CN104826653B - A kind of method for preparing hydrocracking catalyst - Google Patents

Abstract

The invention discloses a kind of method for preparing hydrocracking catalyst.The method includes：By small crystal grain Y-shaped molecular sieve, amorphous silica-alumina and with binding agent mixing, molding made by aluminium oxide, then it is dried and roasting, makes catalyst carrier, then load hydrogenation active metals component, drying and roasting, make catalyst；Wherein using silica alumina ratio is higher, degree of crystallinity is high, the NaY type Molecular sieve raw materials of good stability, sequentially pass through ammonium exchange, first time hydrothermal treatment consists, containing alkaline solution treatment, second hydrothermal treatment consists and after being processed with the mixed solution of ammonium salt with acid, resulting small crystal grain Y-shaped molecular sieve is obtaining higher SiO₂/A1₂O₃While mol ratio, the ratio shared by secondary pore is higher, and maintains the stability of Y type molecular sieve, and molecular sieve has higher specific surface area and higher degree of crystallinity.Hydrocracking catalyst of the present invention suitably as senior middle school's oil hydrocracking catalyst, with good activity, middle distillates oil selectivity and excellent product property.

Description

A kind of method for preparing hydrocracking catalyst

Technical field

The present invention relates to a kind of preparation method of hydrocracking catalyst, more specifically a kind of containing small-grain Y-type point The preparation method of the hydrocracking catalyst of son sieve.

Background technology

As international refined products market is continuously increased to the demand of intermediate oil, in needing more to obtain from mink cell focus Between distillate, and one of important means of hydrocracking process exactly light materialization of heavy oil.As there is the technique raw material to adapt to Property strong, good product quality, adjust flexible operation, midbarrel product yield is high, the features such as product structure is flexible so that hydrogenation splits The status of chemical industry skill becomes more and more important, particular for China be faced with present petroleum resources shortage, environmental requirement it is increasingly tight The problems such as lattice and oil product structure are not suitable with market, the application of hydrocracking technology will become raising petroleum product-quality, Reduce environmental pollution, increase the effective technology measure of market adaptability to changes, it has also become the of paramount importance technique dress in modernization refinery Put.Exactly these factors promote high selectivity to middle distillates hydrocracking technology and rapidly develop, and hydrocracking catalyst is The key of the technology.

Carrier is the important component part of catalyst, not only provides dispersion place for metal active constituent, while carrier sheet Body also assists in reaction, cooperates with and complete whole catalytic reaction together with other active components, and hydrocracking catalyst is a kind of pair of work( Energy catalyst, it contains acidic components and hydrogenation component simultaneously.Hydrogenation activity is selected generally from VI B races in the periodic table of elements and VIII race's metal is provided；And its acidic components is mainly provided by zeolite and inorganic oxide, major part is with aluminium oxide or without fixed Shape sial is carrier, is equipped with a certain amount of molecular sieve.And the key component that cracking is played in such catalyst is usually Y molecules Sieve, the quality of Y molecular sieve performance directly affect the performance and product quality of catalyst.

Y type molecular sieve is at present universal in residual oil cracking field cracking active component, and crystal grain is generally 1000nm or so, its crystal grain are larger, and duct is relatively long, and diffusional resistance is big, and macromole is difficult to be reacted into inside duct, After reaction, product is also more difficult diffuses out, so the selectivity of its cracking activity and purpose product receives restriction.With conventional Y types Molecular sieve is compared, and small crystal grain Y-shaped molecular sieve has bigger external surface area and more outer surface active center, is conducive to improving big point Sub- hydrocarbon cracking capability, thus with more superior catalytic perfomance.Meanwhile, reducing Y type molecular sieve crystallite dimension can be with Improve inner surface active sites utilization rate.In general, diffusion of the reactant molecule in molecular sieve endoporus duct is referred to as transgranular expansion Dissipate.Molecular sieve inner surface is made all to be used for catalyzed conversion, it is necessary to make micropore diffusion speed be more than endoporus catalyzed conversion Speed.It is the best way to shorten the evolving path.The effective way that micropore diffusion is limited is overcome to be to reduce zeolite crystal Size.This can not only increase the external surface area of zeolite crystal, and while shorten diffusion length.EP0204236 is to little Crystal NaY molecular sieve and big crystal grain NaY molecular sieve are compared, and are as a result shown, the former has higher to RFCC Active and preferable selectivity.

Small crystal grain NaY molecular sieve is that do not possess acidity, and needs are modified process, to meet the performance of Cracking catalyst Require.CN1382632A discloses a kind of super stabilizing method of small-grain Y-type zeolite, and the method is to be dried gas with Silicon chloride. Body and fine grain NaY zeolitic contact, obtain after washing, due to the heat and hydrothermal stability of its raw material itself it is just poor, while The method is by the way of gas phase dealumination complement silicon to process molecular sieve, and this causes the heat and hydrothermal stability of product worse, activity It is low.Especially poor to heat stability and hydrothermal stability fine grain NaY zeolite, the sial framing structure stability in zeolite It is poor, the removing of framework aluminum is easily caused in modifying process, while also some framework silicon causes portion also with removing Skeleton is divided the phenomenon caved in occur so that the crystallization reservation degree of product is relatively low, and the activity of zeolite is not high.

CN200910188140.5 discloses a kind of hydrocracking catalyst and preparation method thereof.The catalyst includes hydrogenation The carrier of active metal component and small-grain Y molecular sieve, amorphous silica-alumina and aluminium oxide composition, wherein the small-grain Y-type point Son sieve be using hydrothermal treatment consists after small crystal grain Y-shaped molecular sieve.During raw materials used small crystal grain NaY molecular sieve is CN101722023A Prepared by disclosed method, i.e. SiO₂/Al₂O₃Mol ratio be 4.0～6.0, mean diameter in 100～700nm, after passing sequentially through The mixed aqueous solution of continuous modified i.e. ammonium exchange, ammonium hexafluorosilicate dealumination complement silicon, hydrothermal treatment consists, aluminium salt and acid is processed, and obtains little crystalline substance Grain Y molecular sieve.In the method, after needing first raw material is processed with ammonium hexafluorosilicate dealumination complement silicon, then the process such as hydrothermal treatment consists is carried out, The framing structure that molecular sieve could so be reduced is caved in, and improves the crystallization reservation degree of molecular sieve, but the method due to first with six After the process of ammonium fluosilicate dealumination complement silicon, due to there is sial isomorphous substitution, molecular sieve silica constructed of aluminium is than more complete, then enters water-filling Heat treatment, the secondary pore of formation are few, and secondary pore proportion is low, and used as catalyst molecule screen banks point, middle oil yield is low.

