CN104588076B - Hydrocracking catalyst and preparation method thereof - Google Patents

Abstract

The invention discloses a hydrocracking catalyst and a preparation method thereof. The catalyst comprises a hydrogenation active metal component and a carrier prepared from a small-grain Y type molecular sieve, amorphous silicon aluminum and alumina. According to the preparation method, the small-grain Y type molecular sieve with the characteristics of proper dealumination degree, good crystallinity retentivity and well-developed secondary pores is used as an acid component; and when the small-grain Y type molecular sieve and the amorphous silicon aluminum are cooperatively applied to the hydrocracking catalyst, the hydrocracking catalyst has the advantages of good activity, heavy naphtha selectivity and superior product quality.

Description

Hydrocracking catalyst and preparation method thereof

Technical field

The present invention relates to a kind of hydrocracking catalyst and preparation method thereof, more specifically one kind contain small-grain Y-type The light oil type hydrogen cracking catalyst of molecular sieve.

Background technology

Hydrocracking technology is one of crude oil secondary operation, the important means of heavy oil lighting, because it is fitted to raw material Ying Xingqiang, operation and products scheme are all very flexibly and the features such as good product quality, it has also become produce high grade light-end products and Solve the important channel in industrial chemicals source.

The key of hydrocracking technology is catalyst.Catalyst newly developed is required to have higher active, selectivity, with Improve the adaptability to raw material for the device and the flexibility of processing scheme, voluminous high benefit component, reducing energy consumption, increase benefit.

Hydrocracking catalyst is a kind of bifunctional catalyst, and it contains acidic components and hydrogenation component simultaneously.Hydrogenation is lived Property be selected generally from VI B race in the periodic table of elements and group VIII metal provides；And its acidic components is mainly by zeolite and inorganic Oxide provides, and major part is with aluminum oxide or amorphous silica-alumina as carrier, is equipped with a certain amount of molecular sieve.And such catalyst In play the key component of cracking and be usually Y molecular sieve, the quality of Y molecular sieve performance, directly affect catalyst performance and Product quality.

Y type molecular sieve is cracking active component that at present can be the most universal in residual oil cracking field, and crystal grain is generally 1000nm about, its crystal grain is larger, and duct is relatively long, and diffusional resistance is big, and macromolecular is difficult to enter is reacted 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 type Molecular sieve is compared, and small crystal grain Y-shaped molecular sieve has bigger external surface area and more outer surface activated centre, is conducive to improving big point Sub- hydrocarbon cracking capability, thus there is more superior catalytic perfomance.Meanwhile, reduce Y type molecular sieve crystallite dimension acceptable Improve inner surface active sites utilization rate.In general, diffusion in molecular sieve endoporus duct for the reactant molecule 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.Shortening diffusion path is the best way.The effective way that micropore diffusion limits is overcome to be 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 grain NaY molecular sieve compare, and result shows, the former has higher to RFCC Active and preferable selectivity.

Small crystal grain NaY molecular sieve is that do not possess acidity, needs to be modified processing, to meet the performance of Cracking catalyst Require.CNl382632A discloses a kind of super stabilizing method of small-grain Y-type zeolite, and the method is gas to be dried with silicon tetrachloride Body and fine grain NaY zeolitic contact, obtain after washing, because the heat of its raw material itself and hydrothermal stability are just poor, simultaneously This inventive method is to process molecular sieve by the way of gas phase dealumination complement silicon, and this makes the heat of product and hydrothermal stability worse, Activity is low.Especially poor to heat endurance and hydrothermal stability fine grain NaY zeolite, the sial skeleton structure in molecular sieve Less stable, easily causes the removing of framework aluminum in modifying process, simultaneously also some framework silicon also with removing, Easily cause part skeleton and the phenomenon caved in occurs so that the crystallization reservation degree of product is relatively low, the activity of molecular sieve is not high.

