CN106179466B - The preparation method of hydrocracking catalyst - Google Patents

Abstract

The invention discloses a kind of preparation methods of hydrocracking catalyst.The catalyst is body phase hydrocracking catalyst, it includes hydrogenation active metal component W and Ni that it, which is formed, aluminium oxide, silica and molecular sieve, preparation method is to prepare nickeliferous, aluminum precipitation object slurries I using the acid precipitation method, prepares tungstenic, silicon, aluminum precipitation object slurries II, aging after the two mixing using parallel flow precipitation, urea is added simultaneously in steam treatment, be beaten again be added molecular sieve suspension, after then being impregnated with organic compound, through molding and etc. catalyst is made.The catalyst is especially suitable in single-stage hydrocracking technical process, having many advantages, such as liquid yield height, good product quality.

Description

The preparation method of hydrocracking catalyst

Technical field

The present invention relates to a kind of preparation methods of the hydrocracking catalyst for the treatment of of heavy hydrocarbon class.

Background technique

Currently, worldwide petroleum resources are insufficient, crude quality is deteriorated year by year, and intermediate oil demand increases, Petroleum chemicals upgrading and environmental regulation are more and more stringent, heavy oil lighting are greatly facilitated, and constitute accelerated development The very strong driving force of hydrogen addition technology.Be mainly characterized by adaptability to raw material strong, the products scheme, the selection of purpose product of hydrocracking technology Property high, good product quality and added value it is high, can directly produce a variety of high-quality oil product (such as gasoline, jet fuel, diesel oil, profits Lubricant base oil etc.) and high-quality industrial chemicals (such as benzene,toluene,xylene, ethylene production raw material).

The petroleum refining industry of 21st century must comply with the strategy of sustainable development, it is necessary to while paying attention to economic benefit, protection Environment and the principle to economize on resources.Therefore, become more important using the preparation method production bulk phase catalyst of non-environmental-pollution. Existing coprecipitation method prepares catalyst technology, uses NH mostly₃·H₂For O as precipitating reagent, this will generate the largely waste water containing ammonia, nitrogen, It pollutes the environment.

It is hydrocracked and carries out at elevated pressures, hydrocarbon molecules and hydrogen carry out cracking and adding hydrogen in catalyst surface Reaction generates the conversion process of lighter molecule, while the hydrogenation reaction of hydrodesulfurization, denitrogenation and unsaturated hydrocarbons also occurs.Hydro carbons exists Cracking reaction in hydrocracking process is carried out on the acid centre of catalyst, it then follows carbon ion reaction mechanism, add hydrogen, With the generation of hydro carbons isomerization reaction while cracking reaction.Hydrocracking catalyst is made of hydrogenation component and acidic components , the two is added by a certain percentage as needed, makes that hydrogen and cracking performance is added to reach balance, effect is that hydrocarbon mixture is abundant Add hydrogen, cracking and isomerization orientation reaction.Therefore, the catalyst that distillate hydrocracking process needs should have stronger plus hydrogen There is moderate acid centre in activated centre again.

In general, following method can be used to prepare for hydrocracking catalyst, such as: infusion process, kneading method, beating method, altogether The precipitation method may use ion-exchange for noble metal.Infusion process and kneading method are all made of first by carrier and acidic components Add metal again afterwards, and coprecipitated rule is that acidic components and metal coprecipitation get off, and metal loading is unrestricted.It is such The hydrogenation sites of catalyst be on the catalyst channel surfaces that reactant molecule can approach, and coprecipitation method preparation urge Agent active metal is not fully present in catalyst channel surfaces, and amount of activated metal is present in caltalyst phase, coprecipitated The tenor that method prepares catalyst table phase decides catalyst activity.

US6299760, US6156695, US6537442, US6440888, US6652738 disclose containing group VIII/ VI B race active metal component is used for the bulk phase catalyst and preparation method thereof of hydrotreating.Catalyst metal content can reach 50wt%~100wt%.Active metal component can be Ni-Mo or Ni-Mo-W.Above-mentioned catalyst is prepared using coprecipitation method.US Hydrocracking catalyst disclosed in 3954671, hydrogenation conversion catalyst disclosed in US 4313817 are resistance to disclosed in CN1253988A The hydrocracking catalyst of nitrogen type fecund intermediate oil, heavy hydrocarbons hydrocraking catalyst disclosed in CN1253989A, this A little catalyst are prepared using coprecipitation method, since the deposition condition of different hydrogenation active metals is different, cause different plus hydrogen The distribution of active metal is not easily controlled, thus influence between the distribution and different activities metal of different hydrogenation active metals and Interaction relationship between active metal and carrier, thus prevent hydrogenation activity with cracking activity from being cooperated well, Meanwhile these caltalyst phase active metallic contents are more, table phase active metallic content is relatively fewer, hydrogenation sites density Smaller, final influence catalyst is hydrocracked performance.High activity, High middle distillate disclosed in CN101239324A, which are hydrocracked, urges Agent is the addition precipitating reagent alkalescent ammoniac compounds into the slurries that amorphous silica-alumina, auxiliary agent and active metal are made into, and is carried out Then precipitation reaction is added molecular sieve suspension and is made.This method is also to be prepared using coprecipitation method, however it remains table is mutually lived Property tenor it is relatively fewer, hydrogenation sites density is smaller, and different hydrogenation active metals are unevenly distributed, hydrogenation activity gold Belong to and interactively coordinates bad problem between carrier.

CN103055923A discloses a kind of preparation method of hydrocracking catalyst.Using acid containing hydrogenation active metals Solution, sodium metaaluminate alkaline solution and gas CO₂Plastic in the reactor tank equipped with water purification is added in cocurrent；Then Y type molecule is added The suspension of sieve is uniformly mixed, and hydrocracking catalyst is made through filtering, drying, molding, then washed, dry, roasting.The party Method increases Kong Rong, the specific surface area of catalyst, makes using the releasing of gas in roasting process under the percussion of gas More metal active positions are exposed to the surface of catalyst, but such method can make cell channels collapse, pore size distribution disperse, mechanical Strength reduction, and lead to active metal localized clusters, the metal active position being exposed is limited.