In preparation process, silicon and aluminum are easy to run off existing method fine grain NaY type molecular sieve, and silicon utilization rate is low, and silicon, Aluminum distributing inhomogeneity, easily occurs reuniting, therefore existing method still cannot prepare silica alumina ratio height, and heat stability and hydro-thermal are steady Qualitative and good fine grain NaY type molecular sieve.Through successive modified, it is impossible to obtain structural integrity, degree of crystallinity is high and has more The small crystal grain Y-shaped molecular sieve of secondary pore, used as the cracking component of catalyst, middle oil yield is low.

The content of the invention

For weak point of the prior art, the invention provides a kind of preparation of the good hydrogenation catalyst of catalytic performance Method.A kind of dealumination depth is big, degree of crystallinity holding is good, the little crystalline substance that secondary pore is flourishing using providing for the hydrocracking catalyst Used as acidic components, prepared hydrocracking catalyst has a higher activity to grain Y type molecular sieve, middle distillates oil selectivity and excellent Product property.

The preparation method of hydrocracking catalyst of the present invention, comprises the steps：

By small-grain Y molecular sieve, amorphous silica-alumina and with binding agent mechanical mixture, molding, Ran Hougan made by aluminium oxide Dry and roasting, makes catalyst carrier；Supported active metals component, drying and roasting in the catalyst carrier of gained, make Catalyst；

Wherein described small-grain Y molecular sieve, including following preparation process：

(1) preparation of fine grain NaY type molecular sieve；

(2) by step（1）Fine grain NaY type molecular sieve be prepared into Na₂Little crystal grain NH of O content≤1.5wt%₄NaY；

(3) with little crystal grain NH₄NaY is raw material, carries out first time hydrothermal treatment consists；

(4) molecular sieve for obtaining step (3) is with containing alkaline solution treatment；

(5) molecular sieve that step (4) is obtained is carried out into second hydrothermal treatment consists；

(6) the molecular sieve acid for obtaining step (5) and the mixed solution of ammonium salt are processed, and Jing is washed and is dried to obtain little crystalline substance Grain Y type molecular sieve.

Step（1）Described in small crystal grain NaY molecular sieve, its property is as follows： SiO₂/Al₂O₃Mol ratio is more than 6.0 and not Higher than 9.0, preferably 6.5～9.0, more preferably 7.0～8.0, average grain diameter be 200～700nm, preferably 300～ 500nm；Specific surface area is 800～1000 m²/ g, preferably 850～950 m²/ g, 0.30/～0.45mL/g of pore volume are relative to tie Brilliant degree is 90%～130%, and cell parameter is 2.460～2.470nm, the relative crystallinity Jing after roasting in 650 DEG C of air 3 hours It is for more than 90%, generally 90%～110%, preferably 90% ~ 105%, relative Jing after 700 DEG C of water vapour hydrothermal treatment consists 2 hours Degree of crystallinity is more than 90%, generally 90%～110%, preferably 90% ~ 105%.

In the inventive method, in step (1), the preparation method of fine grain NaY type molecular sieve is as follows：

I, preparation directed agents：Silicon source, silicon source, alkali source and water are fed intake according to following proportioning：(6～30) Na₂O：Al₂O₃：(6 ～30) SiO₂：(100～460) H₂Mixture, after stirring, at 0～20 DEG C is stirred ageing and is obtained for 0.5～24 hour by O Directed agents；

II, using preparing amorphous silicon alumnium using carbonization predecessor, the weight with the butt of amorphous silica-alumina predecessor is as base Standard, the content that silicon is counted with silicon dioxide as 40wt%～75wt%, preferably 55 wt%～70wt%；Its preparation process includes：

A, respectively preparation sodium aluminate solution and sodium silicate solution；

The part sodium silicate solution for adding step a to prepare in b, the sodium aluminate solution prepared to step a, then passes to CO₂ Gas, controlling reaction temperature are 10 ~ 40 DEG C, and preferably 15～35 DEG C, the pH value for controlling cemented into bundles is 8 ~ 11；Wherein when being passed through CO₂Gas flow accounts for the 60% ~ 100% of total intake, when preferably 80% ~ 100%, adds remainder sodium silicate solution, wherein In step b, remainder sodium silicate solution accounts for step b addition sodium silicate solution total amount in terms of silicon dioxide in terms of silicon dioxide 5wt% ~ 85wt%, preferably 30wt% ~ 70wt%；

C, at the control temperature and pH value of step b, said mixture ventilation stablize 10 ~ 30 minutes；

III, prepare silica-alumina gel

By (0.5～6) Na₂O：Al₂O₃：(8～15) SiO₂：(100～460) H₂Total molar ratio of O, at 0～40 DEG C To step under conditions of quick stirring（2）Water, silicon source, directed agents and alkali source are added in the amorphous silica-alumina predecessor of gained, and Control ph is 9.5 ~ 12.0, and uniform stirring obtains silica-alumina gel；Wherein directed agents addition accounts for the 1% of silica-alumina gel weight ～20%,

Two step dynamic crystallizations of reactant mixture Jing obtained by IV, step III, then Jing filtrations, washing, are dried, obtain little crystalline substance Grain NaY molecular sieve.

In the present invention, in step I and III, silicon source, alkali source are respectively selected from sodium silicate and sodium hydroxide.In step I, silicon source Selected from sodium metaaluminate.

In step II, the concentration of the sodium aluminate solution used by step a is preferably 15～55g Al₂O₃/ L, sodium silicate solution Concentration be 50～150 gSiO₂/ L, CO used by step b₂The concentration of gas is 30v% ~ 60v%.

In step III, 0～40 DEG C of controlling reaction temperature, preferably 10 ~ 30 DEG C, pH value 9.5～12.0, preferable ph 10～ 11。

In step IV, the reactant mixture of gained carries out crystallization using two step dynamic crystallizations, and the wherein first step enters Mobile state The condition of crystallization is as follows：At 50～90 DEG C, crystallization time is 0.5～18 hour to temperature control；Second step carries out dynamic crystallization Condition is as follows：At 80～140 DEG C, crystallization time is 3～10 hours to temperature control, and after the completion of crystallization, then Jing is filtered, washs, done It is dry, product is obtained.Two step dynamic crystallization conditions are preferably as follows：The first step：Temperature control at 60～80 DEG C, crystallization time is 1～ 10 hours；Second step：At 80～120 DEG C, crystallization time is 5～10 hours to temperature control.