CN200910188140.5 discloses a kind of hydrocracking catalyst and preparation method thereof.This catalyst includes being hydrogenated with Active metal component and the carrier of small-grain Y molecular sieve, amorphous silica-alumina and aluminum oxide composition, wherein said small-grain Y-type divides Son sieve be using hydro-thermal process after small crystal grain Y-shaped molecular sieve.Raw materials used small crystal grain NaY molecular sieve is in CN101722023A Disclosed method preparation, i.e. SiO₂/Al₂O₃Mol ratio be 4.0～6.0, average grain diameter in 100～700nm, after passing sequentially through Continuous modification is the mixed aqueous solution process of ammonium exchange, ammonium hexafluorosilicate dealumination complement silicon, hydro-thermal process, aluminium salt and acid, obtains little crystalline substance Grain Y molecular sieve.In the method, after needing first raw material to be processed with ammonium hexafluorosilicate dealumination complement silicon, then carry out the process such as hydro-thermal process, The caving in of skeleton structure of molecular sieve so could be reduced, improve the crystallization reservation degree of molecular sieve, but the method is due to first with six After ammonium fluosilicate dealumination complement silicon is processed, due to there are sial same order elements, 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 purpose product selectivity is low.

In preparation process, silicon and aluminium are easy to run off existing method fine grain NaY type molecular sieve, and silicon utilization rate is low, and silicon, Reuniting, easily occurs in aluminium distributing inhomogeneity, and therefore still cannot to prepare silica alumina ratio high for existing method, and heat endurance and hydro-thermal 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, as the cracking component of catalyst, purpose product yield is low.

Content of the invention

For weak point of the prior art, the invention provides a kind of good hydrocracking catalyst of catalytic performance and Its preparation method.This hydrocracking catalyst using provide a kind of silica alumina ratio many compared with high, high-crystallinity, secondary pore, greatly than table As acidic components, prepared hydrocracking catalyst has higher activity, scheelite brain to the small crystal grain Y-shaped molecular sieve of area The selective and excellent product property of oil.

Hydrocracking catalyst of the present invention, including hydrogenation active metals component and by small crystal grain Y-shaped molecular sieve, amorphous silicon Aluminium and the carrier of aluminum oxide composition, wherein said small crystal grain Y-shaped molecular sieve, its property is as follows：SiO₂/A1₂O₃Mol ratio is 10 It is 10～50, preferably 15 ~ 38 less than 40, average grain diameter is 200～700nm, preferably 300～500nm, phase To degree of crystallinity more than 100%, preferably 100% ~ 120%, lattice constant 2.430～2.450nm, preferably 2.435～ 2.445nm, specific surface area is 850～1000m²/ g, pore volume is 0.50～0.80mL/g, shared by the secondary pore of 1.7～10nm Pore volume accounts for more than the 50% of total pore volume, preferably 50% ~ 65%, Na₂O content≤0.15wt%.

Hydrocracking catalyst property 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 40%～70% of total pore volume, preferably 45%～60%.

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 15wt%～50wt%, preferably 20wt%～40wt%, and the content of amorphous silica-alumina is 20wt%～60wt%, excellent Elect 30wt%～50wt% as, the content of aluminum oxide is 10wt%～30wt%, preferably 15wt%～30wt%.

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

The adhesive mixing made small-grain Y molecular sieve, amorphous silica-alumina and with aluminum oxide, shaping, be then dried and Roasting, makes catalyst carrier；Load hydrogenation active metals component, drying and roasting in the catalyst carrier of gained, make Catalyst.

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

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

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

（3）By step（2）The fine grain NaY type molecular sieve obtaining is prepared into Na₂The little crystal grain of O content≤2.5wt% NH₄NaY；

（4）To step（3）Obtain little crystal grain NH₄NaY molecular sieve carries out hydro-thermal process；

（5）By step（4）The molecular sieve obtaining is with containing NH₄ ⁺And H⁺Mixed solution process, scrubbed and be dried, obtain Small crystal grain Y-shaped 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 is 200～700nm, preferably 300～ 500nm；Specific surface area is 800～1000 m²/ g, preferably 850～950 m²/ g, pore volume 0.30/～0.45mL/g, tie relatively Brilliant degree is 90%～130%, and cell parameter is 2.460～2.470nm, through relative crystallinity after 650 DEG C of in the air roastings 3 hours For more than 90%, generally 90%～110%, preferably 90% ~ 105%, through after 700 DEG C of water vapour hydro-thermal process 2 hours relatively Degree of crystallinity is more than 90%, generally 90%～110%, preferably 90% ~ 105%.

