alkalescence sodium aluminate solution 3000ml;

(3) by solution A, solution B and CO ₂gas stream adds plastic in plastic cans, gelling temperature remains on 50 DEG C, and pH value is 7.5.Wherein CO used ₂gas concentration is 45v%, adds CO ₂al in the total amount of gas and alkaline solution ₂o ₃mol ratio 3, adjustment A, B solution flow velocity, ensure to drip off simultaneously, constant to ensure that catalyst distribution evenly forms;

(4) after cemented into bundles, when constantly stirring, add the Y zeolite suspension (preparing by CN96119840.0 embodiment 3) accounting for total catalyst weight 18wt% through hydrothermal treatment consists modification, Y zeolite character is in table 4, in make it be dispersed in mixed serum that plastic obtains, leave standstill aging 2 hours at about 70 DEG C;

(5) filter, 60 DEG C of dryings 6 hours, roll, with the orifice plate extruded moulding of diameter 3 millimeters.Wash with water purification under room temperature.Then 110 DEG C of dryings 8 hours, 500 DEG C of roastings 4 hours, obtain catalyst A.Catalyst composition and main character are in table 1.

Embodiment 2

According to the method for embodiment 1, by the constituent content proportioning of the catalyst B in table 1, Kaolinite Preparation of Catalyst B, is just transferred to 58 DEG C by gelling temperature, and with adjusting hole structure, catalyst composition and main character are in table 1.

Embodiment 3

According to the method for embodiment 2, by the constituent content proportioning of the catalyst C in table 1, Kaolinite Preparation of Catalyst C, just changes zirconium oxychloride into titanium tetrachloride.Catalyst composition and main character are in table 1.

Embodiment 4

According to the method for embodiment 2, by the constituent content proportioning of the catalyst D in table 1, Kaolinite Preparation of Catalyst D, just by CO in plastic ₂consumption changes into and the Al in alkaline solution ₂o ₃mol ratio is 5.Catalyst composition and main character are in table 1.

Comparative example 1

According to method preparation disclosed in CN101239324A, catalyst composition forms identical with embodiment 1, and concrete steps are as follows:

(1) preparation is containing Al ₂o ₃concentration is the liquor alumini chloridi 900 milliliters of 90g/l, is the nickel chloride solution 200 milliliters of 140g/l, containing ZrO containing NiO ₂140g/l zirconyl chloride solution 150 milliliters, and be mixed in the container of 5 liters, add 2000 milliliters of water purification dilutions.

(2) rare water glass solution is prepared, containing SiO ₂(2) are added in (1) by the water glass solution of 75g/l 550 milliliters under agitation;

(3) ammoniacal liquor is added under agitation the mixture of (1) and (2) until pH value 5.2;

(4) sodium tungstate solution 1000 milliliters is prepared, containing WO ₃for 85g/l, and join in the mixture of (1)+(2)+(3) under agitation;

(5) continue to add ammoniacal liquor until pH value is 7.8;

(6) whole plastic process should be carried out at 60 DEG C;

(7) mixture leaves standstill aging 4 hours at 70 DEG C; Add the Y zeolite suspension that molecular sieve is prepared with CN96119840.0 embodiment 3 before aging, Y zeolite accounts for 18% of total catalyst weight, and character is in table 4.

(8) filter, 60 DEG C of oven dryings 6 hours, roll, with the orifice plate extruded moulding of diameter 3 millimeters; Wash with the ammonium acetate solution of pH=8.8 under room temperature; Then 110 DEG C of oven dryings 8 hours, 500 DEG C of roastings 4 hours, obtain reference agent E, composition and main character are in table 1.

Comparative example 2

According to method preparation disclosed in CN101172261A, catalyst composition forms identical with embodiment 1, and add molecular sieve after cemented into bundles, concrete steps are as follows:

(1) acid solution A is prepared: configuration is the nickel chloride solution 200 milliliters of 140g/l containing NiO, containing WO ₃the ammonium metatungstate of 85g/l 1000 milliliters, containing ZrO ₂140g/l zirconyl chloride solution 150 milliliters, and be mixed in the container of 5 liters, add 1100 milliliters of water purification dilutions.Preparation is containing SiO ₂rare water glass solution of 75g/l 550 milliliters, adds in mixing salt solution above under agitation.