Step（2）In, with fine grain NaY type molecular sieve as raw material, with containing H⁺Ammonium salt aqueous solution at 70～120 DEG C, Exchange 0.5～3.0 hour at preferably 80～100 DEG C.Wherein described ammonium salt such as ammonium chloride, ammonium carbonate, ammonium nitrate, sulphuric acid One or more in ammonium, ammonium acetate, ammonium oxalate, ammonium citrate etc..H is provided in aqueous solution⁺Acid can be hydrochloric acid, carbonic acid, One or more in nitric acid, sulphuric acid.In aqueous solution, H⁺Concentration be 0.005～0.5mol/L, NH₄ ⁺Concentration be 0.5～ 5.0mol/L.Y type molecular sieve exchange serosity in concentration be 0.05～0.5g/mL, repeated exchanged l～5 time, filter off mother solution, Washing, is dried prepared Na₂O content is in below 1.5wt%.

Step（3）Described first time hydrothermal treatment consists temperature be 500 DEG C～700 DEG C, water vapor pressure be 0.01～ 1.0MPa, process time are 1.0～10.0 hours.

Step（4）By step（3）The molecular sieve for obtaining is mixed homogeneously with the aqueous solution beating of alkali, and maintains 60～120 DEG C Temperature conditionss under 1～4h of stir process, filter, washing.Alkali is selected from the mixture of NaOH, KOH or NaOH and KOH.The water of alkali The concentration of solution is generally 0.1～3.0 mol/L, and in serosity, the concentration of molecular sieve is 0.05～1.0g/mL.

Step（5）Second described hydrothermal treatment consists temperature is 500～800 DEG C, and water vapor pressure is 0.01～1.0MPa, Process time is 1.0～10.0 hours, and second hydrothermal treatment consists temperature is identical greater than or equal to first time hydrothermal treatment consists temperature.

Step（6）In, by the molecular sieve after hydrothermal treatment consists with acid and containing NH₄ ⁺Salt composition mixed solution contact, exchange Na in molecular sieve⁺With the part non-framework aluminum in removing molecular sieve, acid therein can be hydrochloric acid, carbonic acid, nitric acid, in sulphuric acid One or more, containing NH₄ ⁺Salt be one or more in the ammonium salt containing above acid group；H in mixed solution⁺Concentration be 0.05～0.6mol/L, NH₄ ⁺Concentration be 0.5～3.0mol/L, exchange temperature be 70～120 DEG C, exchange serosity in molecular sieve Concentration be 0.1～0.5g/mL, swap time be 0.5～3.0 hour, exchange step may be repeated 1～4 time.Then remove Mother solution, washes with water, is dried.

Detailed process prepared by carrier of hydrocracking catalyst of the present invention is：By small crystal grain Y-shaped molecular sieve, amorphous silica-alumina Mix with binding agent, extruded moulding, be then dried 3～10 hours and at 500 DEG C～600 DEG C at a temperature of 80 DEG C～150 DEG C Roasting 3～6 hours, is prepared into carrier.

Adhesive therefor of the present invention is made up of little porous aluminum oxide and mineral acid and/or organic acid.Aperture oxidation used Aluminum pore volume is 0.3～0.5 mL/g, and specific surface area is 200～400m²/g。

In catalyst carrier of the present invention, mixing amorphous silica-alumina used with small-grain Y molecular sieve and binding agent can be by altogether Prepared by the sedimentation method or grafting copolymerization process, prepare by conventional method in document.SiO in obtained amorphous silica-alumina₂Weight Content is 20%～60%, preferably 25%～40%, and the pore volume of amorphous silica-alumina is 0.6～1.1 mL/g, preferably 0.8～ 1.0 mL/g, specific surface area are 300～500 m²/ g, preferably 350～500 m²/g。

Catalyst of the present invention can carry out molding according to actual needs, and shape can be cylindrical bars, Herba Trifolii Pratentis etc..Catalyst into During type, shaping assistant, such as peptization acid, extrusion aid etc. can also be added.Catalyst carrier of the present invention is using conventional method It is dried and roasting, it is specific as follows：It is dried 3～10 hours at a temperature of 80 DEG C～150 DEG C and roasts at 500 DEG C～600 DEG C Burn 3～6 hours.

The load of catalyst activity metal of the present invention, can adopt conventional carrying method in prior art, preferred infusion process, Can be saturation leaching, excessive leaching or complexation leaching, i.e., with the solution impregnated catalyst carrier containing required active component, after dipping Carrier is dried l～12 hour at 100 DEG C～150 DEG C, then in 450 DEG C～550 DEG C roastings 3～6 hours, final catalysis is obtained Agent.

Hydrocracking catalyst of the present invention, including hydrogenation active metals component and by small-grain Y molecular sieve, with oxidation aluminum Into binding agent and amorphous silica-alumina composition carrier, wherein described small-grain Y molecular sieve, its property is as follows：SiO₂/ A1₂O₃ Mol ratio be 40～120, average grain diameter be 200～700nm, preferably 300～500nm, relative crystallinity >=95%, structure cell 2.425～2.440nm of constant, 900～1200m of specific surface area²/ g, 0.5/～0.80mL/g of pore volume, 1.7～10nm's are secondary Pore volume shared by hole is total pore volume more than 60%.

Hydrocracking catalyst property of the present invention is as follows：Specific surface area is 300～500 m²/ g, pore volume are 0.35～0.60 ML/g. the pore volume of 4 ~ 10nm of aperture accounts for the 60%～95% of total pore volume, and preferably 70%～90%.

The hydrocracking catalyst of the present invention, described hydrogenation active metals are the metal of vib and/or the VIIIth race, Vib metals are preferably molybdenum and/or tungsten, and the metal of the VIIIth race is preferably cobalt and/or nickel.On the basis of the weight of catalyst, Vib metals（In terms of oxide）Content be 10wt%～30wt% and group VIII metal（In terms of oxide）Content be 4wt%～10wt%, the content of carrier is 61wt%～86wt%.