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

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 is stirred at 0～20 DEG C ageing and is obtained for 0.5～24 hour Directed agents；

II, adopt preparing amorphous silicon alumnium using carbonization predecessor, with the weight of the butt of amorphous silica-alumina predecessor as base Standard, the content that silicon is counted with silica 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 adding step a to prepare in b, the sodium aluminate solution prepared to step a, then passes to CO₂ Gas, controlling reaction temperature is 10 ~ 40 DEG C, preferably 15～35 DEG C, and the pH value 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 silica in terms of silica 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

Press (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 is 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%,

IV, the reactant mixture of step III gained are through two step dynamic crystallizations, then through filtering, wash, and 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 metasilicate and NaOH.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 and adopts 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, after the completion of crystallization, then through filtering, washing, do Dry, prepared product.Two step dynamic crystallization conditions are preferably as follows：The first step：Temperature control at 60～80 DEG C, crystallization time be 1～ 10 hours；Second step：At 80～120 DEG C, crystallization time is 5～10 hours to temperature control.

Step（2）In, small crystal grain NaY molecular sieve is mixed with the aqueous solution making beating of alkali, and maintains 60～120 DEG C Stir process 1～4h under temperature conditionss, filters, washes.Alkali wherein used is the mixture of NaOH, KOH or NaOH and KOH. The concentration of the aqueous solution of alkali is generally 0.1～3 mol/L, and in slurries, the concentration of molecular sieve is 0.05～1.0g/mL.

Step（4）In, the condition of described hydro-thermal process is as follows：Treatment temperature controls at 500～750 DEG C, preferably controls At 600～700 DEG C, pressure is 0.01～0.50MPa, preferably 0.05～0.30MPa, and process time is 1.0～4.0 hours.

Step（5）In, by the molecular sieve after hydro-thermal process with acid and contain 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 sulfuric acid One or more, containing NH₄ ⁺Salt be one or more of 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 slurries 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 liquor, washes with water, is dried.

Other operating procedures in the modified Y molecular sieve preparation method of the present invention, such as ammonium salt exchange can be normal using this area The method of operating of rule and condition.Step（3）The method being exchanged using ammonium salt, specific as follows：With NaY molecular sieve as raw material, 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 exchanging slurry Concentration in liquid is 0.05～0.50g/mL, repeated exchanged l～5 time, filters off mother liquor, washing, is dried.Ammonium salt such as ammonium chloride, carbon One or more of sour ammonium, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate etc., the concentration of ammonium salt solution is 0.5 ～5.0mol/L.

The detailed process of carrier of hydrocracking catalyst of the present invention preparation is：By small crystal grain Y-shaped molecular sieve, amorphous silica-alumina With adhesive mixing, extruded moulding, then it is 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 by little porous aluminum oxide and inorganic acid and/or organic acid system Become.Aperture aluminum oxide pore volume used 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 adhesive can be by altogether The precipitation method or grafting copolymerization process preparation, are prepared by conventional method in document.SiO in prepared 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 is 300～500 m²/ g, preferably 350～500 m²/g.

Catalyst of the present invention can be molded according to actual needs, and shape can be cylindrical bars, clover etc..Become in catalyst During type, shaping assistant can also be added, such as peptization acid, extrusion aid etc..Catalyst carrier of the present invention is using conventional method It is dried and roasting, specific as follows：It is dried 3～10 hours at a temperature of 80 DEG C～150 DEG C and roast at 500 DEG C～600 DEG C Burn 3～6 hours.

The load of catalyst activity metal of the present invention, can be using conventional carrying method in prior art, preferably infusion process, Can be saturation leaching, excessive leaching or complexing leaching, that is, 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 be catalyzed is obtained Agent.