Coprecipitation method prepares catalyst technology, can be to duct table in catalyst using different coprecipitation modes, Gelation Conditions etc. On face between active metallic content and activated centre density, the distribution of different hydrogenation active metals and difference hydrogenation active metals Interaction relationship between hydrogenation active metals and carrier has a great impact.The coprecipitation method of above-mentioned use can make different plus hydrogen The distribution of active metal is not easily controlled, thus influence different hydrogenation active metals distribution and different hydrogenation active metals it Between interaction relationship between active metal and carrier, to prevent hydrogenation activity with cracking activity from being matched well It closes, meanwhile, table phase active metallic content is smaller in catalyst and activated centre density is lower, and final influence catalyst adds hydrogen to split Change performance.Therefore, the distribution for how regulating and controlling hydrogenation active metals, makes between hydrogenation active metal component and hydrogenation active metals There is suitable mating reaction between component and carrier, it is close how to increase table phase active metallic content and activated centre in catalyst Degree, improves the utilization rate of hydrogenation active metal component, is the key that improve coprecipitation method to prepare hydrocracking catalyst Hydrogenation.

Summary of the invention

In view of the deficiencies of the prior art, the present invention provides a kind of preparation methods of body phase hydrocracking catalyst.The party Method improves the distribution of hydrogenation active metals in catalyst, improves the cooperation between hydrogenation active metals and between carrier and makees With, catalyst surface active bit density is improved, improves the utilization rate of hydrogenation active metals, while catalyst pore structure is reasonable, it is living Property metal dispersion more evenly, makes catalyst service performance with higher.

The preparation method of hydrocracking catalyst of the present invention, comprising:

(1), sodium metaaluminate alkaline solution is added dropwise to solution A and carries out plastic reaction by the solution A for preparing the component containing Ni, raw At nickeliferous, aluminum precipitation object slurries I；

(2), the mixed solution B containing W, Si component is prepared, it is anti-that sodium metaaluminate alkaline solution and solution B cocurrent are carried out plastic It answers, generates tungstenic, silicon, aluminum precipitation object slurries II；

(3), the resulting slurries I of step (1) and the resulting slurries II of step (2) is uniformly mixed, under agitation always Change, after aging, filtering, obtained material carries out hydro-thermal process with water vapour, urea is wherein added when hydro-thermal process；

(4), step (3) obtained material is beaten uniformly, and the suspension of molecular sieve is added under stirring condition, and stirring is equal Even, organic compound immersion is added after obtaining material washing in filtering, then through drying, molding；

(5), hydrocracking catalyst is made through dry and roasting in step (4) resulting material.

The preferred Y type molecular sieve of molecular sieve be added in the method for the present invention.Y type molecular sieve is usually with molecular sieve suspension Form is added, i.e., molecular sieve is ground to 80 mesh ~ 140 mesh, preferably 100 mesh ~ 120 mesh, then plus suspension is made in water.Described Y type molecular sieve is Y type molecular sieve used in conventional hydrocracking catalyst.

In hydrocracking catalyst of the present invention, on the basis of the weight of catalyst, WO₃With the total content of NiO be 20%~ 65%, preferably 30%~50%, W/Ni atomic ratio is 0.05~1.0, preferably 0.1~0.7, the content of silica is 1%~ 40%, preferably 5%~35%, the content of aluminium oxide is 10%~40%, preferably 15%~40%, the content of molecular sieve be 5wt%~ 20wt%, preferably 5wt%~15wt%.

In step (1) mixed solution A, weight concentration of the Ni in terms of NiO is 5~80g/L, preferably 10~60g/L.It is described Sodium metaaluminate alkaline solution in contain Al₂O₃Concentration is 5 ~ 70g/L, preferably 5 ~ 50g/L.When preparing mixed solution A, generally The nickel source used can be one or more of nickel sulfate, nickel nitrate, basic nickel carbonate, nickel chloride.

In step (2) mixed solution B, W is with WO₃The weight concentration of meter is 10~100g/L, preferably 20~90g/L.Si With SiO₂Weight concentration is 10~120g/L, preferably 20~80g/L.Contain Al in the sodium aluminate solution₂O₃Concentration is 5 ~ 60g/L, preferably 5 ~ 40g/L.When preparing mixed solution B, the tungsten source generally used can be ethyl ammonium metatungstate, metatungstic acid One or more of ammonium；Silicon source can be one of silica solution, sodium metasilicate or a variety of.

Reaction temperature is 20~90 DEG C, preferably 30~70 DEG C in step (1).When cemented into bundles pH value control for 6.0 ~ 11.0, preferably 7.0 ~ 9.0.Gelation time is 0.2 ~ 4.0 hour, preferably 0.5 ~ 3.0 hour.

Weight content of Si, the Al introduced in step (2) in terms of oxide in the catalyst is 5wt%~70wt%, preferably 10wt%~90wt% of the total weight of Si, Al in terms of oxide is accounted in terms of silica for 10wt%~55wt%, active wherein Si, compared with It is well 30wt%~80wt%；Weight content of the Al introduced in step (1) in terms of oxide in the catalyst for 5wt%~ 45wt%, preferably 10wt%~30wt%.

Reaction temperature is 30~90 DEG C, preferably 40~80 DEG C in step (2).When cocurrent plastic pH value control for 6.0 ~ 11.0, preferably 7.0 ~ 9.0.Gelation time is 0.2 ~ 4.0 hour, preferably 0.5 ~ 3.0 hour.

Gelling temperature and time can be the same or different in step (1) and step (2).Step (1) and step (2) can Can also be different when progress simultaneously.

Aging temperature is 40~90 DEG C, preferably 50~80 DEG C in step (3).PH value control is 6.0 ~ 10.0 when aging, Preferably 6.5 ~ 9.0.Ageing time is 0.5 ~ 6.0 hour, preferably 1.0 ~ 4.0 hours.

Hydrothermal conditions described in step (3) are as follows: carrying out under closed container, temperature is 200 ~ 300 DEG C, excellent 210 ~ 260 DEG C are selected as, pressure is 1.0 ~ 8.0MPa, preferably 3.0 ~ 6.0MPa, and the processing time is 0.5 ~ 10.0 hour, preferably 1.0 ~ 6.0 hours.

In step (3), when hydro-thermal process, active metal (tungsten, nickel) atom total amount in the additional amount and catalyst of urea Molar ratio is 0.5:1 ~ 10.0:1, preferably 2.0:1 ~ 8.0:1.