Described carrier of hydrocracking catalyst, on the basis of the weight of carrier, its composition includes：Small-grain Y-type molecule The content of sieve is 5wt%～40wt%, and it is 10 that the content of amorphous silica-alumina is 20 wt%～65 wt%, the content of aluminium oxide Wt%～40 wt%.

Hydrocracking catalyst of the present invention is used for hydrocracking process, is suitable for treatment of heavy hydrocarbon material, it is adaptable to this law Heavy charge scope it is very wide, they include vacuum gas oil (VGO), and coker gas oil, deasphalted oil, thermal cracking gas oil, catalysis split Change the various hydrocarbon-type oils such as gas oil, catalytic cracking recycle oil, can also be used in mixed way, raw material usually contains 300～600 DEG C of boiling point Hydro carbons, nitrogen content can be in 50～2500mg/g.

The hydrocracking catalyst of the present invention is particularly well-suited to single hop once by, in method for hydrogen cracking, operating condition is such as Under：350～420 DEG C of reaction temperature, more preferably 360～390 DEG C, 6～20MPa of hydrogen dividing potential drop, more preferably 9～15MPa, hydrogen oil volume Than 500～2000:1, more preferably 800～1500：1,0.5～1.8 h of volume space velocity during liquid^-1, more preferably 0.8～1.5h^-1。

Due to the small-grain Y molecular sieve that catalyst of the present invention is adopted, the silica alumina ratio of its NaY type Molecular sieve raw material is higher, knot Brilliant degree is high, good stability, so in follow-up modification process, the crystal structure that saboteur does not sieve, so as to not affect most The stability of whole molecular sieve.The present invention is by hydrothermal treatment consists twice, and coordinates alkali process process twice between hydrothermal treatment consists, i.e., Preferable dealumination depth is reached, and has preferably maintained the rock-steady structure of molecular sieve, while substantial amounts of secondary pore is generated, no Only promote the performance of hydrogenation activity, and be conducive to the diffusion of product, hold charcoal ability and also greatly enhance, reduce excessively Cracking and the occurrence probability of second pyrolysises, have activity, middle distillates oil selectivity and excellent product well so as to make catalyst Property.

In addition adopt small crystal grain molecular sieve for Cracking Component in carrier of the present invention, with bigger external surface area and it is more outward Active sites, are conducive to improving macromole hydrocarbon cracking capability, can make being hydrocracked for active component by this molecular sieve The activity increase of catalyst, while the performance of catalyst hydrogenation performance can be advantageously promoted.

Specific embodiment

In order to the present invention is better described, the present invention is further illustrated with reference to embodiment and comparative example.But this Bright scope is not limited solely to the scope of these embodiments.Analysis method of the present invention：Specific surface area, pore volume adopt low temperature liquid nitrogen physics Absorption method, relative crystallinity and cell parameter adopt x-ray diffraction method, silica alumina ratio to adopt chemical method, and the crystal grain of molecular sieve is big It is little to be determined by the way of SEM (scanning electron microscope).Wt% is mass fraction.

Embodiment 1

The present embodiment is preparing raw material fine grain NaY type molecular sieve

The preparation of NY-1

（1）The preparation of directed agents：Take 10 g sodium hydrate solids to be dissolved in 80g water, add sodium metaaluminate 2g (Al₂O₃Contain Measure as 45wt%, Na₂O content is 41wt%), then add 36g waterglass (SiO₂Content is 28wt%, Na₂O content is 8 Wt%), in 15 DEG C of stirring 4 hours prepared directed agents of ageing after mix homogeneously.

（2）The preparation of amorphous silica-alumina predecessor

Solid sodium aluminate is configured to into concentration for 40gAl₂O₃/ L sodium aluminate working solutions, take containing SiO₂The silicic acid of 28wt% Sodium solution, then concentration is diluted to for 100g SiO₂/ L sodium silicate working solutions.Take 1L sodium aluminate working solutions and be placed in plastic cans In, 0.2L sodium silicate working solutions are subsequently adding, 20 DEG C of controlling reaction temperature is passed through the CO that concentration is 50v%₂Gas, works as pH value Stop logical CO when reaching 10.0₂, 0.4L sodium silicate working solutions are added, then ventilation stablizes 20 minutes.

（3）The preparation of gel

In step（2）100g SiO are added in resulting serosity₂/ L sodium silicate working solution 1.5L and step（1）Prepare Directed agents 120g, the pH value of gel is 12, and 20 DEG C of controlling reaction temperature, uniform stirring 30 minutes staticize 2 hours.

（4）Crystallization

By step（2）Resulting gel is poured in stainless steel cauldron, is stirred crystallization 4 hours at 70 DEG C, is then heated up To 100 DEG C, stirring crystallization 8 hours, then filter, washing, dry NaY molecular sieve product NY-1, product property is shown in Table 1.

The preparation of NY-2

（1）The preparation of directed agents：Take 8 g sodium hydrate solids to be dissolved in 80g water, add 2.5 g (Al of sodium metaaluminate₂O₃ Content is 45wt%, Na₂O content is 41wt%).Then 40g waterglass (SiO are added₂Content is 28wt%, Na₂O content is 8 Wt%), in 18 DEG C of stirring 4 hours prepared directed agents of ageing after mix homogeneously.

（2）The preparation of amorphous silica-alumina predecessor

Solid sodium aluminate is configured to into concentration for 30gAl₂O₃/ L sodium aluminate working solutions, take containing SiO₂The silicic acid of 28wt% Sodium solution, then concentration is diluted to for 70g SiO₂/ L sodium silicate working solutions.Take 1L sodium aluminate working solutions to be placed in plastic cans, 0.4L sodium silicate working solutions are subsequently adding, 18 DEG C of controlling reaction temperature is passed through the CO that concentration is 50v%₂Gas, when pH value reaches To the logical CO of stopping when 10.2₂, 0.6L sodium silicate working solutions are added, then ventilation stablizes 20 minutes.

（3）The preparation of gel

In step（2）70g SiO are added in resulting serosity₂/ L sodium silicate working solution 1.5L and step（1）Prepare Directed agents 100g, the pH value of gel is 11.5, and 15 DEG C of controlling reaction temperature, uniform stirring 30 minutes staticize 2.5 hours.

（4）Crystallization

By step（2）Resulting gel is poured in stainless steel cauldron, is stirred crystallization 5 hours at 75 DEG C, is then heated up To 110 DEG C, stirring crystallization 7 hours, then filter, washing, dry NaY molecular sieve product NY-2, product property is shown in Table 1.