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 very wide, they include vacuum gas oil (VGO), coker gas oil, deasphalted oil, thermal cracking gas oil, and catalysis is split Change gas oil, the various hydrocarbon-type oil such as catalytic cracking recycle oil, also can be used in mixed way, raw material is usually and 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 to be passed through in method for hydrogen cracking, and operating condition is such as Under：350～420 DEG C of reaction temperature, 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.

Hydrocracking catalyst of the present invention is because using small crystal grain Y-shaped molecular sieve, as acidic components, this molecular sieve has , feature of bigger serface many compared with high silica alumina ratio, high-crystallinity, secondary pore, with amorphous silica-alumina and hydrogenation active metals Component matches, and is particularly suitable as light oil type hydrogen cracking catalyst.

The small-grain Y molecular sieve being adopted due to catalyst of the present invention, 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 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 before ammonium exchange, matches with hydro-thermal process afterwards, that is, reaches Arrive preferable dealumination depth, and preferably maintained molecular sieve structure, created by substantial amounts of secondary pore simultaneously, not only promote The performance of hydrogenation activity, and be conducive to the diffusion of product, holds charcoal ability and also greatly enhances, reduce excessive fragmentation and The occurrence probability of second pyrolysis, thus can make catalyst have good activity, the selective and excellent product of heavy naphtha Matter.

In addition it is Cracking Component using small crystal grain molecular sieve in carrier of the present invention, there is bigger external surface area and more outer Active sites, are conducive to improving macromolecular 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.

Specific embodiment

In order to the present invention is better described, to further illustrate the present invention 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, and silica alumina ratio adopts chemical method, and the crystal grain of molecular sieve is big Measure by the way of little (SEM) using SEM.Wt% is mass fraction.

Embodiment 1

The present embodiment is preparing raw material small crystal grain NaY 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 mixing.

（2）The preparation of amorphous silica-alumina predecessor

It is 40gAl that solid sodium aluminate is configured to concentration₂O₃/ L sodium aluminate working solution, takes containing SiO₂The silicic acid of 28wt% Sodium solution, then it is diluted to concentration for 100g SiO₂/ L sodium metasilicate working solution.1L sodium aluminate working solution is taken to be placed in plastic cans In, it is subsequently adding 0.2L sodium metasilicate working solution, 20 DEG C of controlling reaction temperature, be passed through the CO that concentration is 50v%₂Gas, works as pH value Reach and when 10.0, stop logical CO₂, add 0.4L sodium metasilicate working solution, then ventilation stablizes 20 minutes.

（3）The preparation of gel

In step（2）100g SiO is added in obtained slurries₂/ L sodium metasilicate working solution 1.5L and step（1）Preparation Directed agents 120g, the pH value of gel is 12,20 DEG C of controlling reaction temperature, and uniform stirring 30 minutes staticizes 2 hours.

（4）Crystallization

By step（2）Obtained gel is poured in stainless steel cauldron, stirs crystallization 4 hours at 70 DEG C, then heats 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 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%), in 18 DEG C of stirring 4 hours prepared directed agents of ageing after mixing.

（2）The preparation of amorphous silica-alumina predecessor

It is 30gAl that solid sodium aluminate is configured to concentration₂O₃/ L sodium aluminate working solution, takes containing SiO₂The silicic acid of 28wt% Sodium solution, then it is diluted to concentration for 70g SiO₂/ L sodium metasilicate working solution.1L sodium aluminate working solution is taken to be placed in plastic cans, It is subsequently adding 0.4L sodium metasilicate working solution, 18 DEG C of controlling reaction temperature, be passed through the CO that concentration is 50v%₂Gas, when pH value reaches To the logical CO of stopping when 10.2₂, add 0.6L sodium metasilicate working solution, then ventilation stablizes 20 minutes.

（3）The preparation of gel

In step（2）70g SiO is added in obtained slurries₂/ L sodium metasilicate working solution 1.5L and step（1）Preparation Directed agents 100g, the pH value of gel is 11.5,15 DEG C of controlling reaction temperature, and uniform stirring 30 minutes staticizes 2.5 hours.