Step (4) organic compound is selected from oxygen-containing or nitrogenous one or more of organic compound, wherein containing Oxygen organic compound is preferably one or more of Organic Alcohol and organic acid, such as: ethylene glycol, glycerine, diethylene glycol, fourth One of glycol, aminotriacetic acid, xylitol, butantriol, pentanediol etc. are a variety of, the preferred organic amine of organic compounds containing nitrogen One or more of, such as: hexa, ethylenediamine tetra-acetic acid (EDTA), benzylamine, methyl diethanolamine, N- methyl Diethanol amine, ethanol amine, n-butylamine, cyclohexylamine, phenyl ethylamine, phenylpropanolamine, triethylenediamine (TEDA), diethylenetriamines (DETA), one of methyl diethanolamine (MDEA), isobutyl amine etc. or a variety of.The organic compound in terms of oxide The molar ratio of the sum of active metal nickel and tungsten is 0.1 ~ 3.0, preferably 0.3 ~ 2.0.Liquid solid when being impregnated with organic compound For product than being 1.0 ~ 3.0, preferably 1.0 ~ 2.0, soaking time is 0.5~12 hour, preferably 2~10 hours.

Drying described in step (4), molding can be carried out using conventional method in that art.The drying generally 50 ~ 200 DEG C drying 1 ~ 48 hour.In forming process, it can according to need and conventional shaping assistant, such as peptizing agent, extrusion aid is added Deng one of or it is a variety of.The peptizing agent is one or more in hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid etc., described Extrusion aid refers to one or more of the substance for being conducive to extrusion forming, such as sesbania powder, carbon black, graphite powder, citric acid, helps The dosage of agent accounts for 1wt%~10wt% of total material butt.Washing is usually used deionized water or containing decomposable salt (such as vinegar Sour ammonium, ammonium chloride, ammonium nitrate etc.) solution washing, it is washed till neutrality.The molding, the shape of catalyst can according to need as piece Shape, spherical, cylindrical bars and irregular bar (clover, bunge bedstraw herb), preferably cylindrical bars and irregular bar (clover, bunge bedstraw herb).It carries The diameter of body can be the slice of 0.8 ~ 2.0mm and the thick item of > 2.5mm.

Drying described in step (5) and roasting can use this field normal condition, such as small in 50 ~ 200 DEG C of dryings 1 ~ 48 When, it is roasted 1 ~ 24 hour, preferably 2 ~ 8 hours at 450 ~ 600 DEG C.

In hydrocracking catalyst of the present invention, adjuvant component can also be contained, the adjuvant component is the IVth B race metal, Content of the IVth B family metal oxide in hydrocracking catalyst is 1wt%~10wt%.IVth B race metal is preferably Ti and/or Zr.In hydrocracking catalyst preparation process of the present invention, group containing auxiliary agent is added during preparing mixed solution A The compound divided, i.e. titanium source and/or zirconium source.One of Titanium Nitrate, titanium sulfate, titanium chloride etc. or a variety of, zirconium can be used in titanium source One of zirconium nitrate, zirconium chloride, zirconium oxychloride etc. or a variety of can be used in source.

In hydrocracking catalyst of the present invention, all in the prior art can be used for plus hydrogen is can be used in Y type molecular sieve used Y type molecular sieve in Cracking catalyst, such as: CN101343068A, CN1508228A, CN101450319A, CN 1209357A Disclosed in Y type molecular sieve.Y type molecular sieve disclosed in the preferred CN101343068A of the present invention, property are as follows: comparing table Area is 700m²/ g~950m²/ g, preferably 800~950m²/ g, total pore volume is 0.30mL/g~0.55mL/g, opposite to crystallize Degree is 90%~130%, SiO₂/Al₂O₃Molar ratio is 30~150, preferably 50~150, and cell parameter is 2.425~2.445nm, Meleic acid amount is 0.1~1.0mmol/g, and B Suan ∕ L acid is 7.0 or more, preferably 8.0 or more, sodium oxide content≤0.05wt%, Preferably≤0.01wt%.

The hydrocracking catalyst of the method for the present invention preparation is body phase hydrocracking catalyst, and composition includes hydrogenation activity Metal component W and Ni, aluminium oxide, silica and molecular sieve；Wherein table phase active metal component WO₃Weight content mutually live with body Property metal component WO₃Weight content ratio be 1.2:1 ~ 6.0:1, preferably 1.8:1 ~ 4.5:1, table phase active metal component The ratio of the weight content of NiO and the weight content of body phase active metal component NiO is 1.2:1 ~ 5.0:1, preferably 1.5 ~ 3.5: 1。

In the present invention, table phase active metal component WO₃Weight content be table phase in WO₃Weight content, body mutually activity gold Belong to component WO₃Weight content be catalyst in WO₃Weight content；The weight content of table phase active metal component NiO is table phase The weight content of middle NiO, the weight content of body phase active metal component NiO are the weight content of NiO in catalyst.

The property of the hydrocracking catalyst of the method for the present invention preparation is as follows: specific surface area is 250~650m²/ g, Kong Rong For 0.35~0.80mL/g, pore-size distribution is as follows: diameter is that Kong Rong shared by the hole below 4nm accounts for the 1% ~ 20% of total pore volume, directly It is 55% ~ 80% that Kong Rong shared by hole of the diameter for 4 ~ 8nm, which accounts for total pore volume, and diameter is that Kong Rong shared by the hole of 8 ~ 15nm accounts for total pore volume 2% ~ 20%, it is 0.1% ~ 5.0% that the Kong Rong that diameter is 15nm or more, which accounts for total pore volume, and preferred pore-size distribution is as follows: diameter 4nm Kong Rong shared by hole below accounts for the 5% ~ 17% of total pore volume, diameter be Kong Rong shared by the hole of 4 ~ 8nm account for total pore volume be 61% ~ 75%, diameter is that Kong Rong shared by the hole of 8 ~ 15nm accounts for the 4% ~ 17% of total pore volume, and diameter is that the Kong Rong of 15nm or more accounts for total pore volume It is 0.5% ~ 5.0%.

In hydrocracking catalyst of the present invention, adjuvant component can also be contained, the adjuvant component is the IVth B race metal, Content of the IVth B family metal oxide in hydrocracking catalyst is 1wt%~10wt%.IVth B race metal is preferably Ti and/or Zr.

Hydrocracking catalyst of the present invention is the body phase hydrocracking catalyst of oxidation state, and conventional side can be used before use Method carries out presulfurization.

The heavy charge range that the catalyst of the method for the present invention preparation is applicable is very wide, they include vacuum gas oil (VGO), coking The various hydrocarbon ils such as gas oil, deasphalted oil, thermal cracking gas oil, catalytic gas oil, catalytic cracking recycle oil, can also group It closes and uses, the hydro carbons that raw material is usually 250~550 DEG C containing boiling point, nitrogen content can be in 50~2500 μ g/g.