Embodiment 2

Ammonium exchange is carried out to raw material fine grain NaY type molecular sieve NY-1 first.Prepare containing NH₄ ⁺And H⁺Concentration be respectively 10 liters of the solution (ammonium chloride and hydrochloric acid mixed solution) of 1.0mol/L and 0.02mol/L.Weigh small crystal grain NaY molecular sieve 1000 Gram, it is added in above-mentioned mixed solution, speed of agitator is 300rpm, the constant temperature stirring l hours at 90 DEG C, then filtering molecular Sieve, and sample is stayed, analyze Na₂O content；Repeat aforesaid operations, the Na in molecular sieve₂O content reaches 1.5wt%, is done Sample number into spectrum after dry is NNY-1.

Embodiment 3

Ammonium exchange is carried out to raw material fine grain NaY type molecular sieve NY-2 first.Prepare containing NH₄ ⁺And H⁺Concentration be respectively 0.8.0mol/L with 10 liters of the solution of 0.01mol/L (ammonium nitrate and nitric acid mixed solution).Weigh small crystal grain NaY molecular sieve 1000 grams, it is added in above-mentioned mixed solution, speed of agitator is 300rpm, then the constant temperature stirring l hours at 95 DEG C filter and divide Son sieve, and sample is stayed, analyze Na₂O content；Repeat aforesaid operations, the Na in molecular sieve₂O content reaches 1.5wt%, obtains Dried sample number into spectrum is NNY-2.

Embodiment 4

Take 100 grams of NNY-1 type molecular sieves to be placed in heat-treatment furnace, control 400 DEG C/h of heating rate, by temperature liter To 650 DEG C, while the steam partial pressure 0.08MPa of the system of maintenance, is processed 2 hours, sample is taken out in cooling；By the molecule for obtaining Sieve is that the beating of 0.5mol/L KOH solutions is mixed homogeneously with 600mL concentration, and maintains stir process 2h under 90 DEG C of temperature conditionss, Filter, be washed to the close neutrality of solution；Wet cake is placed in heat-treatment furnace, temperature is risen to into 700 DEG C, and control water in stove and steamed Steam pressure is 0.1MPa, and constant temperature 2 hours, cooling take out sample；Final sample is with containing NH₄ ⁺And H⁺Concentration be respectively 1.0mol/ The mixed solution 600mL of L ammonium nitrates and 0.15mol/L nitric acid is contacted with sample and is stirred, and is processed 3 hours, mistake at 100 DEG C Filter, washing are dried, and obtain modified small-grain Y -1.The physico-chemical property of Y-1 is shown in Table 1.

Embodiment 5

Take 100 grams of NNY-2 type molecular sieves to be placed in heat-treatment furnace, control 450 DEG C/h of heating rate, by temperature liter To 650 DEG C, while the steam partial pressure 0.15MPa of the system of maintenance, is processed 2 hours, sample is taken out in cooling；By the molecule for obtaining Sieve contains H with 500mL⁺KOH the and NaOH mixed solutions beating mix homogeneously of concentration 0.8mol/L, and maintain 100 DEG C of temperature strip Stir process 2h under part, filters, is washed to the close neutrality of solution；Wet cake is placed in heat-treatment furnace, temperature is risen to into 650 DEG C, and to control in stove water vapor pressure be 0.15MPa, constant temperature 2 hours, cooling take out sample；Final sample is with containing NH₄ ⁺And H⁺ Concentration be respectively 1.5mol/L and 0.3mol/L solution (ammonium nitrate and nitric acid mixed solution) 600mL contact with sample and stir Mix, process 3 hours at 95 DEG C, filter, washing is dried, obtain modified small-grain Y -2.The physico-chemical property of Y-2 is shown in Table 1.

Embodiment 6

By 30 grams of Y-1 molecular sieves (butt 90wt%), 100 grams of amorphous silica-aluminas (pore volume 0.9ml/g, than

Surface area 350m²/ g, butt 70wt%), (butt 20wt%'s 120 grams of binding agents, nitric acid are rubbed with little porous aluminum oxide You than 0.25) to be put into mixed grind in chaser, adding water, being rolled into paste, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then In 550 DEG C of roastings 4 hours, carrier TCAT-1 is obtained.

The impregnation liquid room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, catalyst CAT-1 is obtained, carrier and corresponding catalyst property are shown in Table 2.

Embodiment 7

By 40 grams of Y-2 molecular sieves (butt 90wt%), 90 grams of amorphous silica-aluminas (pore volume 0.9ml/g, than

Surface area 350m²/ g, butt 70wt%), (butt 20wt%'s 120 grams of binding agents, nitric acid are rubbed with little porous aluminum oxide You than 0.25) to be put into mixed grind in chaser, adding water, being rolled into paste, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then In 550 DEG C of roastings 4 hours, carrier TCAT-2 is obtained.

The impregnation liquid room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, catalyst CAT-2 is obtained, carrier and corresponding catalyst property are shown in Table 2.

Comparative example 1

1st, fine grain NaY is prepared with reference to CN101722023A.

In this comparative example, feedstock property used is as follows：Low alkali sodium metaaluminate：Na₂O content 120g/L, Al₂O₃Content 40g/L；Waterglass：SiO₂Content 250g/L；Aluminum sulfate：Al₂O₃Content 90g/L.

(1) preparation of directed agents：The preparation of directed agents is with NY-1 in embodiment 1.

(2) preparation of gel：Temperature is 8 DEG C, under stirring condition, sequentially adds 59.4mL sulfur in the waterglass of 208mL Sour aluminum, the low sodium metaaluminate of 62.7mL and 42.2mL directed agents, then constant temperature constant speed stirring 1.5 hours, then by the conjunction for obtaining Into liquid static aging 8 hours at the temperature disclosed above, gel is obtained.

(3) crystallization：Under agitation, the gel in synthesis reactor is raised to into 50 DEG C in 20 minutes, constant temperature stirring crystallization 7 Hour；After low temperature crystallized end, the temperature in synthesis reactor is brought up to into 120 DEG C in 20 minutes, then constant temperature is stirred 6 hours. Jing is filtered, washs and is dried, and obtains product little crystal grain CNY-l.