（4）Crystallization

By step（2）Obtained gel is poured in stainless steel cauldron, stirs crystallization 5 hours at 75 DEG C, then heats 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

First alkali process are carried out to raw material small crystal grain NaY molecular sieve, 1000 grams of NY-1 and 5L concentration are 1 mol/L NaOH solution making beating mixes, and maintains stir process 2h under 80 DEG C of temperature conditionss, filter, be washed to solution close in Property；Filter cake is contacted with 10 liters of 0.5mol/L aqueous ammonium nitrate solution, 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, Na in molecular sieve₂O content Reach 2.5wt%, obtaining dried sample number into spectrum is NNY-1.

Embodiment 3

First alkali process are carried out to raw material small crystal grain NaY molecular sieve, 1000 grams of NY-2 and 5L concentration are 0.8 mol/L KOH solution making beating mixes, and maintains stir process 2h under 80 DEG C of temperature conditionss, filters, is washed to solution close to neutral； Filter cake is contacted with 10 liters of 0.5mol/L aqueous ammonium nitrate solution, speed of agitator is 300rpm, at 95 DEG C, constant temperature stirring l is little When, then filtering molecular sieve, and stay sample, analyze Na₂O content；Repeat aforesaid operations, 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 to be placed in heat-treatment furnace, control 400 DEG C/h of heating rate, temperature is risen to 650 DEG C, Maintain the steam partial pressure 0.08MPa of system simultaneously, process 2 hours, cooling, take out sample；Sample is contained NH with 400mL₄ ⁺And H⁺Concentration be respectively 0.8mol/L and 0.2mol/L mixed solution (ammonium nitrate and nitric acid) process, removing sample in non-bone Frame aluminium, dealuminzation condition is to process 3 hours at 70 DEG C, filters, and washs filter cake with hot deionized water, is connect with the pH value of cleaning solution Stop washing, filter cake 120 DEG C of dryings 5 hours in an oven after nearly 7, 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 to be placed in hydro-thermal process stove, control 400 DEG C/h of heating rate, temperature is risen to 700 DEG C, maintain the steam partial pressure 0.1MPa of system simultaneously, process 2 hours, cooling, take out sample；Sample is contained NH with 400mL₄ ⁺ And H⁺Concentration be respectively 1.0mol/L and 0.2mol/L mixed solution (ammonium chloride and hydrochloric acid) process, removing sample in Non-framework aluminum, dealuminzation condition is to process 3 hours to filter at 75 DEG C, and washs filter cake with hot deionized water, with the pH of cleaning solution Value stops washing, filter cake 120 DEG C of dryings 6 hours in an oven after 7, obtains modified small-grain Y -2.The physico-chemical property of Y-2 It is shown in Table 1.

Embodiment 6

By 40 grams of Y-1 molecular sieves (butt 90wt%), 100 grams of amorphous silica-aluminas (pore volume 1.0ml/g, than

Surface area 380m²/ g, butt 70wt%), (butt 20wt%, nitric acid is rubbed 160 grams of adhesives with little porous aluminum oxide You are than being 0.25) put into mixed grind in roller, add water, be rolled into paste, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then In 550 DEG C of roastings 4 hours, obtain carrier TCAT-1.

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

Embodiment 7

By 55 grams of Y-1 molecular sieves (butt 90wt%), 80 grams of amorphous silica-aluminas (pore volume 0.9ml/g, than

Surface area 350m²/ g, butt 70wt%), (butt 20wt%, nitric acid is rubbed 160 grams of adhesives with little porous aluminum oxide You are than being 0.25) put into mixed grind in roller, add water, be rolled into paste, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then In 550 DEG C of roastings 4 hours, obtain carrier TCAT-2.

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

Comparative example 1

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

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

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

4th, by 40 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 is rubbed 160 grams of adhesives with little porous aluminum oxide You are than being 0.25) put into mixed grind in roller, add water, be rolled into paste, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then In 550 DEG C of roastings 4 hours, obtain carrier TCCAT-1.