Using positive addition, (the acid precipitation method, that is, alkaline precipitating agent is added in acid metal salt solution and carries out the method for the present invention Precipitating) nickel aluminium mixed sediment is prepared, tungsten, silicon and aluminium mixed sediment are prepared using parallel flow precipitation, then after the two is mixed Aging, after adding organic compound mashing, molding is prepared into hydrocracking catalyst.The present invention is prepared by using positive addition The relatively large nickel of crystal grain, aluminum precipitation object, cocurrent process prepare the relatively small tungsten of crystal grain, silicon and aluminum precipitation object, will be above two heavy Starch mixing, can control the distribution of different hydrogenation active metals, be conducive to form high activity phase between active metal tungsten, nickel, and Improve the interaction between active metal and carrier, obtains the hydrogenation activity of resulting hydrocracking catalyst with cracking activity Good cooperation improves the service performance of hydrocracking catalyst.

In the preparation method of catalyst of the present invention, steam treatment is simultaneously under appropriate conditions for the material obtained after co-precipitation Urea is added, urea is decomposed into NH under high temperature environment₃And CO₂, NH₃And CO₂NH is generated in the presence of water vapour₄ ⁺With HCO₃ ^-Ion, NH₄ ⁺And HCO₃ ^-Ion at high temperature under high pressure has a significant impact the micromorphology of material, material before hydro-thermal process Phase structure is in cylinder, and material phase structure is changed into the irregular body that irregular sheet is piled into from cylinder after hydro-thermal process, this The transformation of structure obviously increases distribution of the active metal in table phase, and disperses more evenly, and it is living to be conducive to raising surface The density of property position.In addition, urea is added in steam treatment, make the transformation of material form that can also make the pore size distribution of catalyst It is more uniform, be conducive to the mechanical strength for improving catalyst.

In the preparation method of catalyst of the present invention, obtained filter cake is added the solution containing organic compound and impregnates, and can control The distribution of different hydrogenation active metals, enhances the interaction in table phase between W, Ni, Mo active metal, improves in phase of tabulating The hydrogenation activity of catalyst.

In the preparation method of catalyst of the present invention, the sodium metaaluminate alkaline solution containing Al is used to avoid use for precipitating reagent NH₃·H₂O generates the largely waste water containing ammonia, nitrogen, simultaneous reactions precipitate particles are uniform, are more advantageous in W, Ni as precipitating reagent Active metal is distributed in table phase, and W, Ni active metal be distributed in table phase it is more uniform, be conducive to improve body be mutually catalyzed The hydrogenation activity of agent.

In catalyst of the present invention, different hydrogenation active metals have good distribution, and surface-active bit density is big, activity Intermetallic cooperation is good, and active metal utilization rate is high, and improves the interaction between active metal and carrier, makes resulting The hydrogenation activity and cracking activity of hydrocracking catalyst obtain good cooperation, while catalyst pore structure is reasonable, mechanical strong Degree is high, has excellent hydrogenation cracking activity.

The present invention adds hydrogen particularly suitable as High middle distillate using hydrocracking catalyst made of preferred Y type molecular sieve Cracking catalyst not only has high hydrogenation cracking activity, but also has high middle distillates oil selectivity, while also having relatively strong resistance to nitrogen ability Etc. good service performance.Catalyst of the present invention is suitable for single hop and once passes through in hydrocracking process, hydrocracking operation Condition is as follows: reaction temperature is 300~500 DEG C, more preferably 350~450 DEG C；Pressure be 6~20MPa, more preferably 13~ 17MPa；Volume space velocity is 0.5~3 h when liquid^-1, preferably 0.8~1.5 h^-1；Hydrogen to oil volume ratio is 400~2000:1, best It is 800~1500:1.The catalyst is in single-stage hydrocracking technical process, having liquid yield height, good product quality etc. Advantage.

Specific embodiment

In the present invention, specific surface area and Kong Rong use low temperature liquid nitrogen physisorphtion, and relative crystallinity and cell parameter are adopted With x-ray diffraction method, silica alumina ratio uses chemical method, and sodium content uses plasma emission spectrometry, and mutually activity is golden for catalyst table Belong to content to measure using x-ray photoelectron spectroscopy (XPS), caltalyst phase active metallic content uses inductively coupled plasma Body atomic emission spectrum (ICP-AES) measurement, transmission electron microscope (TEM) measure catalyst surface WS₂Density.Mechanical strength is to use The measurement of side pressure method.In the present invention, wt% is mass fraction, and v% is volume fraction.

Embodiment 1

Nickel chloride and zirconium oxychloride are dissolved in water purification respectively, are configured to mixed solution A, the weight concentration of NiO is in solution A 21g/L, ZrO₂Weight concentration 5g/L.Ammonium metatungstate is dissolved in water purification, dilute water glass solution is added, is configured to mixed solution B, WO in solution B₃Weight concentration be 25g/L, SiO₂Weight concentration be 20g/L.Al will be contained₂O₃The sodium metaaluminate of 10g/L 600 milliliters of solution are added solution A under stiring, and gelling temperature is maintained at 55 DEG C, at the end of pH value control 7.6, gelation time Control generated nickeliferous, aluminum precipitation object slurries I at 60 minutes.1000mL water purification is added in reactor tank, Al will be contained₂O₃20g/L's 800 milliliters of sodium aluminate solution and solution B cocurrent are added in reactor tank, and gelling temperature is maintained at 55 DEG C, and cocurrent plastic was reacted 7.6, gelation time control generated tungstenic, silicon, aluminum precipitation object slurries II at 60 minutes for pH value control in journey.It will be above two Containing aging after sediment slurry mixing, ageing time 2 hours, 75 DEG C of aging temperature, pH value control was 7.6 at the end of aging, then Filtering, filter cake carry out hydro-thermal process, the condition of hydro-thermal process under the water vapour containing urea are as follows: urea and active metal atom The molar ratio of total amount is 7:1, and temperature is 230 DEG C, pressure 4.5MPa, and the processing time is 3 hours, is beaten filter cake after processing, The Y type molecular sieve suspension (in terms of butt) that addition accounts for total catalyst weight 10wt% into mix slurry (is pressed It is prepared by CN101343068A embodiment 7), Y type molecular sieve property is shown in Table 6, is dispersed in it in mixed serum, filters, and uses Water purification is washed 3 times, by filter cake and glycerin solution (the sum of active metal nickel and tungsten in glycerine and catalyst in terms of oxide Molar ratio be 1.0) impregnate 8 hours, liquid consolidate volume ratio be 1.1,100 DEG C dry 8 hours, roll, extruded moulding.At room temperature It is washed with water purification.Then 10 hours dry at 80 DEG C, 550 DEG C roast 4 hours, obtain catalyst A.Catalyst composition, pore size distribution And main character is shown in Table 1.