(2) alkaline solution B is configured: configuration is containing Al ₂o ₃concentration is 27g/l alkalescence sodium aluminate solution 3000ml.

(3) by solution A, solution B drip enters plastic in plastic cans, gelling temperature remains on 60 DEG C, and pH value is in 6.5 ~ 8.5 scopes.Solution A, solution B will ensure to drip off simultaneously, constant to ensure that catalyst distribution evenly forms.

(4) after cemented into bundles, when constantly stirring, add the Y zeolite suspension prepared with CN96119840.0 embodiment 3, Y zeolite accounts for total catalyst weight 18wt%, character is in table 4, in make it be dispersed in mixed serum that plastic obtains, leave standstill aging 4 hours at about 70 DEG C.

(5) filter, 60 DEG C of dryings 6 hours, roll, with the orifice plate extruded moulding of diameter 3 millimeters.Wash with water purification under room temperature.Then 110 DEG C of dryings 8 hours, 500 DEG C of roastings 4 hours, obtain reference agent F, and composition and main character are in table 1.

Embodiment 5

Middle oil type hydrocracking catalyst A, B, D of the present invention and reference catalyst E, F evaluation result on midget plant are compared.Evaluation raw material is Iranian VGO heavy distillate, and its main character is in table 2, and table 3 lists evaluation result.

As can be seen from catalyst preparation process, prepare metalliferous material bad adhesion in reference agent F plastic process, leaf grass cannot be shaping, have to cylinder shaping, material particles is large, intensity difference.Can find out that catalyst A, catalyst B, the activity of catalyst D and the middle distillates oil selectivity adopting the present invention to prepare all slightly is better than reference agent E and F from the data of table 3.

Table 1 catalyst composition and character

Catalyst is numbered	A	B	C	D	E	F
							Catalyst forms
NiO， wt%	10	9	11	12	10	10
							WO 3，wt%	22	24	23	25	22	22
SiO 2，wt%	28	29	30	26	28	28
							Al 2O 3，wt%	33	32	31	37	33	33
Other/wt%	ZrO 2/7.0	ZrO 2/6.0	TiO 2/6.0	-	ZrO 2/7.0	ZrO 2/7.0
							The content of Y molecular sieve in catalyst, wt%	18	15	13	20	18	18
Shape	Clover	Clover	Clover	Clover	Clover	Cylinder
							Catalyst property
Specific area, m 2/g	260	275	288	279	185	157
							Pore volume, mL/g	0.340	0.350	0.355	0.365	0.212	0.197
Intensity, N/mm	20.6	21.4	22.6	23.1	18.7	13.5

Table 2 feedstock oil main character

Project	Analysis result
		Density (20 DEG C), g/cm 3	0.9113
Boiling range scope, DEG C	314-539
		S，μg/g	9800
N，μg/g	1710
		Carbon residue, wt%	0.14
Condensation point, DEG C	34
		Cetane number	43.9

Table 3 evaluating catalyst result

Catalyst is numbered	A	B	D	E	F
						Reaction temperature, DEG C	393	392	394	399	397
Product slates, wt%
						-light naphthar (C 5~82℃）	5.5	5.4	5.4	5.7	5.9
-heavy naphtha (82 ~ 138 DEG C)	11.1	11.3	11.4	11.9	11.5
						-jet fuel (138 DEG C ~ 249 DEG C)	27.5	27.4	27.2	27.0	26.7
-diesel oil (249 DEG C ~ 371 DEG C)	25.4	26.6	26.1	24.0	25.7
						-tail oil (> 371 DEG C)	29.8	28.7	29.2	30.2	29.2
C 5 +Liquid is received, wt%	99.3	99.4	99.3	98.8	99.0
						Chemical hydrogen consumption, wt%	2.41	2.39	2.40	2.37	2.40
Middle distillates oil selectivity, wt%	76.2	76.3	76.0	74.3	75. 1

The character of the modified molecular screen that table 4 the present invention relates to