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

Comparative example 2

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

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

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

4th, by 40 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 is rubbed 160 grams of adhesives with little porous aluminum oxide You are than being 0.25) put into mixed grind in roller, add water, be rolled into paste, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then In 550 DEG C of roastings 4 hours, obtain carrier TCCAT-2.

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

Comparative example 3

1st, fine grain NaY preparation

（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.

It is 40gAl that solid sodium aluminate is configured to concentration₂O₃/ L sodium aluminate working solution, takes containing SiO₂The silicic acid of 28wt% Sodium solution, then it is diluted to concentration for 100g SiO₂/ L sodium metasilicate working solution.1L sodium aluminate working solution is taken to be placed in plastic cans In, it is subsequently adding 0.6L sodium metasilicate working solution, 20 DEG C of controlling reaction temperature, be passed through the CO that concentration is 50v%₂Gas, works as pH value Reach and when 10.0, stop logical CO₂, then divulge information and stablize 20 minutes.

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

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

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

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

4th, by 55 grams of Y-1 molecular sieves (butt 90wt%), 80 grams of amorphous silica-aluminas (pore volume 0.9ml/g, than

Surface area 350m²/ g, butt 70wt%), (butt 20wt%, nitric acid is rubbed 160 grams of adhesives with little porous aluminum oxide You are than being 0.25) put into mixed grind in roller, add water, be rolled into paste, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then In 550 DEG C of roastings 4 hours, obtain carrier TCCAT-3.

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

Comparative example 4

1st, the preparation of CNNY-4 is with comparative example 1.Then the method adopting CN200910165116.X is modified, specific as follows： Take 100 grams of CNNY-4 100mL deionized water making beating, and be brought rapidly up 95 DEG C under conditions of stirring, then with uniform Speed drips by the aqueous solution of 25 grams of ammonium hexafluorosilicate and the configuration of 150m1 deionized water in 2 hours, adds rear slurry 95 2 hours of constant temperature under DEG C stirring condition, stand 10 minutes, through 3 washings, filter, be dried；Sample after above-mentioned drying is placed in In heat-treatment furnace, control the heating rate of 500 DEG C/h, temperature is risen to 600 DEG C, the water vapor pressure of maintenance system is simultaneously 0.15MPa, is processed 2 hours, and sample is taken out in cooling；Final sample contains Al with 400mL³⁺And H⁺Concentration be respectively 1.0mol/L Remove the non-framework aluminum in sample with the mixed solution (aluminum nitrate and nitric acid) of 0.5mol/L, dealuminzation condition is to process 2 at 80 DEG C Hour, and wash filter cake with hot deionized water, washing, filter cake are stopped after 7 with the pH value of cleaning solution and does for 120 DEG C in an oven Dry 5 hours, obtain CY-4.The physico-chemical property of CY-4 is shown in Table 1.

2nd, by 40 grams of Y-1 molecular sieves (butt 90wt%), 100 grams of amorphous silica-aluminas (pore volume 1.0ml/g, than

Surface area 380m²/ g, butt 70wt%), (butt 20wt%, nitric acid is rubbed 160 grams of adhesives with little porous aluminum oxide You are than being 0.25) put into mixed grind in roller, add water, be rolled into paste, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then Obtain carrier TCCAT-4 in 550 DEG C of roastings within 4 hours.

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

Comparative example 5

1st, fine grain NaY is prepared with reference to CN92105661.3

Feedstock property used by NaY 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：The low sodium metaaluminate of 60mL aluminum sulfate, 60mL is sequentially added in the waterglass of 220mL, Then constant temperature constant speed stirs 0.5 hour, prepared silica-alumina gel.

(3) crystallization：Under agitation, in 30 minutes, the gel in synthesis reactor is raised to 140 DEG C, constant temperature stirs crystallization 2 hours；Add 35mL directed agents, mixing and stirring, then continue crystallization 15 hours at 100 DEG C, through filtering, washing and do Dry, obtain products C NY-5, 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, with embodiment 2, obtain dried Sample number into spectrum is CNNY-5.

