CN104826651B - The preparation method of hydrocracking catalyst - Google Patents

Abstract

The invention discloses the preparation method of a kind of hydrocracking catalyst.The method includes: by small crystal grain Y-shaped molecular sieve, amorphous silica-alumina and the binding agent mechanical mixture made with aluminium oxide, molding, is then dried and roasting, makes catalyst carrier, and then load hydrogenation active metals component, drying and roasting, make catalyst.Silica alumina ratio is higher, degree of crystallinity is high, the NaY type Molecular sieve raw material of good stability in the method employing, after sequentially passing through alkali cleaning, ammonium exchange, dealumination complement silicon, hydrothermal treatment consists and processing with the mixed solution of acid and ammonium salt, obtained 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, has the product property of good activity, middle distillates oil selectivity and excellence.

Description

The preparation method of hydrocracking catalyst

Technical field

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

Background technology

Along with the demand of intermediate oil is continuously increased by international refined products market, in needing to obtain from mink cell focus more Between distillate, and one of important means of hydrocracking process light materialization of heavy oil just.Adapt to owing to this technique has raw material Property strong, good product quality, adjust flexible operation, midbarrel product yield is high, the product structure feature such as flexibly so that hydrogenation splits The status of metallization processes becomes more and more important, be faced with at present particular for China petroleum resources shortage, environmental requirement the tightest Lattice and oil product structure have been not suitable with the problems such as market, the application of hydrocracking technology will become raising petroleum product-quality, Reduce environmental pollution, the effective technology measure of increase market adaptability to changes, it has also become modernization refinery of paramount importance technique dress Put.These factors promote high selectivity to middle distillates hydrocracking technology and develop rapidly just, and hydrocracking catalyst is The key of this technology.

Carrier is the important component part of catalyst, not only provides dispersion place for metal active constituent, and carrier is originally simultaneously Body also assists in reaction, has worked in coordination with whole catalytic reaction together with other active component, and hydrocracking catalyst is a kind of double merit Energy catalyst, it contains acidic components and hydrogenation component simultaneously.The VI B race and that hydrogenation activity is selected generally from the periodic table of elements VIII race's metal provides；And its acidic components are 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 playing cracking in this type of catalyst is usually Y molecule Sieve, the quality of Y molecular sieve performance, directly affect performance and the product quality of catalyst.

Y type molecular sieve is cracking active component the most universal in residual oil cracking field, and crystal grain is generally About 1000nm, its crystal grain is relatively big, and duct is relatively long, and diffusional resistance is big, and macromole is difficult to inside entrance duct react, Afterproduct is the most difficult diffuses out, so the selectivity of its cracking activity and purpose product receives restriction in reaction.With conventional Y type 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 there is the most superior catalytic perfomance.Meanwhile, Y type molecular sieve crystallite dimension is reduced all right Improve inner surface active sites utilization rate.In general, reactant molecule diffusion in molecular sieve endoporus duct is referred to as intracrystalline expansion Dissipate.Molecular sieve inner surface to be made all is used for catalyzed conversion, it is necessary to make micropore diffusion speed more than endoporus catalyzed conversion Speed.Shortening the evolving path is the best way.The effective way overcoming micropore diffusion to limit is to reduce zeolite crystal Size.This not only can increase the external surface area of zeolite crystal, and shorten diffusion length simultaneously.EP0204236 is to little Crystal NaY molecular sieve and big crystal NaY molecular sieve compare, and result shows, RFCC is had higher by the former Active and preferable selectivity.

Small crystal grain NaY molecular sieve is not possess acidity, needs to be modified processing, to meet the performance of Cracking catalyst Requirement.CN1382632A discloses a kind of super stabilizing method of small-grain Y-type zeolite, and the method is with the dry gas of Silicon chloride. Body and fine grain NaY zeolitic contact, obtain after washing, owing to heat and the hydrothermal stability of its raw material self are the most poor, simultaneously The method is that the mode using gas phase dealumination complement silicon processes molecular sieve, and this makes the heat of product and hydrothermal stability worse, activity Low.Sial framing structure stability especially to the fine grain NaY zeolite that heat stability and hydrothermal stability are poor, in zeolite Poor, modifying process easily causes the removing of framework aluminum, the most also some framework silicon, also with removing, causes portion Divide skeleton that the phenomenon caved in occurs so that the crystallization reservation degree of product is relatively low, and the activity of zeolite is the highest.

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

Existing method fine grain NaY type molecular sieve is in preparation process, and silicon and aluminum are easy to run off, and silicon utilization rate is low, and silicon, Reuniting, easily occurs in aluminum distributing inhomogeneity, and it is high that the most existing method still cannot prepare silica alumina ratio, and heat stability and hydro-thermal steady The best qualitative 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, as the cracking component of catalyst, middle oil yield is low.

Summary of the invention

For weak point of the prior art, the invention provides the good hydrocracking catalyst of a kind of catalytic performance Preparation method.This hydrocracking catalyst a kind of high silica alumina ratio of employing, high-crystallinity, secondary pore are many, the little crystalline substance of bigger serface Grain Y type molecular sieve has higher activity, middle distillates oil selectivity and excellence as acidic components, prepared hydrocracking catalyst Product property.

The hydrocracking catalyst of the present invention, described hydrogenation active metals is vib and/or the metal of the VIIIth race, Vib metals is 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, The content of vib metals (in terms of oxide) is as 10wt%～the content of 30wt% and group VIII metal (in terms of oxide) is 4wt%～10wt%, the content of carrier is 61.0%～87.0%.