Molecular sieve character	Y
		Relative crystallinity, %	95
Cell parameter, nm	2.439
		SiO 2/Al 2O 3，mol/mol	12.05
Specific area, m 2/g	839
		Pore volume, ml/g	0.506
1.7 ~ 10nm secondary pore accounts for total pore volume, %	48.0
		Infrared total acid, mmol/g	0.999
Na 2O，wt%	0.093

Claims (10)

1. the preparation method of a hydrocracking catalyst, described hydrocracking catalyst comprises amorphous aluminum silicide, Y zeolite, hydrogenation active metals component, wherein hydrogenation active metals component is group vib metal and group VIII metal, preparation process is as follows: preparation contains the acidic mixed solution A of hydrogenation active metals and silicon, preparation sodium metaaluminate alkaline solution B, then acidic mixed solution A, alkaline solution B and gas CO ₂and stream add water purification is housed retort in plastic, plastic pH value controls 6.5 ~ 8.5; Then the suspension adding Y zeolite mixes, and the mixture of gained filters, the filter cake drying obtained, then obtains hydrocracking catalyst through shaping, washing, drying, roasting; Wherein, CO is added ₂al in the total amount of gas and alkaline solution B ₂o ₃mol ratio be 2 ~ 8; Described acidic mixed solution A, alkaline solution B and gas CO ₂and flow in plastic process that to control gelling temperature be 40 ~ 70 DEG C, control gelation time at 0.5 ~ 3.0 hour;

The character of Y zeolite used is as follows: the pore volume that bore dia is greater than 1.7nm accounts for more than 45% of total pore volume, and specific area is 750 ~ 900m ²/ g, cell parameter is at 2.423nm ~ 2.545nm, and relative crystallinity is 95% ~ 110%, SiO ₂/ Al ₂o ₃mol ratio is 7 ~ 60.

2. in accordance with the method for claim 1, it is characterized in that CO used ₂the volumetric concentration of gas is 30% ~ 60%.

3. in accordance with the method for claim 1, it is characterized in that in described hydrocracking catalyst, with the weight of catalyst for benchmark, the content of group VIB metal oxide is 10wt% ~ 50wt%, the content of group VIII metal oxide is 1wt% ~ 20wt%, the content of Y zeolite is 10wt% ~ 40wt%, and the content of amorphous aluminum silicide is 30wt% ~ 60wt%.

4., according to the method described in claim 1 or 3, it is characterized in that in described hydrocracking catalyst, group vib metal is W and/or Mo, group VIII metal is Co and/or Ni.

5. in accordance with the method for claim 4, it is characterized in that adjuvant component is IVB race metal, and the content of IVB family metal oxide in hydrocracking catalyst is 1wt% ~ 10wt% containing adjuvant component in described hydrocracking catalyst.

6. in accordance with the method for claim 5, it is characterized in that described IVB race metal is Ti and/or Zr.

7. in accordance with the method for claim 4, it is characterized in that containing in the process of the acidic mixed solution A of hydrogenation active metals and silicon in preparation, hydrogenation active metals adopts water soluble compound soluble in water formulated, wherein tungsten source adopts one or more in ammonium metatungstate, sodium tungstate, molybdenum source adopts molybdenum trioxide, one or more in ammonium molybdate, cobalt source adopts cobalt nitrate, and nickel source adopts nickel nitrate, nickel chloride, one or more in basic nickel carbonate; Silicon source adopts Ludox, one or more in sodium metasilicate.

8. in accordance with the method for claim 7, it is characterized in that containing in the process of the acidic mixed solution A of hydrogenation active metals and silicon in preparation, add titanium source and/or zirconium source, titanium source adopts Titanium Nitrate, titanium sulfate, one or more in titanium chloride, zirconium source adopt in zirconium nitrate, zirconium chloride, zirconium oxychloride one or more.

9. in accordance with the method for claim 1, it is characterized in that in described sodium metaaluminate alkaline solution B containing Al ₂o ₃concentration is 10 ~ 40g/L solution.

10. in accordance with the method for claim 1, it is characterized in that, the drying condition before shaping of catalyst is as follows: drying 2 ~ 10 hours at 100 ~ 150 DEG C; Drying condition after shaping of catalyst is as follows: at 100 ~ 150 DEG C dry 2 ~ 10 hours, and described roasting is roasting 3 ~ 10 hours at 450 ~ 650 DEG C.