3rd, CNNY-5 is carried out with subsequent treatment, processing mode and condition, with embodiment 4, obtain Reference Product CY-5.CY-5 Physico-chemical property be shown in Table 1.

4th, by 40 grams of Y-1 molecular sieves (butt 90wt%), 100 grams of amorphous silica-aluminas (pore volume 1.0ml/g, than

Surface area 380m²/ g, butt 70wt%), (butt 20wt%, nitric acid is rubbed 160 grams of adhesives with little porous aluminum oxide You are than being 0.25) put into mixed grind in roller, add water, be rolled into paste, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then In 550 DEG C of roastings 4 hours, obtain carrier TCCAT-5.

The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, obtain catalyst CCAT-5, carrier and corresponding catalyst property are shown in Table 2.

Comparative example 6

1st, take 100gNNY-1, adopt the method for CN200910165116.X modified the NNY-1 of the present invention, specifically modified Method, with comparative example 4, obtains Reference Product CY-6.The physico-chemical property of CY-6 is shown in Table 1.

2nd, by 55 grams of Y-1 molecular sieves (butt 90wt%), 80 grams of amorphous silica-aluminas (pore volume 0.9ml/g, specific surface areas 350m²/ g, butt 70wt%), 160 grams of adhesives (butt 20wt%, nitric acid is 0.25 with the mol ratio of little porous aluminum oxide) put Enter mixed grind in roller, add water, be rolled into paste, extrusion, extrusion bar is in 110 DEG C of dryings 4 hours, then little in 550 DEG C of roastings 4 When, obtain carrier TCCAT-6.

The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, obtain catalyst CCAT-6, carrier and corresponding catalyst property are shown in Table 2.

The property 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	CY-5	CY-6
											Feed intake SiO2/Al2O3Mol ratio	9.1	10.1
SiO2/Al2O3Mol ratio	7.5	8.4	32	35	20	18	19	63	24	65
											Specific surface area, m2/g	916	898	931	927	880	861	875	921	711	935
Pore volume, mL/g	0.39	0.38	0.47	0.45	0.39	0.37	0.41	0.48	0.30	0.51
											Secondary pore（1.7-10nm）, %			56.4	61.2	40.1	27.5	35.2	42.1	25.2	44.0
External surface area, m2/g	191	182	244	233	170	169	190	189	145	209
											Lattice constant, nm	2.461	2.462	2.439	2.438	2.441	2.442	2.441	2.436	2.449	2.436
Relative crystallinity, %	101	110	104	105	86	81	82	116	78	117
											Average crystallite size, nm	380	430	380	430	470	450	400	400	450	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	TCCAT-5	TCCAT-6
									Y molecular sieve, wt%	26	36	26	26	36	26	26	36
Amorphous silica-alumina, wt%	51	41	51	51	41	51	51	41
									Aluminum oxide, wt%	23	23	23	23	23	23	23	23
Specific surface area, m2/g	496	516	415	408	390	510	382	516
									Pore volume, ml/g	0.59	0.63	0.51	0.47	0.46	0.62	0.41	0.64
Pore size distribution（4-10nm）, %	52	57	41.2	29.3	36.9	44.3	27.2	44.1
									Catalyst is numbered	CAT-1	CAT-2	CCAT-1	CCAT-2	CCAT-3	CCAT-4	CCAT-5	CCAT-6
Specific surface area, m2/g	395	409	301	296	280	411	260	415
									Pore volume, ml/g	0.52	0.55	0.40	0.38	0.36	0.54	0.32	0. 55
Pore size distribution（4-10nm）, %	50.5	53.1	36.2	26.6	34.7	40.1	23.9	43.2