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

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

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

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

(2) by fine grain NaY with containing alkaline solution treatment；

(3) the fine grain NaY type molecular sieve that step (2) obtains is prepared as Na₂The little crystal grain of O content≤2.5wt% NH₄NaY；

(4) the molecular sieve hexafluorosilicic acid aqueous ammonium of step (3) gained carries out dealumination complement silicon, the molecular sieve obtained and pair Product separates；

(5) step (4) is obtained little crystal grain NH₄NaY molecular sieve carries out hydrothermal treatment consists；

(6) molecular sieve step (5) obtained is with containing NH₄ ⁺And H⁺Mixed solution process, scrubbed and dry, obtain little Grain Y-molecular sieve.

The preparation method of fine grain NaY type molecular sieve in step (1) in the inventive method, including:

A, preparation directed agents: silicon source, aluminum source, alkali source and water are fed intake according to following proportioning: (6～30) Na₂O:Al₂O₃: (6 ～30) SiO₂: (100～460) H₂O, after stirring, stirs mixture ageing at 0～20 DEG C and prepares for 0.5～24 hour Directed agents；

B, employing acid-base precipitation method prepare amorphous silica-alumina predecessor, with the weight of the butt of amorphous silica-alumina predecessor are Benchmark, the content that silicon is counted with silicon dioxide is as 40wt%～75wt%, preferably 55 wt%～70wt%；Its preparation process includes acid In alkali and plastic, aging, wherein silicon introduces the method for reaction system is in aluminiferous material and before plastic and/or during plastic Introducing portion contains silicon materials, and remainder is in aluminiferous material containing silicon materials and after plastic and introduces before ageing；

C, prepare silica-alumina gel

By (0.5～6) Na₂O:Al₂O₃: (7～11) SiO₂: (100～460) H₂Total molar ratio of O, at 0～40 DEG C In the amorphous silica-alumina predecessor of step (2) gained, quickly add water, silicon source, directed agents and alkali source under conditions of stirring, 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%,

D, step C gained reactant mixture through two step dynamic crystallizations, then through filter, washing, be dried, obtain little crystal grain NaY molecular sieve.

In the present invention, in step A and C, silicon source, alkali source can use routine to prepare silicon source and alkali source, the present invention of molecular sieve In preferably silicon source use sodium silicate, alkali source uses sodium hydroxide.In step A, aluminum source can use routine to prepare the aluminum source of molecular sieve, The present invention preferably employs sodium metaaluminate.

In the present invention, the silicon that step B preferably and after plastic and introduces in aluminiferous material before ageing is in terms of silicon dioxide Account for the 5wt% ~ 85wt% in terms of silicon dioxide of the silicon in amorphous silica-alumina predecessor, preferably 30wt% ~ 70wt%.

In the present invention, the preparation method of the amorphous silica-alumina predecessor of step B uses conventional acid-base precipitation method, wherein wraps Including acid-base neutralization plastic, aging, wherein the neutralization of the most acid material of acid-base neutralization plastic process and alkaline material was reacted Journey.Neutralizing plastic process can be in the way of using acid material or the continuous acid-base titration of alkaline material, it would however also be possible to employ acid Material and alkaline material also flow the mode of neutralization.The method that wherein silicon introduces in reaction system is as follows: in aluminiferous material and plastic Before and/or plastic during introducing portion containing silicon materials, remainder be in aluminiferous material containing silicon materials and after plastic and Introduce before aging.Silicon can be according to the different property containing silicon materials in aluminiferous material and before plastic and/or during plastic Matter be neutralized again after mix with acid material or alkaline material plastic (time such as containing silicon materials employing sodium metasilicate, metasilicic acid Sodium can mix with alkaline material；When using Ludox containing silicon materials, add acid aluminiferous material), it is also possible to silicon materials will be contained And it is individually added in reaction system during plastic in aluminiferous material, it is also possible to be the combination of said method.Plastic material one As include aluminiferous material (Al₂(SO₄)₃、AlCl₃、Al(NO₃)₃And NaAlO₂One or more in Deng), containing silicon materials (water glass One or more in glass, Ludox and organic silicon-containing compound etc., the most organic silicon-containing compound is silanol, silicon ether and silica One or more in alkane, precipitant is divided into acidic precipitation agent and alkaline precipitating agent, and wherein alkaline precipitating agent is sodium hydroxide, ammonia One or more in water, sodium carbonate, sodium bicarbonate, acidic precipitation agent is CO₂Or nitric acid, according to the different choice of plastic process Using, conventional mode of operation mainly has: (1) acid aluminium salt (Al₂(SO₄)₃、AlCl₃、Al(NO₃)₃) and basic aluminium salt (NaAlO₂) or alkaline precipitating agent (NaOH, NH₄OH) plastic, (2) basic aluminium salt (NaAlO are neutralized₂) and acidic precipitation agent (CO₂) Neutralize plastic.Described plastic process is typically carried out at room temperature ~ 85 DEG C, is relatively suitably for 40 ~ 80 DEG C, preferably 50 ~ 70 DEG C.Institute The pH value of the plastic process control system stated is 7.0 ~ 10.0, preferably 7.5 ~ 9.0.When using continuous acid-base titration, control The pH value of final plastic system is 7.0 ~ 10.0, preferably 7.5 ~ 9.0, make colloid system when using and flowing neutralization plastic time control PH value remains 7.0 ~ 10.0, and preferably 7.5 ~ 9.0.Carrying out aging after plastic, aging condition is as follows: pH is 7.0 ~ 10.0, excellent Elect 7.0 ~ 9.5 as, ageing time 0.2 ~ 8.0 hour, relatively it is suitable at 0.5 ~ 5 hour, preferably 1 ~ 3 hour, aging temperature was room Temperature ~ 85 DEG C, preferably 40 ~ 80 DEG C.Temperature and pH time aging are preferably identical with temperature during neutralization and pH.

In step C, control reaction temperature 0～40 DEG C, preferably 10 ~ 30 DEG C, pH value 9.5～12.0, preferable ph 10～11.