2nd, ammonium exchange is carried out to raw material small crystal grain NaY molecular sieve CNY-1, treatment conditions obtain dried with embodiment 2 Sample number into spectrum is CNNY-1.

3rd, subsequent treatment is carried out to CNNY-1, processing mode and condition obtain Reference Product CY-1 with embodiment 4.CY-1 Physico-chemical property be shown in Table 1.

4th, by 30 grams of CY-1 molecular sieves (butt 90wt%), 100 grams of amorphous silica-aluminas (pore volume 0.9ml/g, than

Surface area 350m²/ g, butt 70wt%), (butt 20wt%'s 120 grams of binding agents, nitric acid are rubbed with little porous aluminum oxide You than 0.25) to be put into mixed grind in chaser, adding water, being rolled into paste, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then In 550 DEG C of roastings 4 hours, carrier TCCAT-1 is obtained.

The impregnation liquid room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, catalyst CCAT-1 is obtained, carrier and corresponding catalyst property are shown in Table 2.

Comparative example 2

1st, fine grain NaY is prepared with reference to CN1785807A.

The preparation of directed agents：The preparation of directed agents is with NY-1 in embodiment 1.

14.21g water is positioned in beaker, it is 60 DEG C to control temperature of liquid in beaker, quick stirring is lower to be added simultaneously The A1 of 12.79g50wt%₂(SO₄)₃) solution and 31.91g waterglass.After stirring, above-mentioned directed agents 1.90g, gel are added PH value be 12.5, after stirring, be loaded in stainless steel cauldron, stir crystallization 6 hours at 60 DEG C, then heat to 100 DEG C of static crystallizations 60 hours, then filter, washing, dry CNY-2 molecular sieves.

2nd, ammonium exchange is carried out to raw material small crystal grain NaY molecular sieve CNY-2, treatment conditions obtain dried with embodiment 2 Sample number into spectrum is CNNY-2.

3rd, subsequent treatment is carried out to CNNY-2, processing mode and condition obtain Reference Product CY-2 with embodiment 4.CY-2 Physico-chemical property be shown in Table 1.

4th, by 30 grams of CY-2 molecular sieves (butt 90wt%), 100 grams of amorphous silica-aluminas (pore volume 0.9ml/g, than

Surface area 350m²/ g, butt 70wt%), (butt 20wt%'s 120 grams of binding agents, nitric acid are rubbed with little porous aluminum oxide You than 0.25) to be put into mixed grind in chaser, adding water, being rolled into paste, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then In 550 DEG C of roastings 4 hours, carrier TCCAT-2 is obtained.

The impregnation liquid room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, catalyst CCAT-2 is obtained, carrier and corresponding catalyst property are shown in Table 2.

Comparative example 3

1st, prepared by fine grain NaY

（1）The preparation of directed agents：The preparation of directed agents is with NY-1 in embodiment 1.

（2）The preparation of amorphous silica-alumina predecessor.

Solid sodium aluminate is configured to into concentration for 40gAl₂O₃/ L sodium aluminate working solutions, take containing SiO₂The silicic acid of 28wt% Sodium solution, then concentration is diluted to for 100g SiO₂/ L sodium silicate working solutions.Take 1L sodium aluminate working solutions and be placed in plastic cans In, 0.6L sodium silicate working solutions are subsequently adding, 20 DEG C of controlling reaction temperature is passed through the CO that concentration is 50v%₂Gas, works as pH value Stop logical CO when reaching 10.0₂, then divulge information and stablize 20 minutes.

（3）The preparation of gel is with embodiment 1.

（4）Crystallization obtains products C NY-3 with embodiment 1, and product property is shown in Table 1.

2nd, ammonium exchange is carried out to raw material small crystal grain NaY molecular sieve CNY-3, treatment conditions obtain dried with embodiment 2 Sample number into spectrum is CNNY-3.

3rd, subsequent treatment is carried out to CNNY-3, processing mode and condition obtain Reference Product CY-3 with embodiment 4.CY-3 Physico-chemical property be shown in Table 1.

By 40 grams of CY-3 molecular sieves (butt 90wt%), 90 grams of amorphous silica-aluminas (pore volume 0.9ml/g, than

Surface area 350m²/ g, butt 70wt%), (butt 20wt%'s 120 grams of binding agents, nitric acid are rubbed with little porous aluminum oxide You than 0.25) to be put into mixed grind in chaser, adding water, being rolled into paste, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then In 550 DEG C of roastings 4 hours, carrier TCCAT-3 is obtained.

The impregnation liquid room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, catalyst CCAT-3 is obtained, carrier and corresponding catalyst property are shown in Table 2.

The property of 1 Y type molecular sieve of table

Production code member	NY-1	NY-2	Y-1	Y-2	CY-1	CY-2	CY-3
								Feed intake SiO2/Al2O3Mol ratio	9.1	10.1
SiO2/Al2O3Mol ratio	7.5	8.4	115	89	50	25	28
								Specific surface area, m2/g	916	898	1140	1090	940	801	815
Pore volume, mL/g	0.39	0.38	0.72	0.66	0.35	0.33	0.36
								Secondary pore（1.7-10nm）, %			80.4	66.2	39.1	27.9	36.2
External surface area, m2/g	191	182	299	255	170	159	180
								Lattice constant, nm	2.461	2.462	2.426	2.429	2.432	2.433	2.433
Relative crystallinity, %	101	110	108	112	89	82	83
								Average crystallite size, nm	380	430	380	430	400	450	400

The physico-chemical property of 2 carrier of table and catalyst

Bearer number	TCAT-1	TCAT-2	TCCAT-1	TCCAT-2	TCCAT-3
						Small-grain Y molecular sieve, wt%	22	29	29	29	22
Amorphous silica-alumina, wt%	58	51	51	51	58
						Aluminium oxide, wt%	20	20	20	20	20
Specific surface area, m2/g	525	550	455	438	430
						Pore volume, mL/g	0.61	0.66	0.51	0.47	0.46
Pore size distribution（4-10nm）, %	76	68	49	46	43
						Catalyst is numbered	CAT-1	CAT-2	CCAT-1	CCAT-2	CCAT-3
Specific surface area, m2/g	405	420	325	309	301
						Pore volume, mL/g	0.57	0.60	0.46	0.43	0.42
Pore size distribution（4-10nm）, %	71	63	45	42	41

The invention described above catalyst CAT-1, CAT-2 and comparative example catalyst CCAT-1, CCAT-2 and CCAT-3 are carried out Active evaluation test.Test is carried out on 200ml small hydrogenation devices, using one-stage serial technological process, raw materials used Oil nature is shown in Table 3.Operating condition is as follows：Hydrogen dividing potential drop 14.7MPa, hydrogen to oil volume ratio 1500：1, air speed 1.5h^{- 1}, control cracking zone 5～10 g/g of nitrogen content.Catalyst Activating Test the results are shown in Table 4.