Embodiment 2

According to the method for embodiment 1, it is matched by the constituent content of the catalyst B in table 1, nitric acid is added into dissolving tank 1 Nickel, titanium chloride prepare working solution A, after addition ammonium metatungstate is dissolved in water purification into dissolving tank 2, dilute waterglass are added and prepares work Make solution B.Solution A is added in ammonium hydroxide under stiring, gelling temperature is maintained at 45 DEG C, at the end of pH value control at 8.0, plastic Between control at 60 minutes, generate nickeliferous, aluminum precipitation object slurries I.800mL water purification is added in reactor tank, simultaneously by ammonium hydroxide and solution B Stream is added in reactor tank, and gelling temperature is maintained at 50 DEG C, and pH value control is 8.2 in cocurrent plastic reaction process, gelation time control System generated tungstenic, silicon, aluminum precipitation object slurries II at 60 minutes.By aging after the above two mixing containing sediment slurry, ageing time 3 hours, 70 DEG C of aging temperature, at the end of aging then pH value control was filtered, filter cake is under the water vapour containing urea 8.0 Carry out hydro-thermal process, the condition of hydro-thermal process are as follows: the molar ratio of urea and active metal atom total amount is 6:1, temperature 250 DEG C, pressure 3.5MPa, the processing time is 3 hours, is beaten filter cake after processing, accounts for total catalyst weight to slurries addition The Y type molecular sieve suspension (in terms of butt) (preparing by CN101343068A embodiment 7) of 12wt%, Y type molecular sieve property is shown in Table 6, it is dispersed in it in mixed serum, filters, washed 3 times with water purification, by filter cake and butanediol solution (butanediol and catalysis The molar ratio of active metal nickel and the sum of tungsten in agent in terms of oxide is 1.5) to impregnate 8 hours, and it is 1.2 that liquid, which consolidates volume ratio, 120 DEG C drying 7 hours, roll, extruded moulding.It is washed at room temperature with water purification.Then 12 hours dry at 100 DEG C, 500 DEG C of roastings 5 hours, obtain catalyst B.Catalyst composition, pore size distribution and main character are shown in Table 1.

Embodiment 3

According to the method for embodiment 1, it is matched by the constituent content of the catalyst C in table 1, chlorination is added into dissolving tank 1 Nickel prepares working solution A, after addition ammonium metatungstate is dissolved in water purification into dissolving tank 2, dilute waterglass is added and prepares working solution B. Solution A is added in ammonium hydroxide under stiring, gelling temperature is maintained at 55 DEG C, at the end of pH value control 7.6, gelation time control exists 90 minutes, generate nickeliferous, aluminum precipitation object slurries I.It is added in reactor tank and 900mL water purification is housed, ammonium hydroxide and solution B cocurrent are added In reactor tank, gelling temperature is maintained at 45 DEG C, and pH value control is 8.0 in cocurrent plastic reaction process, and gelation time control is 60 Minute, generate tungstenic, silicon, aluminum precipitation object slurries II.It is mixed above two containing sediment slurry.Contain sediment slurry for above two Aging after mixing, ageing time 2.5 hours, 72 DEG C of aging temperature, at the end of aging then pH value control was filtered, filter cake 7.8 Hydro-thermal process, the condition of hydro-thermal process are carried out under the water vapour containing urea are as follows: urea and active metal atom total amount are rubbed You are than being 4:1, and temperature is 240 DEG C, pressure 6.0MPa, and the processing time is 4 hours, is beaten filter cake after processing, to sediment The Y type molecular sieve suspension (in terms of butt) for accounting for total catalyst weight 15wt% is added (by CN101343068A embodiment 7 in slurries Preparation), Y type molecular sieve property is shown in Table 6, is dispersed in it in mixed serum, filters, and water purification is washed 3 times, by filter cake and three Ethylene diamine (TEDA) solution (triethylenediamine in catalyst in terms of oxide active metal nickel and the sum of tungsten rub You are 10 hours dry at 70 DEG C than 0.8) to impregnate 8 hours, it is 1.2 that liquid, which consolidates volume ratio, rolls, extruded moulding.At room temperature with net Water washing.Then 8 hours dry at 80 DEG C, 530 DEG C roast 4.5 hours, obtain catalyst C.Catalyst composition, pore size distribution and master Property is wanted to be shown in Table 1.

Embodiment 4

According to the method for embodiment 1, it is matched by the constituent content of the catalyst D in table 1, chlorination is added into dissolving tank 1 Nickel preparating acid sex work solution A after addition ammonium metatungstate is dissolved in water purification into dissolving tank 2, is added dilute waterglass and prepares acid work Make solution B.Solution A is added in ammonium hydroxide under stiring, gelling temperature is maintained at 45 DEG C, at the end of pH value control at 7.6, plastic Between control at 80 minutes, generate nickeliferous, aluminum precipitation object slurries I.It is added in reactor tank and 1000mL water purification is housed, by ammonium hydroxide and solution B cocurrent is added in reactor tank, and gelling temperature is maintained at 55 DEG C, and pH value control is 8.0 in cocurrent plastic reaction process, gelation time Control generated tungstenic, silicon, aluminum precipitation object slurries II at 60 minutes.It is mixed above two containing sediment slurry.Contain above two Aging after sediment slurry mixing, ageing time 2 hours, 75 DEG C of aging temperature, pH value control was 7.8 at the end of aging, then mistake Filter, filter cake carry out hydro-thermal process, the condition of hydro-thermal process under the water vapour containing urea are as follows: urea and active metal atom are total The molar ratio of amount is 3.0:1, and temperature is 260 DEG C, pressure 5.0MPa, and the processing time is 5 hours, is beaten filter cake after processing, The Y type molecular sieve suspension (in terms of butt) for accounting for total catalyst weight 8wt% to the mixing addition of sediment slurries (is pressed It is prepared by CN101343068A embodiment 7), Y type molecular sieve property is shown in Table 6, is dispersed in it in mixed serum, filters, only Water washing 2 times, by filter cake and aminotriacetic acid (active metal nickel and tungsten in aminotriacetic acid and catalyst in terms of oxide it The molar ratio of sum is 1.0) to impregnate 9 hours, and it is 1.0 that liquid, which consolidates volume ratio, 10 hours dry at 80 DEG C, is rolled, extruded moulding.Room temperature Lower to be washed with water purification, then 10 hours dry at 110 DEG C, 480 DEG C roast 6 hours, obtain catalyst D.Catalyst composition, hole point Cloth and main character are shown in Table 1.