The reactant mixture of step D gained carries out crystallization and uses two step dynamic crystallizations, and wherein the first step carries out dynamic crystallization Condition as follows: temperature controls at 50～90 DEG C, and crystallization time is 0.5～18 hour；Second step carries out the condition of dynamic crystallization As follows: temperature controls at 80～140 DEG C, and crystallization time is 3～10 hours, after crystallization completes, then through filtering, washing, be dried, system Obtain product.Two step dynamic crystallization conditions are preferably as follows: the first step: temperature controls at 60～80 DEG C, and crystallization time is 1～10 little Time；Second step: temperature controls at 80～120 DEG C, and crystallization time is 5～10 hours.

Small crystal grain NaY molecular sieve described in step (1), its character is as follows: SiO₂/Al₂O₃Mol ratio is 5.0 ~ 9.0, excellent Select 6.0～9.0, more preferably 7.0～8.0, average grain diameter is 200～700nm, preferably 300～500nm；Compare table Face 800～1000 m²/ g, preferably 850～950 m²/ g, pore volume 0.30/～0.45mL/g, relative crystallinity be 90%～ 130%, cell parameter is 2.460～2.470nm, after roasting in 650 DEG C of air 3 hours relative crystallinity be generally 85% with On, preferably 90%～110%, after 700 DEG C of water vapour hydrothermal treatment consists 2 hours, relative crystallinity is generally more than 85%, excellent Elect 90%～110% as.

In step (2), small crystal grain NaY molecular sieve is pulled an oar with the aqueous solution of alkali and mixs homogeneously, and maintain 60～120 DEG C Stir process 1～4h under temperature conditions, filters, washes.The wherein used mixture that alkali is NaOH, KOH or NaOH and KOH. The concentration of the aqueous solution of alkali is generally 0.1～3 mol/L, and the concentration of serosity Middle molecule sieve is 0.05～1.0g/mL.

In step (4), aqueous medium adds little crystal grain NH₄NaY(solid-liquid weight ratio 1:4 ~ 1:8), stir and be warmed up to 90～120 DEG C, being then added dropwise to hexafluorosilicic acid aqueous ammonium, after dropping, constant temperature stirs 1～2 hour, separates molecular sieve And by-product, and filter, be dried.The concentration 10 wt% ~ 40wt% of hexafluorosilicic acid aqueous ammonium, ammonium hexafluorosilicate addition is little Crystal grain NH₄10wt% ~ the 50wt% of NaY molecular sieve.

In step (5), the condition of described hydrothermal treatment consists is as follows: treatment temperature controls, at 500～750 DEG C, preferably to control At 600～700 DEG C, pressure is 0.01～0.50MPa, preferably 0.05～0.30MPa, and the process time is 1.0～4.0 hours.

In step (6), by the molecular sieve after hydrothermal treatment consists and acid with 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 in hydrochloric acid, carbonic acid, nitric acid, 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 is 70～120 DEG C, exchange serosity Middle molecule sieve Concentration be 0.1～0.5g/mL, swap time is 0.5～3.0 hour, and exchange step may be repeated 1～4 time.Then remove Mother solution, washes with water, is dried.

Other operating procedure in the modified Y molecular sieve preparation method of the present invention, as ammonium salt exchange can use this area normal The operational approach of rule and condition.Step (3) uses the method for ammonium salt exchange, specific as follows: with NaY molecular sieve as raw material, and using can The aqueous solution of undissolved ammonium salt, at 70～120 DEG C, exchanges 0.5～3.0 hour at preferably 80～100 DEG C, and Y molecular sieve is at exchange slurry Concentration in liquid is 0.05～0.50g/mL, repeated exchanged l～5 times, filters off mother solution, washing, is dried.Ammonium salt such as ammonium chloride, carbon One or more in acid ammonium, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate etc., the concentration of ammonium salt solution is 0.5 ～5.0mol/L.

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, be prepared as 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, mix with small-grain Y molecular sieve and binding agent used by amorphous silica-alumina can be by altogether Prepared by the sedimentation method or grafting copolymerization process, prepare by conventional method in document.SiO in the amorphous silica-alumina prepared₂Weight 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 is 300～500 m²/ g, preferably 350～500 m²/g。

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

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 the content of amorphous silica-alumina is 20wt%～65wt%, and the content of aluminium oxide is 10wt% ～40wt%.

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

Hydrocracking catalyst of the present invention, including hydrogenation active metals component and by small-grain Y molecular sieve, aluminium oxide and nothing The carrier of amorphous silicon-alumina composition, wherein said small-grain Y molecular sieve, its character is as follows: SiO₂/ A1₂O₃Mol ratio be 30～ 120, average grain diameter is 200～700nm, preferably 300～500nm, relative crystallinity more than 100%, preferably 100% ~ 120%, lattice constant 2.425～2.450nm, specific surface area is 850～1000m²/ g, pore volume is 0.40～0.60mL/g, 1.7 ～more than 50% that the pore volume shared by the secondary pore of 10nm is total pore volume, preferably 50% ~ 80%, Na₂O content≤0.15wt%.

Hydrocracking catalyst character of the present invention is as follows: specific surface area is 300～500 m²/ g, pore volume is 0.35～0.60 ML/g, the pore volume of aperture 4 ~ 10nm accounts for the 55%～90% of total pore volume, preferably 65%～80%.

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 the widest, they include vacuum gas oil (VGO), coker gas oil, deasphalted oil, thermal cracking gas oil, and catalysis is split Changing gas oil, the various hydrocarbon-type oils such as catalytic cracking recycle oil, it is possible to be used in mixed way, raw material is usually containing boiling point 300～600 DEG C Hydro carbons, nitrogen content can be at 50～2500 g/g.