3 raw material oil nature of table

Raw oil	Iranian VGO
		Density (20 DEG C), g/cm-3	0.9025
Boiling range, DEG C	308～560
		Condensation point, DEG C	33
Acid number, mgKOH/g	0.53
		Carbon residue, wt%	0.2
S, wt%	1.5
		N, wt%	0.11
C, wt%	84.93
		H, wt%	12.52
Aromatic hydrocarbons, wt%	39.2
		BMCI values	41.5
Refractive power/nD 70	1.48570

4 catalyst activity evaluation result of table

Catalyst is numbered	CAT-1	CAT-2	CCAT-1	CCAT-2	CCAT-3
						Reaction temperature, DEG C	377	376	380	381	382
Product slates
						<370 DEG C of conversion ratios, wt%	64.8	65.0	64.8	64.9	64.9
Middle distillates oil selectivity, %（132～370 DEG C）	86.5	87.4	81.8	81.9	82.0
						Major product property
Jet fuel（132~282℃）
						Freezing point, DEG C	<- 60	<- 60	<- 60	<- 60	<- 60
Aromatic hydrocarbons, wt%	3.0	2.9	4.0	4.6	4.5
						Smoke point, mm	28	27	26	25	26
Diesel oil（282~370℃）
						Cetane number	63	64	59	58	57
Condensation point, DEG C	-5	-7	-2	-1	0

Can be seen that by the evaluation result of 4 catalyst of table, the catalyst prepared by the present invention has on the basis of greater activity There is good selectivity, product property is good.

Claims (25)

1. a kind of preparation method of hydrocracking catalyst, including：By small crystal grain Y-shaped molecular sieve, amorphous silica-alumina and with oxidation Binding agent mechanical mixture, molding made by aluminum, are then dried and roasting, make catalyst carrier；In the catalyst carrier of gained Load hydrogenation active metals component, drying and roasting, make catalyst；The preparation method of the small crystal grain Y-shaped molecular sieve, bag Include：

(1) preparation of fine grain NaY type molecular sieve；

(2) by step（1）Fine grain NaY type molecular sieve be prepared into Na₂Little crystal grain NH of O content≤1.5wt%₄NaY；

(3) with little crystal grain NH₄NaY is raw material, carries out first time hydrothermal treatment consists；

(4) molecular sieve for obtaining step (3) is with containing alkaline solution treatment；

(5) molecular sieve that step (4) is obtained is carried out into second hydrothermal treatment consists；

(6) the molecular sieve acid for obtaining step (5) and the mixed solution of ammonium salt are processed, and Jing is washed and is dried, and obtains small-grain Y Type molecular sieve；

Small crystal grain NaY molecular sieve wherein used by step (1), its property are as follows：SiO₂/Al₂O₃Mol ratio is not more than 6.0 and high In 9.0, average grain diameter is 200～700nm, 800～1000 m of specific surface²/ g, 0.30/～0.45mL/g of pore volume, relatively Degree of crystallinity is 90%～130%, and cell parameter is 2.460～2.470nm, relative Jing after roasting in 650 DEG C of air 3 hours to crystallize Spend for more than 90%, Jing after 700 DEG C of water vapour hydrothermal treatment consists 2 hours, relative crystallinity is more than 90%.

2. in accordance with the method for claim 1, it is characterised in that：The SiO of small crystal grain NaY molecular sieve used₂/Al₂O₃Mole Than for 6.5～9.0.

3. in accordance with the method for claim 1, it is characterised in that：The SiO of small crystal grain NaY molecular sieve used₂/Al₂O₃Mole Than for 7.0～8.0.

4. in accordance with the method for claim 1, it is characterised in that：The average grain diameter of small crystal grain NaY molecular sieve used For 300～500nm.

5. in accordance with the method for claim 1, it is characterised in that：Roast in 650 DEG C of air of small crystal grain NaY molecular sieve Jing used After burning 3 hours, relative crystallinity is 90%～110%, and Jing after 700 DEG C of water vapour hydrothermal treatment consists 2 hours, relative crystallinity is 90% ～110%.

6. in accordance with the method for claim 1, it is characterised in that：The preparation method of small crystal grain NaY molecular sieve used, bag Include：

I, preparation directed agents：Silicon source, silicon source, alkali source and water are fed intake according to following proportioning：(6～30) Na₂O：Al₂O₃：(6～ 30)SiO₂：(100～460) H₂O, after stirring, mixture at 0～20 DEG C is stirred to be aged to be obtained for 0.5～24 hour and is led To agent；

II, using preparing amorphous silicon alumnium using carbonization predecessor, on the basis of the weight of the butt of amorphous silica-alumina predecessor, The content that silicon is counted with silicon dioxide as 40wt%～75wt%；Its preparation process includes：

A, respectively preparation sodium aluminate solution and sodium silicate solution；

The part sodium silicate solution for adding step a to prepare in b, the sodium aluminate solution prepared to step a, then passes to CO₂Gas, Controlling reaction temperature is 10 ~ 40 DEG C, and the pH value for controlling cemented into bundles is 8 ~ 11；Wherein as the CO being passed through₂Gas flow is accounted for and is always passed through Amount 60% ~ 100% when, add remainder sodium silicate solution, wherein in step b, remainder sodium silicate solution is with silicon dioxide Meter accounts for step b and adds 5wt% ~ 85wt% of the sodium silicate solution total amount in terms of silicon dioxide；

C, at the control temperature and pH value of step b, said mixture ventilation stablize 10 ~ 30 minutes；

III, prepare silica-alumina gel：By (0.5～6) Na₂O：Al₂O₃：(8～15) SiO₂：(100～460) H₂O's always feeds intake mole Than, 0～40 DEG C it is quick stir under conditions of water, silicon source, guiding are added in the amorphous silica-alumina predecessor obtained by step II Agent and alkali source, and control ph is 9.5 ~ 12.0, uniform stirring obtains silica-alumina gel；Wherein directed agents addition accounts for sial and coagulates The 1%～20% of glue weight,

Two step dynamic crystallizations of reactant mixture Jing obtained by IV, step III, then Jing filtrations, washing, are dried, obtain little crystal grain NaY molecular sieve.