Comparative example 1

It is prepared according to method disclosed in CN101239324A, catalyst composition is with example 1 group at identical, and specific steps are such as Under:

(1) it prepares and contains Al₂O₃Concentration is 320 milliliters of liquor alumini chloridi of 120g/L, molten containing the nickel chloride that NiO is 44g/L 270 milliliters of liquid, contain ZrO₂50 milliliters of 100g/L zirconyl chloride solution is simultaneously mixed in the container of a 5L, is added 2000 milliliters only Water dilution；

(2) dilute water glass solution is prepared, SiO is contained₂310 milliliters of the water glass solution of 100g/L under agitation will (2) it is added in (1)；

(3) ammonium hydroxide is added to the mixture of (1) and (2) under agitation until pH value 5.2；

(4) 240 milliliters of sodium tungstate solution are prepared, WO is contained₃For 80g/L, and be added under agitation (1)+(2)+ (3) in mixture；

(5) ammonium hydroxide is continuously added until pH value is 7.6；

(6) entire plastic process should be carried out at 55 DEG C；

(7) mixture 75 DEG C standing aging 2.0 hours, at the end of aging pH value control 7.6；It is added and accounts for before aging The Y type molecular sieve suspension (in terms of butt) (being prepared by CN101343068A embodiment 7) of total catalyst weight 10wt%, Y type point Son sieve property is shown in Table 6,

(8) filter, 100 DEG C oven drying 8 hours, roll, with 3 millimeters of diameter of orifice plate extruded moulding；At room temperature It is washed with the ammonium acetate solution of pH=8.8；Then 80 DEG C oven drying 10 hours, 550 DEG C roast 4 hours, obtain reference agent E, Catalyst composition, pore size distribution and main character are shown in Table 1.

Comparative example 2

It is added without urea by 1 catalyst of embodiment composition and preparation method, when hydro-thermal process, prepares reference agent F.Catalyst Composition, pore size distribution and main character are shown in Table 1.

Comparative example 3

By 1 catalyst of embodiment composition and preparation method, when hydro-thermal process, is added without urea, but NH is added₃, NH₃And work Property metallic atom total amount molar ratio be 7:1, temperature be 230 DEG C, pressure 4.5MPa, processing the time be 3 hours, prepare reference Agent G.Catalyst composition, pore size distribution and main character are shown in Table 1.

Comparative example 4

By 1 catalyst of embodiment composition and preparation method, when hydro-thermal process, is added without urea, but CO is added₂, CO₂And work Property metallic atom total amount molar ratio be 7:1, temperature be 230 DEG C, pressure 4.5MPa, processing the time be 3 hours, prepare reference Agent H.Catalyst composition, pore size distribution and main character are shown in Table 1.

Comparative example 5

It is prepared by method disclosed in CN103055923A, catalyst composition is with example 1 group at identical, and specific steps are such as Under:

(1) it prepares acid solution A: being formed by 1 catalyst of embodiment, nickel chloride, ammonium metatungstate, zirconium oxychloride are mixed In one 5 liters of container, 1000 milliliters of water purification dilutions are added.It prepares containing with SiO in embodiment 1₂The identical dilute water glass of content Glass solution is added under agitation in mixing salt solution above.

(2) configure alkaline solution B: configuration is containing the same as Al in embodiment 1₂O₃The identical alkaline sodium aluminate solution of content 3000mL。

(3) by solution A, solution B and CO₂Plastic in plastic cans is added in gas cocurrent, and gelling temperature is maintained at 55 DEG C, pH Value is 7.6.Wherein CO used₂Gas concentration is 45v%, and CO is added₂Al in the total amount and alkaline solution of gas₂O₃Molar ratio 3, A, B solution flow velocity are adjusted, guarantee while being dripped off, to guarantee that it is constant that catalyst distribution uniformly forms.

(4) after cemented into bundles, in the case where being stirred continuously, the Y type molecular sieve for accounting for total catalyst weight 10wt% is added Suspension (in terms of butt) (is prepared) by CN101343068A embodiment 7, and Y type molecular sieve property is shown in Table 6, is dispersed in it In the mixed serum that plastic obtains, 75 DEG C or so standing aging 2 hours.

(5) it filters, it is 9 hours dry at 80 DEG C, it rolls, extruded moulding.It is washed at room temperature with water purification.Then dry at 100 DEG C Dry 12 hours, 530 DEG C roasted 4 hours, obtained catalyst I.Catalyst composition, pore size distribution and main character are shown in Table 1.

Embodiment 5

By middle oil type hydrocracking catalyst A, B, C, D of the invention and reference catalyst E, F, G, H, I in midget plant Upper evaluation result is compared.Evaluation condition are as follows: reaction stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, volume space velocity when liquid 1.5h^-1, evaluation is Iranian VGO heavy distillate with raw material, and main character is shown in Table 4, and table 5 lists evaluation result.

From table 2 and table 3 as can be seen that catalyst table phase active metallic content prepared by the method for the present invention is apparently higher than body phase Active metallic content, activity mutually increases considerably in catalyst.It can be seen that from the data of table 5 using catalysis prepared by the present invention The activity and middle distillates oil selectivity of agent A, B, C, D are better than reference agent, illustrate the catalyst activity metal benefit of the method for the present invention preparation With rate height, catalyst reaction activity is significantly improved.