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

The small-grain Y molecular sieve used due to catalyst of the present invention, the silica alumina ratio of its NaY type Molecular sieve raw material is higher, knot Crystalline substance degree is high, good stability, thus in follow-up modification process, the not crystal structure of saboteur's sieve, and do not affect final The stability of molecular sieve.Molecular sieve of the present invention has carried out alkali process, with chemical dealuminization afterwards and hydrothermal treatment consists before ammonium exchanges Match, i.e. reached preferable dealumination depth, the most preferably maintain molecular sieve structure, create by substantial amounts of secondary simultaneously Hole, not only promotes the performance of hydrogenation activity, and the diffusion of beneficially product, hold charcoal ability and also greatly enhance, reduce The occurrence probability of excessive fragmentation and second pyrolysis, thus can make the catalyst have good activity, middle distillates oil selectivity and excellence Product property.

In carrier the most of the present invention use small crystal grain molecular sieve be Cracking Component, have bigger external surface area and more outside Active sites, is conducive to improving macromole hydrocarbon cracking capability, and can make by this molecular sieve is being hydrocracked of active component The activity increase of catalyst, can advantageously promote the performance of catalyst hydrogenation performance simultaneously.

Detailed description of the invention

In order to the present invention is better described, further illustrate the present invention below in conjunction with embodiment and comparative example.But this Bright scope is not limited solely to the scope of these embodiments.The present invention analyzes method: specific surface area, pore volume use low temperature liquid nitrogen physics Absorption method, relative crystallinity and cell parameter use x-ray diffraction method, and silica alumina ratio uses chemical method, and the crystal grain of molecular sieve is big The mode of little employing SEM (scanning electron microscope) measures.Wt% is mass fraction.

Embodiment 1

The present embodiment is to prepare raw material small crystal grain NaY molecular sieve

The preparation of NY-1

(1) preparation of directed agents: take 8g sodium hydrate solid and be dissolved in 80g water, adds sodium metaaluminate 2.5 g (Al₂O₃ Content is 45wt%, Na₂O content is 41wt%), then add 40g waterglass (SiO₂Content is 28wt%, Na₂O content is 8 Wt%), 18 DEG C of stirring 4 hours prepared directed agents of ageing after mix homogeneously.

(2) preparation of amorphous silica-alumina predecessor

It is 100g A1 that solid sodium aluminate is configured to 0.3L concentration₂O₃ / L sodium aluminate working solution (a).Strong aqua ammonia is added Enter appropriate distilled water diluting and become about 10wt% weak ammonia (b).Take containing SiO₂The sodium silicate solution of 28wt%, then it is dense to be diluted to 0.5L Degree is 140g SiO₂/ L sodium silicate working solution (c).Take the steel retort of one 5 liters, tank adds 0.5 liter of distilled water and stirs Mix after being heated to 70 DEG C, open the valve having (a) and (b) and (c) Sulfur capacity device respectively simultaneously, control the flow of (a) and (c) with Making the neutralization response time at 40 minutes, and the flow adjusting rapidly (b) makes the pH value of system be maintained at 7～8, and controls system Temperature is at about 60 DEG C.After reacting aluminum sulfate completes, stopping adding (b), the addition of (c) is 0.17L, the silicon-aluminum sol of generation After stablizing 20 minutes, continuously add (c) 0.33L, add in 10 minutes, start system ageing process, keep pH value 8.0, Temperature 60 C, aging 30 minutes.

(3) preparation of gel

Serosity obtained by step (2) adds 1L H₂O、140g SiO₂/ L sodium silicate working solution 0.6L and step (1) directed agents 100g prepared, the pH value of gel is 11.5, controls reaction temperature 15 DEG C, uniform stirring 30 minutes, staticizes 2.5 Hour.

(4) crystallization

Gel obtained by step (2) is poured in stainless steel cauldron, stirs crystallization 5 hours at 75 DEG C, then heat up To 110 DEG C, stirring crystallization 7 hours, then filter, wash, be dried to obtain NaY molecular sieve product NY-1, character is listed in table l.

The preparation of NY-2

(1) preparation of directed agents: take 10 g sodium hydrate solids and be dissolved in 90g water, adds sodium metaaluminate 3 g (Al₂O₃ Content is 45wt%, Na₂O content is 41wt%), then add 50g waterglass (SiO₂Content is 28wt%, Na₂O content is 8wt%), 20 DEG C of stirring 4 hours prepared directed agents of ageing after mix homogeneously.

(2) preparation of amorphous silica-alumina predecessor

It is 80g A1 that Solid aluminum sulfate is configured to 0.5L concentration₂O₃ / L aluminum sulfate working solution (a).Strong aqua ammonia is added Appropriate distilled water diluting becomes about 10wt% weak ammonia (b).Take containing SiO₂The sodium silicate solution of 28wt%, then it is diluted to 0.4L concentration For 150g SiO₂/ L sodium silicate working solution (c).Take the steel retort of one 5 liters, tank adds 0.5 liter of distilled water and stirs After being heated to 70 DEG C, open the valve having (a) and (b) and (c) container respectively simultaneously, control the flow of (a) and (c) so that in With the response time at 40 minutes, and the flow adjusting rapidly (b) makes the pH value of system be maintained at 7～8, and controls the temperature of system At about 60 DEG C.After reacting aluminum sulfate completes, stopping adding (b), the addition of (c) is 0.2L, and the silicon-aluminum sol of generation is stable After 20 minutes, continuously add (c) 0.2L, add in 10 minutes, start system ageing process, keep pH value 8.0, temperature 60 DEG C, aging 30 minutes.

(3) preparation of gel

Serosity obtained by step (2) adds 1.2L H₂O、150g SiO₂/ L sodium silicate working solution 0.8L and step Suddenly directed agents 120g that prepared by (1), the pH value of gel is 12, controls reaction temperature 30 DEG C, uniform stirring 30 minutes, staticizes 3 little Time.

(4) crystallization

Gel obtained by step (2) is poured in stainless steel cauldron, stirs crystallization 6 hours at 80 DEG C, then heat up To 120 DEG C, stirring crystallization 5 hours, then filter, wash, be dried to obtain NaY molecular sieve product NY-2, character is listed in table l.