7. in accordance with the method for claim 6, it is characterised in that in step II, amorphous silica-alumina predecessor, with amorphous silicon On the basis of the weight of the butt of aluminum predecessor, the content that silicon is counted with silicon dioxide is as 55 wt%～70wt%.

8. in accordance with the method for claim 6, it is characterised in that：Step b controlling reaction temperature is 15～35 DEG C.

9. in accordance with the method for claim 6, it is characterised in that：In step b, as the CO being passed through₂Gas flow accounts for total intake When 80% ~ 100%, remainder sodium silicate solution is added.

10. in accordance with the method for claim 6, it is characterised in that：In step b, remainder sodium silicate solution is with silicon dioxide Meter accounts for step b and adds 30wt% ~ 70wt% of the sodium silicate solution total amount in terms of silicon dioxide.

11. in accordance with the method for claim 6, it is characterised in that in step I and III, and silicon source, alkali source are respectively selected from sodium silicate And sodium hydroxide, in step I, silicon source is selected from sodium metaaluminate.

12. in accordance with the method for claim 6, it is characterised in that in step III, 10 ~ 30 DEG C of controlling reaction temperature, pH value 10 ～11.

13. in accordance with the method for claim 6, it is characterised in that step IV adopts two step dynamic crystallizations, wherein the first stepping The condition of Mobile state crystallization is as follows：At 50～90 DEG C, crystallization time is 0.5～18 hour to temperature control；Second step enters Mobile state The condition of crystallization is as follows：At 80～140 DEG C, crystallization time is 3～10 hours to temperature control.

14. in accordance with the method for claim 6, it is characterised in that step IV adopts two step dynamic crystallizations, wherein the first stepping The condition of Mobile state crystallization is as follows：At 60～80 DEG C, crystallization time is 1～10 hour to temperature control；It is brilliant that second step enters Mobile state The condition of change is as follows：At 80～120 DEG C, crystallization time is 5～10 hours to temperature control.

15. in accordance with the method for claim 1, it is characterised in that step（2）In, with fine grain NaY type molecular sieve as raw material, With containing H⁺The aqueous solution of ammonium salt exchange 0.5～3.0 hour at 70～120 DEG C；Containing H⁺Ammonium salt aqueous solution in, H⁺It is dense Spend for 0.005～0.5mol/L, NH₄ ⁺Concentration be 0.5～5.0mol/L, molecular sieve exchange serosity in concentration be 0.05～ 0.50 g/mL, repeated exchanged l～5 time.

16. in accordance with the method for claim 15, it is characterised in that step（2）In, described ammonium salt is ammonium chloride, carbonic acid One or more in ammonium, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate, provides H in aqueous solution⁺Acid be salt Acid, carbonic acid, nitric acid, one or more in sulphuric acid.

17. in accordance with the method for claim 1, it is characterised in that step（3）Described first time hydrothermal treatment consists temperature is 500 DEG C～700 DEG C, water vapor pressure is 0.01～1.0MPa, and process time is 1.0～10.0 hours.

18. in accordance with the method for claim 1, it is characterised in that step（4）By step（3）The molecular sieve for obtaining and the water of alkali Solution is beaten mix homogeneously, and maintains 1～4h of stir process under 60～120 DEG C of temperature conditionss, filters, washes；Described alkali Selected from NaOH, KOH or NaOH and the mixture of KOH, the concentration of the aqueous solution of alkali is 0.1～3.0 mol/L, molecular sieve in serosity Concentration be 0.05～1.0g/mL.

19. in accordance with the method for claim 1, it is characterised in that step（5）Second described hydrothermal treatment consists temperature is 500 ～800 DEG C, water vapor pressure is 0.01～1.0MPa, and process time is 1.0～10.0 hours, and second hydrothermal treatment consists temperature is high In or be equal to first time hydrothermal treatment consists temperature it is identical.

20. in accordance with the method for claim 1, it is characterised in that step（6）In, processed with the mixed solution of acid and ammonium salt, Acid therein be hydrochloric acid, carbonic acid, nitric acid, one or more in sulphuric acid, containing NH₄ ⁺Salt be in the ammonium salt containing above acid group one Plant or various；H in mixed solution⁺Concentration be 0.05～0.6mol/L, NH₄ ⁺Concentration be 0.5～3.0mol/L, exchange temperature For 70～120 DEG C, the concentration for exchanging molecular sieve in serosity is 0.1～0.5g/mL, and swap time is 0.5～3.0 hour, is exchanged Step may be repeated 1～4 time.

21. in accordance with the method for claim 1, it is characterised in that：Used by mixing with small crystal grain Y-shaped molecular sieve and binding agent SiO in amorphous silica-alumina₂Weight content be 20%～60%, the pore volume of amorphous silica-alumina is 0.6～1.1 mL/g, specific surface Product is 300～500 m²/g。

22. in accordance with the method for claim 1, it is characterised in that：The condition of carrier drying and roasting is as follows：80 DEG C～ It is dried 3～10 hours and in 500 DEG C～600 DEG C roastings 3～6 hours at a temperature of 150 DEG C；The drying of catalyst and roasting condition It is as follows：L～12 hour are dried at 100 DEG C～150 DEG C, then in 450 DEG C～550 DEG C roastings 3～6 hours.

23. in accordance with the method for claim 1, it is characterised in that：Described carrier of hydrocracking catalyst, with the weight of carrier On the basis of amount, its composition includes：The content of small crystal grain Y-shaped molecular sieve is 5wt%～40wt%, and the content of amorphous silica-alumina is 20wt%～65wt%, the content of aluminium oxide is 10wt%～40wt%.

24. in accordance with the method for claim 1, it is characterised in that：Described hydrogenation active metals are vib and/or the The metal of VIII race, vib metals are molybdenum and/or tungsten, and the metal of the VIIIth race is cobalt and/or nickel.

25. in accordance with the method for claim 24, it is characterised in that：On the basis of the weight of catalyst, vib metals with The content that the content of oxide meter is 10wt%～30wt% and group VIII metal to be counted with oxide as 4wt%～10wt%, carrier Content is 61wt%～86wt%.