1 catalyst of table composition and property

Catalyst number	A	B	C	D	E
						Catalyst composition
NiO, wt%	20	17	15	18	20
						WO3, wt%	24	23	27	20	24
SiO2, wt%	19	15	20	20	19
						Al2O3, wt%	22	26	23	34	22
Y molecular sieve, wt%	10	12	15	8	10
						Other/wt%	ZrO2/5.0	TiO2/7.0	-	-	ZrO2/5.0
Catalyst property
						Specific surface area, m2/g	392	389	394	383	288
Kong Rong, mL/g	0.409	0.394	0.397	0.402	0.285
						Mechanical strength, N/mm	22.7	22.2	23.1	22 .9	19.7
Pore size distribution, %
						< 4nm	15.78	16.25	15.39	15.36	52.33
4nm~8nm	66.12	65.74	66.11	67.98	44.15
						8nm~15nm	14.21	14.96	15.28	14.22	1.41
> 15nm	3.89	3.05	3.22	2.44	2.11

Continued 1

Catalyst number	F	G	H	I
					Catalyst composition
NiO, wt%	20	20	20	20
					WO3, wt%	24	24	24	24
SiO2, wt%	19	19	19	19
					Al2O3, wt%	22	22	22	22
Y molecular sieve, wt%	10	10	10	10
					Other/wt%	ZrO2/5.0	ZrO2/5.0	ZrO2/5.0	ZrO2/5.0
Catalyst property
					Specific surface area, m2/g	358	356	364	312
Kong Rong, mL/g	0.354	0.361	0.376	0.355
					Intensity, N/mm	19.1	18.4	18.1	17.8
Pore size distribution, %
					< 4nm	28.98	25.34	25.07	14.25
4nm~8nm	34.75	37.25	34.68	35.42
					8nm~15nm	24.92	23.54	24.59	36.84
> 15nm	11.35	13.87	15.66	13.49

The weight content of the weight content and body phase reactive metal oxides of 2 catalyst table phase reactive metal oxides of table The ratio between

Catalyst number	A	B	C	D	E
						Table phase IW/ body phase IW	4.32	3.87	3.58	3.24	0.95
Table phase INi/ body phase INi	3.52	3.48	3.35	3.14	0.91

Continued 2

Catalyst number	F	G	H	I
					Table phase IW/ body phase IW	1.10	1.07	1.08	1.22
Table phase INi/ body phase INi	1.05	1.14	1.19	1.18

3 catalyst surface WS of table₂Density

Catalyst number	A	B	C	D	E	F	G	H	I
										WS2Density, grain/100nm	79	77	77	78	39	44	45	46	47

4 feedstock oil main character of table

Project	Analyze result
		Density (20 DEG C), g/cm3	0.9113
Boiling range range, DEG C	314-539
		S, μ g/g	9800
N, μ g/g	1710
		Carbon residue, wt%	0.14
Condensation point, DEG C	34
		Cetane number	43.9

5 evaluating catalyst result of table

Catalyst number	A	B	C	D	E
						Reaction temperature, DEG C	390	389	389	390	397
Product distribution, wt%
						Light naphthar (C5~ 82 DEG C)	5.4	5.6	5.1	5.5	6.9
Heavy naphtha (82 ~ 138 DEG C)	8.2	8.5	9.0	8.8	9.9
						Jet fuel (138 DEG C ~ 249 DEG C)	27.8	27.1	26.4	25.3	23.0
Diesel oil (249 DEG C ~ 371 DEG C)	27.1	27.2	27.7	28.4	24.5
						Tail oil (> 371 DEG C)	31.5	31.6	31.8	32.0	35.7
Middle distillates oil selectivity, wt%	80.1	79.4	79.3	78.9	73.8

Continued 5

Catalyst number	F	G	H	I
					Reaction temperature, DEG C	398	398	397	397
Product distribution, wt%
					Light naphthar (C5~ 82 DEG C)	6.8	6.3	6.9	5.8
Heavy naphtha (82 ~ 138 DEG C)	9.7	10.4	9.5	10.0
					Jet fuel (138 DEG C ~ 249 DEG C)	23.5	23.1	22.3	23.1
Diesel oil (249 DEG C ~ 371 DEG C)	24.9	24.7	25.5	24.2
					Tail oil (> 371 DEG C)	35.1	35.5	35.8	36.9
Middle distillates oil selectivity, wt%	74.5	72.9	74.4	74.9

The property of Y type molecular sieve used in 6 embodiment of the present invention of table and comparative example

Molecular sieve property	Y
		Relative crystallinity, %	117
Cell parameter, nm	2.429
		SiO2/Al2O3Molar ratio	80.4
Specific surface area, m2/g	876
		Kong Rong, mL/g	0.493
Infrared total acid, mmol/g	0.240
		B Suan ∕ L acid	11.36
Na2O, wt%	<0.01

Claims (27)

1. a kind of preparation method of hydrocracking catalyst, comprising:

(1), sodium metaaluminate alkaline solution is added dropwise to solution A and carries out plastic reaction by the solution A for preparing the component containing Ni, and generation contains Nickel, aluminum precipitation object slurries I；

(2), the mixed solution B containing W, Si component is prepared, sodium metaaluminate alkaline solution and solution B cocurrent are subjected to plastic reaction, Generate tungstenic, silicon, aluminum precipitation object slurries II；

(3), the resulting slurries I of step (1) and the resulting slurries II of step (2) is uniformly mixed, aging under agitation, always After change, filtering, obtained material carries out hydro-thermal process with water vapour, urea is wherein added when hydro-thermal process；

(4), step (3) obtained material is beaten uniformly, and the suspension of molecular sieve is added under stirring condition, stirs evenly, Organic compound immersion is added after obtaining material washing in filtering, then through drying, molding；

(5), hydrocracking catalyst is made through dry and roasting in step (4) resulting material.

2. according to the method for claim 1, it is characterised in that: molecular sieve be added is Y type molecular sieve, molecular sieve suspension Molecular sieve is ground to 80 mesh ~ 140 mesh, then plus suspension is made in water.

3. according to the method for claim 2, it is characterised in that: molecular sieve be added is Y type molecular sieve, molecular sieve suspension Molecular sieve is ground to 100 mesh ~ 120 mesh, then plus suspension is made in water.

4. according to the method for claim 1, it is characterised in that: on the basis of the weight of catalyst, WO₃With the total content of NiO It is 0.05~1.0 for 20%~65%, W/Ni atomic ratio, the content of silica is 1wt%~40wt%, and the content of aluminium oxide is 10wt%~40wt%, the content of molecular sieve are 5wt%~20wt%.

5. according to the method for claim 1, it is characterised in that: on the basis of the weight of catalyst, WO₃With the total content of NiO It is 0.1~0.7 for 30%~50%, W/Ni atomic ratio, the content of silica is 5wt%~35wt%, and the content of aluminium oxide is 15wt% ~40wt%, the content of molecular sieve are 5wt%~15wt%.

6. according to the method for claim 1, it is characterised in that: the molecular sieve is Y type molecular sieve, and property is as follows: ratio Surface area is 700m²/ g~950m²/ g, total pore volume are 0.30mL/g~0.55mL/g, and relative crystallinity is 90%~130%, SiO₂/Al₂O₃Molar ratio is 30~150, and cell parameter is 2.425~2.445nm, and meleic acid amount is 0.1~1.0mmol/g, B Suan ∕ L acid is 7.0 or more, sodium oxide content≤0.05wt%.