Embodiment 2

First raw material small crystal grain NaY molecular sieve is carried out alkali process, be 1 mol/L's by 1000 grams of NY-1 Yu 5L concentration NaOH solution making beating mix homogeneously, and maintains stir process 2h under the temperature conditions of 80 DEG C, filter, be washed to solution close in Property；Being contacted by the 0.5mol/L aqueous ammonium nitrate solution of filter cake and 10 liters, speed of agitator is 300rpm, constant temperature stirring at 90 DEG C L hour, then filtering molecular sieve, and stay sample, analyze Na₂O content；Repeat aforesaid operations, until Na in molecular sieve₂O content Reaching 2.5wt%, obtaining dried sample number into spectrum is NNY-1.

Embodiment 3

First raw material small crystal grain NaY molecular sieve is carried out alkali process, be 0.8 mol/L's by 1000 grams of NY-2 Yu 5L concentration KOH solution making beating mix homogeneously, and maintain stir process 2h under the temperature conditions of 80 DEG C, filter, be washed to solution close to neutral； Being contacted by the 0.5mol/L aqueous ammonium nitrate solution of filter cake and 10 liters, speed of agitator is 300rpm, and at 95 DEG C, constant temperature stirring l is little Time, then filtering molecular sieve, and stay sample, analyze Na₂O content；Repeat aforesaid operations, until Na in molecular sieve₂The content of O reaches To 2.5wt%, obtaining dried sample number into spectrum is NNY-2.

Embodiment 4

Take 100 grams of NNY-1 deionized water making beating, and be brought rapidly up 90 DEG C, then with uniformly under conditions of stirring Speed in 2 hours, drip the aqueous solution configured by 30 grams of ammonium hexafluorosilicate and 150m1 deionized water, add rear slurry and exist Constant temperature 2 hours under 90 DEG C of stirring conditions, stands 10 minutes, is dried, is placed in by dried sample after 3 washings and filtration In heat-treatment furnace, control the heating rate of 400 DEG C/h, temperature is risen to 650 DEG C, maintains the steam partial pressure of system simultaneously 0.08MPa, processes 2 hours, cooling, takes out sample；By filter cake with 400mL containing NH₄ ⁺And H⁺Concentration be respectively 0.8mol/L and The mixed solution (ammonium nitrate and nitric acid) of 0.2mol/L processes, and the non-framework aluminum in removing sample, dealuminzation condition is at 70 DEG C Process 3 hours, filter, and wash filter cake with hot deionized water, after 7, stop washing, filter cake in baking with the pH value of cleaning mixture In case, 120 DEG C are dried 5 hours, 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 deionized water making beating, and be brought rapidly up 100 DEG C, then with uniformly under conditions of stirring Speed in 2 hours, drip the aqueous solution configured by 20 grams of ammonium hexafluorosilicate and 150m1 deionized water, add rear slurry and exist Constant temperature 2 hours under 100 DEG C of stirring conditions, stands 10 minutes, is dried, is put by dried sample after 3 washings and filtration In hydrothermal treatment consists stove, control the heating rate of 400 DEG C/h, temperature is risen to 700 DEG C, maintains the water vapour of system simultaneously Dividing potential drop 0.1MPa, processes 2 hours, cooling, takes out sample；By filter cake with 400mL containing NH₄ ⁺And H⁺Concentration be respectively 1.0mol/L Processing with the mixed solution (ammonium chloride and hydrochloric acid) of 0.2mol/L, the non-framework aluminum in removing sample, dealuminzation condition is at 75 DEG C Lower process is filtered for 3 hours, and washs filter cake with hot deionized water, stops washing, filter cake in baking with the pH value of cleaning mixture after 7 In case, 120 DEG C are dried 6 hours, 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%, nitric acid rubs 120 grams of binding agents with little porous aluminum oxide Your ratio is 0.25) put into mixed grind in chaser, add water, be rolled into paste, extrusion, extrusion bar 110 DEG C dry 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier TCAT-1.

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

Embodiment 7

By 40 grams of Y-1 molecular sieves (butt 90wt%), 90 grams of amorphous silica-aluminas (pore volume 0.9ml/g, than

Surface area 350m²/ g, butt 70wt%), (butt 20wt%, nitric acid rubs 120 grams of binding agents with little porous aluminum oxide Your ratio is 0.25) put into mixed grind in chaser, add water, be rolled into paste, extrusion, extrusion bar 110 DEG C dry 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier TCAT-2.

The impregnation liquid room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C are dried 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, obtain catalyst CAT-2, carrier and corresponding catalyst character and be shown in Table 2.

Comparative example 1

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

Feedstock property used in this comparative example 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, be sequentially added into 59.4mL sulfur in the waterglass of 208mL Acid aluminum, the low sodium metaaluminate of 62.7mL and 42.2mL directed agents, then constant temperature constant speed stirs 1.5 hours, the conjunction that then will obtain Become liquid the most static aging 8 hours, obtain gel.

(3) crystallization: under agitation, was raised to 50 DEG C by the gel in synthesis reactor in 20 minutes, constant temperature stirring crystallization 7 Hour；After low temperature crystallized end, in 20 minutes, the temperature in synthesis reactor being brought up to 120 DEG C, then constant temperature stirs 6 hours. Through filtering, washing and be dried, obtain product little crystal grain CNY-l.

2, raw material small crystal grain NaY molecular sieve being carried out ammonium exchange, treatment conditions, with embodiment 2, obtain dried sample Numbered CNNY-1.

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

4, 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%, nitric acid rubs 120 grams of binding agents with little porous aluminum oxide Your ratio is 0.25) put into mixed grind in chaser, add water, be rolled into paste, extrusion, extrusion bar 110 DEG C dry 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier TCCAT-1.

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

Comparative example 2

1, 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.

Being positioned in beaker by 14.21g water, in control beaker, temperature of liquid is 60 DEG C, is quickly simultaneously introduced under stirring The A1 of 12.79g50wt%₂(SO₄)₃) solution and 31.91g waterglass.After stirring, add above-mentioned directed agents 1.90g, gel PH value be 12.5, after stirring, be loaded in stainless steel cauldron, 60 DEG C of stirring crystallization 6 hours, then heat to 100 DEG C of static crystallizations 60 hours, then filter, wash, are dried and to obtain CNY-2 molecular sieve.

2, raw material small crystal grain NaY molecular sieve being carried out ammonium exchange, treatment conditions, with embodiment 2, obtain dried sample Numbered CNNY-2.

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

4, by 30 grams of CY-2 molecular sieves (butt 90wt%), 100 grams of amorphous silica-aluminas (pore volume 0.9ml/g, specific surface areas 350m²/ g, butt 70wt%), 120 grams of binding agents (butt 20wt%, nitric acid is 0.25 with the mol ratio of little porous aluminum oxide) put Entering mixed grind in chaser, add water, be rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, then little 550 DEG C of roastings 4 Time, obtain carrier TCCAT-2.

The impregnation liquid room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C are dried 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, obtain catalyst CCAT-2, carrier and corresponding catalyst character and be shown in Table 2.

Comparative example 3

1, prepared by fine grain NaY

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

(2) preparation of amorphous silica-alumina predecessor.

It is 100g A1 that solid sodium aluminate is configured to 0.3L concentration₂O₃ / L sodium aluminate working solution (a).Strong aqua ammonia is added Enter appropriate distilled water diluting and become about 10wt% weak ammonia (b).Take containing SiO₂The sodium silicate solution of 28wt%, then it is dense to be diluted to 0.5L Degree is 140g SiO₂/ L sodium silicate working solution (c).Take the steel retort of one 5 liters, tank adds 0.5 liter of distilled water and stirs Mixing after being heated to 70 DEG C, open the valve having (a) and (b) and (c) container respectively simultaneously, controlling the flow of (a) so that neutralizing anti- At 40 minutes between Ying Shi, and the flow adjusting rapidly (b) makes the pH value of system be maintained at 7～8, and controls the temperature of system 60 About DEG C.After reacting aluminum sulfate completes, stopping adding (b), the silicon-aluminum sol of generation stablizes 40 minutes.

(3) preparation of gel is with embodiment 1.

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

2, raw material small crystal grain NaY molecular sieve being carried out ammonium exchange, treatment conditions, with embodiment 2, obtain dried sample Numbered CNNY-3.

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

4, 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%, nitric acid rubs 120 grams of binding agents with little porous aluminum oxide Your ratio is 0.25) put into mixed grind in chaser, add water, be rolled into paste, extrusion, extrusion bar 110 DEG C dry 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier TCCAT-3.

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

Comparative example 4

1, the CNNY-1 using comparative example 1 preparation is raw material, and the method then using CN200910165116.X is modified, tool Body is as follows: takes the making beating of 100 grams of CNNY-1 100mL deionized waters, and is brought rapidly up 95 DEG C under conditions of stirring, then with Uniform speed dripped the aqueous solution configured by 25 grams of ammonium hexafluorosilicate and 150m1 deionized water in 2 hours, starched after adding Liquid is constant temperature 2 hours under 95 DEG C of stirring conditions, stand 10 minutes, through washing for 3 times, filter, being dried；By above-mentioned dried sample Product are placed in heat-treatment furnace, control the heating rate of 500 DEG C/h, temperature rise to 600 DEG C, maintains the water vapor pressure of system simultaneously Power is 0.15MPa, processes 2 hours, cooling, takes out sample；Final sample 400mL contains Al³⁺And H⁺Concentration be respectively 1.0mol/L and 0.5mol/L mixed solution (aluminum nitrate and nitric acid) removing sample in non-framework aluminum, dealuminzation condition be 80 DEG C process 2 hours, and wash filter cake with hot deionized water, stop washing, filter cake at baking oven with the pH value of cleaning mixture after 7 In 120 DEG C be dried 5 hours, obtain CY-4.The physico-chemical property of CY-4 is shown in Table 1.

2, by 40 grams of CY-4 molecular sieves (butt 90wt%), 90 grams of amorphous silica-aluminas (pore volume 0.9ml/g, specific surface areas 350m²/ g, butt 70wt%), 120 grams of binding agents (butt 20wt%, nitric acid is 0.25 with the mol ratio of little porous aluminum oxide) put Entering mixed grind in chaser, add water, be rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, then little 550 DEG C of roastings 4 Time, obtain carrier TCCAT-4.

The impregnation liquid room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C are dried 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, obtain catalyst CCAT-4, carrier and corresponding catalyst character and be shown in Table 2.

The character of table 1 Y type molecular sieve

Production code member	NY-1	NY-2	Y-1	Y-2	CY-1	CY-2	CY-3	CY-4
									Feed intake SiO2/Al2O3Mol ratio	8.8	8.0
SiO2/Al2O3Mol ratio	6.8	6.3	81	103	54	25	28	63
									Specific surface area, m2/g	898	884	990	1020	926	788	865	921
Pore volume, mL/g	0.38	0.37	0.56	0.60	0.49	0.32	0.34	0.48
									Secondary pore (1.7-10nm), %			64.4	69.2	45.1	27.5	35.2	42.1
External surface area, m2/g	189	180	249	240	196	164	195	189
									Lattice constant, nm	2.461	2.461	2.432	2.430	2.437	2.450	2.443	2.436
Relative crystallinity, %	100	105	118	116	114	80	85	116
									Average crystallite size, nm	400	430	400	430	400	450	400	400