7. according to the method for claim 1, it is characterised in that: in step (1) mixed solution A, weight of the Ni in terms of NiO is dense Degree is 5~80g/L；Contain Al in sodium metaaluminate alkaline solution described in step (1)₂O₃Concentration is 5 ~ 70g/L.

8. according to the method for claim 7, it is characterised in that: in step (1) mixed solution A, weight of the Ni in terms of NiO is dense Degree is 10~60g/L；Contain Al in sodium metaaluminate alkaline solution described in step (1)₂O₃Concentration is 5 ~ 50g/L.

9. according to the method for claim 1, it is characterised in that: in step (2) mixed solution B, W is with WO₃The weight concentration of meter For 10~100g/L, Si is with SiO₂Weight concentration is 10~120g/L；Contain in sodium metaaluminate alkaline solution described in step (2) Al₂O₃Concentration is 5 ~ 60g/L.

10. according to the method for claim 9, it is characterised in that: in step (2) mixed solution B, W is with WO₃The weight of meter is dense Degree is 20~90g/L, and Si is with SiO₂Weight concentration is 20~80g/L；Contain in sodium metaaluminate alkaline solution described in step (2) Al₂O₃Concentration is 5 ~ 40g/L.

11. according to the method for claim 1, it is characterised in that: reaction temperature is 20~90 DEG C, when plastic in step (1) Between be 0.2 ~ 4.0 hour, pH value control is 6.0 ~ 11.0 when cemented into bundles.

12. according to the method for claim 11, it is characterised in that: reaction temperature is 30~70 DEG C, when plastic in step (1) Between be 0.5 ~ 3.0 hour, pH value control is 7.0 ~ 9.0 when cemented into bundles.

13. according to the method for claim 1, it is characterised in that: Si, the Al introduced in step (2) is being urged in terms of oxide Weight content in agent is 10wt%~70wt%, and wherein Si accounts for the total weight of Si, Al in terms of oxide in terms of silica 10wt%~90wt%；Weight content of the Al introduced in step (1) in terms of oxide in the catalyst is 5wt%~45wt%.

14. according to the method for claim 13, it is characterised in that: Si, the Al introduced in step (2) is being urged in terms of oxide Weight content in agent is 20wt%~55wt%, and wherein Si accounts for the total weight of Si, Al in terms of oxide in terms of silica 30wt%~80wt%；Weight content of the Al introduced in step (1) in terms of oxide in the catalyst is 10wt%~30wt%.

15. according to the method for claim 1, it is characterised in that: in step (2) reaction temperature be 30~90 DEG C, cocurrent at PH value control is 6.0 ~ 11.0 when glue, and gelation time is 0.2 ~ 4.0 hour.

16. according to the method for claim 15, it is characterised in that: in step (2) reaction temperature be 40~80 DEG C, cocurrent at PH value control is 7.0 ~ 9.0 when glue, and gelation time is 0.5 ~ 3.0 hour.

17. according to the method for claim 1, it is characterised in that: aging temperature is 40~90 DEG C, when aging in step (3) PH value control is 6.0 ~ 10.0, and ageing time is 0.5 ~ 6.0 hour.

18. according to the method for claim 17, it is characterised in that: aging temperature is 50~80 DEG C, when aging in step (3) PH value control is 6.5 ~ 9.0, and ageing time is 1.0 ~ 4.0 hours.

19. according to the method for claim 1, it is characterised in that: hydrothermal conditions described in step (3) are as follows: It is carried out under closed container, temperature is 200 ~ 300 DEG C, and pressure is 1.0 ~ 8.0MPa, and the processing time is 0.5 ~ 10.0 hour；Step (3) in, when hydro-thermal process, the molar ratio of active metal atom total amount is 0.5:1 ~ 10.0 in the additional amount and catalyst of urea: 1。

20. according to the method for claim 19, it is characterised in that: hydrothermal conditions described in step (3) are as follows: It is carried out under closed container, temperature is 210 ~ 260 DEG C, and pressure is 3.0 ~ 6.0MPa, and the processing time is 1.0 ~ 6.0 hours；Step (3) in, when hydro-thermal process, the molar ratio of active metal atom total amount is 2.0:1 ~ 8.0:1 in the additional amount and catalyst of urea.

21. according to the method for claim 1, it is characterised in that: step (4) organic compound is selected from oxygen-containing or nitrogenous One or more of organic compound, wherein oxygen-containing organic compound is one or more of Organic Alcohol and organic acid, Organic compounds containing nitrogen is organic amine, the molar ratio of the organic compound and active metal nickel and the sum of tungsten in terms of oxide It is 0.1 ~ 3.0.

22. according to the method for claim 21, it is characterised in that: the organic compound and the activity gold in terms of oxide The molar ratio for belonging to the sum of nickel and tungsten is 0.3 ~ 2.0.

23. according to the method for claim 21, it is characterised in that: the oxygen-containing organic compound be ethylene glycol, glycerine, One of diethylene glycol, butanediol, aminotriacetic acid, xylitol, butantriol, pentanediol are a variety of, organic compounds containing nitrogen For hexa, ethylenediamine tetra-acetic acid, benzylamine, methyl diethanolamine, ethanol amine, n-butylamine, cyclohexylamine, phenyl ethylamine, benzene One of Propanolamine, triethylenediamine, diethylenetriamines, isobutyl amine are a variety of.

24. according to the method for claim 1, it is characterised in that: when step (4) is impregnated with organic compound, liquid solid product Than being 1.0 ~ 3.0, soaking time is 0.5~12 hour.

25. according to the method for claim 24, it is characterised in that: when step (4) is impregnated with organic compound, liquid solid product Than being 1.0 ~ 2.0, soaking time is 2~10 hours.

26. according to the method for claim 1, it is characterised in that: drying described in step (5) and roasting condition are as follows: 50 ~ 200 DEG C drying 1 ~ 48 hour, 450 ~ 600 DEG C roast 1 ~ 24 hour.

27. according to the method for claim 1, it is characterised in that: molten mixing in hydrocracking catalyst preparation process The compound containing adjuvant component, i.e. titanium source and/or zirconium source are added in liquid A, titanium source is using in Titanium Nitrate, titanium sulfate, titanium chloride One or more, zirconium source uses one of zirconium nitrate, zirconium chloride, zirconium oxychloride or a variety of.