Table 2 carrier and the physico-chemical property of catalyst

Bearer number	TCAT-1	TCAT-2	TCCAT-1	TCCAT-2	TCCAT-3	TCCAT-4
							Small-grain Y molecular sieve, wt%	22	29	29	29	22	22
Amorphous silica-alumina, wt%	58	51	51	51	58	58
							Aluminium oxide, wt%	20	20	20	20	20	20
Specific surface area, m2/g	517	536	455	438	430	490
							Pore volume, ml/g	0.60	0.63	0.51	0.47	0.46	0.55
Pore size distribution (4-10nm), %	64	72	47	45	42	53
							Catalyst is numbered	CAT-1	CAT-2	CCAT-1	CCAT-2	CCAT-3	CCAT-4
Specific surface area, m2/g	401	422	321	306	300	360
							Pore volume, ml/g	0.52	0.56	0.46	0.43	0.42	0.49
Pore size distribution (4-10nm), %	62	68	43	40	39	50

By the invention described above catalyst CAT-1, CAT-2 and comparative example catalyst CCAT-1, CCAT-2, CCAT-3 and CCAT-4 carries out active evaluation test.Test is carried out on 200ml small hydrogenation device, uses one-stage serial technique stream Journey, 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 nitrogen content 5～10 g/g.Catalyst Activating Test the results are shown in Table 4.

Table 3 raw oil character

Raw oil	Iran VGO
		Density (20 DEG C), g/cm3	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 value	41.5
Refractive power/nD 70	1.48570

Table 4 catalyst activity evaluation result

Catalyst is numbered	CAT-1	CAT-2	CCAT-1	CCAT-2	CCAT-3	CCAT-4
							Reaction temperature, DEG C	380	378	380	381	384	382
< 370 DEG C of conversion ratios, wt%	64.8	65.0	64.8	64.9	64.9	64.5
							Middle distillates oil selectivity, %(132～370 DEG C)	86.2	87.0	81.8	81.9	82.0	84.1
Major product character
							Jet fuel (132 ~ 282 DEG C)
Freezing point, DEG C	<-60	<-60	<-60	<-60	<-60	<-60
							Aromatic hydrocarbons, wt%	3.2	3.1	4.0	4.6	4.5	4.0
Smoke point, mm	28	27	26	25	26	26
							Diesel oil (282 ~ 370 DEG C)
Cetane number	62	63	59	58	57	60
							Condensation point, DEG C	-4	-6	-2	-1	0	-3

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

Claims (23)

1. a preparation method for hydrocracking catalyst, including: by small crystal grain Y-shaped molecular sieve, amorphous silica-alumina and with oxidation Binding agent mechanical mixture that aluminum is made, molding, be 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 described small crystal grain Y-shaped molecular sieve, bag Include:

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

(2) by fine grain NaY with containing alkaline solution treatment；

(3) the fine grain NaY type molecular sieve that step (2) obtains is prepared as Na₂The little crystal grain NH of O content≤2.5wt%₄NaY；

(4) the molecular sieve hexafluorosilicic acid aqueous ammonium of step (3) gained carries out dealumination complement silicon, the molecular sieve obtained and by-product Separate；

(5) step (4) is obtained little crystal grain NH₄NaY molecular sieve carries out hydrothermal treatment consists；

(6) molecular sieve step (5) obtained is with containing NH₄ ⁺And H⁺Mixed solution process, scrubbed and dry, obtain little crystal grain Y type molecular sieve；

The wherein preparation method of fine grain NaY type molecular sieve in step (1), including:

A, preparation directed agents: silicon source, aluminum source, alkali source and water are fed intake according to following proportioning: (6～30) Na₂O:Al₂O₃: (6～ 30)SiO₂: (100～460) H₂O, after stirring, stirs mixture to be aged 0.5～24 hour to prepare at 0～20 DEG C and leads To agent；

B, acid-base precipitation method is used to prepare amorphous silica-alumina predecessor, with the weight of the butt of amorphous silica-alumina predecessor as base Standard, the content that silicon is counted with silicon dioxide is as 40wt%～75wt%；Its preparation process includes acid-base neutralization plastic, aging, wherein silicon Introduce the method for reaction system be in aluminiferous material and before plastic and/or during plastic introducing portion containing silicon materials, residue Part is in aluminiferous material containing silicon materials and after plastic and introduces before ageing；

C, prepare silica-alumina gel: by (0.5～6) Na₂O:Al₂O₃: (7～11) SiO₂: (100～460) H₂O always feeds intake mole Ratio, adds water, silicon source, directed agents under conditions of 0～40 DEG C of quick stirring in the amorphous silica-alumina predecessor of step B gained And alkali source, and control ph is 9.5 ~ 12.0, uniform stirring, obtains silica-alumina gel；Wherein directed agents addition accounts for silica-alumina gel The 1%～20% of weight,

D, step C gained reactant mixture through two step dynamic crystallizations, then through filter, washing, be dried, obtain fine grain NaY and divide Son sieve.

The most in accordance with the method for claim 1, it is characterised in that in step B, amorphous silica-alumina predecessor, with amorphous silica-alumina On the basis of the weight of the butt of predecessor, silicon content in terms of silicon dioxide is 55 wt%～70wt%.

The most in accordance with the method for claim 1, it is characterised in that in step B, in the preparation process of amorphous silica-alumina predecessor, In aluminiferous material and after plastic and the silicon that introduces the before ageing silicon that accounts in amorphous silica-alumina predecessor in terms of silicon dioxide with 5wt% ~ the 85wt% of silicon dioxide meter.

The most in accordance with the method for claim 1, it is characterised in that in step B, the preparation process of amorphous silica-alumina predecessor In, the silicon and after plastic and introduced before ageing in aluminiferous material accounts for the silicon in amorphous silica-alumina predecessor in terms of silicon dioxide 30wt% ~ 70wt% in terms of silicon dioxide.

The most in accordance with the method for claim 1, it is characterised in that in step A and C, silicon source, alkali source are respectively sodium silicate and hydrogen Sodium oxide；In step A, aluminum source is selected from sodium metaaluminate.

The most in accordance with the method for claim 1, it is characterised in that in step B, aluminiferous material is Al₂(SO₄)₃、AlCl₃、Al (NO₃)₃And NaAlO₂In one or more, containing silicon materials be the one in waterglass, Ludox and organic silicon-containing compound or Several, the most organic silicon-containing compound is one or more in silanol, silicon ether and siloxanes, precipitant be acidic precipitation agent or Alkaline precipitating agent, one or more during wherein alkaline precipitating agent is sodium hydroxide, ammonia, sodium carbonate, sodium bicarbonate, acid heavy Shallow lake agent carbon dioxide or nitric acid.

The most in accordance with the method for claim 1, it is characterised in that in the acid-base precipitation method that step B uses, acid-base neutralization plastic Process is acid material and the neutralization course of reaction of alkaline material, neutralizes plastic process and uses acid material or alkaline material continuous The mode of acid-base titration, or use acid material and alkaline material and flow the mode of neutralization.

The most in accordance with the method for claim 7, it is characterised in that in step B, containing silicon materials in aluminiferous material and before plastic And/or during plastic introduce, be according to the different character containing silicon materials with acidity material or alkaline material mix after enter again Row neutralizes plastic, or will contain silicon materials in aluminiferous material and be individually added in reaction system during plastic, or on State the combination of method.

The most in accordance with the method for claim 1, it is characterised in that in step B, described plastic process is entered at room temperature ~ 85 DEG C OK, the pH value controlling system is 7.0 ~ 10.0；Carrying out aging after plastic, aging condition is as follows: aging pH is 7.0 ~ 10.0, aging 0.2 ~ 8.0 hour time, aging temperature is room temperature ~ 85 DEG C.

The most in accordance with the method for claim 1, it is characterised in that in step C, control reaction temperature 10 ~ 30 DEG C, pH value 10～ 11。

11. in accordance with the method for claim 1, it is characterised in that step D uses two step dynamic crystallizations, and wherein the first step is carried out The condition of dynamic crystallization is as follows: temperature controls at 50～90 DEG C, and crystallization time is 0.5～18 hour；Second step carries out dynamic crystalline substance The condition changed is as follows: temperature controls at 80～140 DEG C, and crystallization time is 3～10 hours.

12. in accordance with the method for claim 1, it is characterised in that step D uses two step dynamic crystallizations, and wherein the first step is carried out The condition of dynamic crystallization is as follows: temperature controls at 60～80 DEG C, and crystallization time is 1～10 hour；Second step carries out dynamic crystallization Condition as follows: temperature controls at 80～120 DEG C, and crystallization time is 5～10 hours.

13. in accordance with the method for claim 1, it is characterised in that in step (2), by the water of small crystal grain NaY molecular sieve Yu alkali Solution making beating mix homogeneously, and maintain stir process 1～4h under the temperature conditions of 60～120 DEG C；Alkali wherein used be NaOH, The mixture of KOH or NaOH and KOH；The concentration of the aqueous solution of alkali is 0.1～3 mol/L, and the concentration of serosity Middle molecule sieve is 0.05～1.0g/mL.

14. in accordance with the method for claim 1, it is characterised in that in step (4), presses solid-liquid weight ratio 1:4 in aqueous medium ~ 1:8 adds little crystal grain NH₄NaY molecular sieve, stirs and is warmed up to 90～120 DEG C, being then added dropwise to hexafluorosilicic acid aqueous ammonium, After dropping, constant temperature stirs 1～2 hour, separates molecular sieve and by-product, and filters, is dried；Hexafluorosilicic acid aqueous ammonium Concentration 10 wt% ~ 40wt%, ammonium hexafluorosilicate addition is little crystal grain NH₄10 wt% of NaY molecular sieve ~ 50wt%.

15. in accordance with the method for claim 1, it is characterised in that in step (5), the condition of described hydrothermal treatment consists is as follows: Treatment temperature controls at 500～750 DEG C, and pressure is 0.01～0.50MPa, and the process time is 1.0～4.0 hours.

16. in accordance with the method for claim 1, it is characterised in that in step (5), the condition of described hydrothermal treatment consists is as follows: Treatment temperature controls at 600～700 DEG C, and pressure is 0.05～0.30MPa, and the process time is 1.0～4.0 hours.

17. in accordance with the method for claim 1, it is characterised in that in step (6), by the molecular sieve after hydrothermal treatment consists with acid and Containing NH₄ ⁺Salt composition mixed solution contact, acid therein is one or more in hydrochloric acid, carbonic acid, nitric acid, sulphuric acid, 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 is 70～120 DEG C, exchange serosity Middle molecule sieve concentration be 0.1～0.5g/ ML, swap time is 0.5～3.0 hour, and exchange step repeats 1～4 time.

18. in accordance with the method for claim 1, it is characterised in that: step (3) uses the method for ammonium salt exchange, and process is as follows: With NaY molecular sieve as raw material, exchanging 0.5～3.0 hour at 70～120 DEG C with the aqueous solution of solubility ammonium salt, molecular sieve exists Concentration in exchange serosity is 0.05～0.50g/mL, repeated exchanged l～5 times, filters off mother solution, washing, is dried；Ammonium salt is chlorination One or more in ammonium, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate, the concentration of ammonium salt solution is 0.5～5.0mol/L.

19. 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 Amassing is 300～500 m²/g。

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

21. 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%.

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

23. in accordance with the method for claim 22, it is characterised in that: on the basis of the weight of catalyst, vib metals with The content of oxide meter is 10wt%～30wt% and the content counted with oxide of group VIII metal is as 4wt%～10wt%, carrier Content is 61wt%～86wt%.