By the invention described above catalyst CAT-1, CAT-2 and comparative example catalyst CCAT-1, CCAT-2, CCAT-3, CCAT- 4th, CCAT-5 and CCAT-6 carries out active evaluation test.Test is carried out on 200mL small hydrogenation device, is gone here and there using one section Connection>177 DEG C of fraction complete alternation technological processes, raw materials used oil nature is shown in Table 3.Operating condition is as follows：Hydrogen dividing potential drop 14.7MPa, hydrogen Oil volume compares 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 material oil nature

Feedstock oil	Iranian 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	CCAT-5	CCAT-6
									Reaction temperature, DEG C	364	360	374	372	371	371	376	369
Heavy naphtha（65～177 DEG C）
									Yield, wt%	71.1	73.1	66.1	65.8	67.3	68.4	63.6	69.1
Aromatic hydrocarbons, wt%	4.7	4.3	6.2	6.5	6.0	5.8	6.7	5.2
									Virtue is latent, %	53.4	56.6	48.1	47.6	49.2	50.1	48.9	51.9
C5 +Liquid is received, wt%	91.72	92.33	89.44	89.88	89.10	90.01	88.10	90.98
									Chemical hydrogen consumption	2.50	2.40	3.30	3.41	3.28	3.24	3.56	3.26

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 There is very high heavy naphtha yield, product property is good.

Claims (31)

1. a kind of hydrocracking catalyst, including hydrogenation active metals component with small-grain Y molecular sieve, amorphous silica-alumina and oxygen Change the carrier made of aluminium, wherein said small crystal grain Y-shaped molecular sieve, its property is as follows：SiO₂/A1₂O₃Mol ratio more than 10 and Less than 40, average grain diameter be 200～700nm, relative crystallinity more than 100%, lattice constant 2.430～2.450nm, Specific surface area is 850～1000m²/ g, pore volume is 0.50～0.80mL/g, and the pore volume shared by the secondary pore of 1.7～10nm accounts for always More than 50%, Na of pore volume₂O content≤0.15wt%.

2. according to the catalyst described in claim 1 it is characterised in that the SiO of described small crystal grain Y-shaped molecular sieve₂/A1₂O₃Rub That ratio is 15 ~ 38.

3. according to the catalyst described in claim 1 it is characterised in that in described small crystal grain Y-shaped molecular sieve, 1.7～10nm's Pore volume shared by secondary pore accounts for the 50% ~ 65% of total pore volume.

4. according to the catalyst described in claim 1 it is characterised in that the lattice constant of described small crystal grain Y-shaped molecular sieve 2.435～2.445nm.

5. according to the catalyst described in claim 1 it is characterised in that the relative crystallinity of described small crystal grain Y-shaped molecular sieve is 100%~120%.

6. according to the catalyst described in claim 1 it is characterised in that SiO in described amorphous silica-alumina₂Weight content be 20%～60%, the pore volume of amorphous silica-alumina is 0.6～1.1 mL/g, and specific surface area is 300～500 m²/g.

7. according to the catalyst described in claim 1 it is characterised in that described hydrocracking catalyst property is as follows：Specific surface area It is 300～500 m²/ g, pore volume is 0.35～0.60 mL/g, and the pore volume of aperture 4 ~ 10nm accounts for the 40%～70% of total pore volume.

8. according to the catalyst described in 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 15wt%～50wt%, and the content of amorphous silica-alumina is 20wt%～60wt%, the content of aluminum oxide is 10wt%～30wt%.

9. according to the catalyst described in 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 20wt%～40wt%, and the content of amorphous silica-alumina is 30wt%～50wt%, the content of aluminum oxide is 15wt%～30wt%.

10. according to the catalyst described in 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.

11. according to the catalyst described in claim 10 it is characterised in that on the basis of the weight of catalyst, vib metals The content counted with oxide as 10wt%～content counted with oxide of 30wt% and group VIII metal as 4wt%～10wt%, carrier Content be 61wt%～86wt%.

The preparation method of the arbitrary described catalyst of 12. claims 1 ~ 11, including：By small-grain Y molecular sieve, amorphous silica-alumina and The adhesive mechanical mixture made with aluminum oxide, shaping, are then dried and roasting, make catalyst carrier；The catalyst of gained Supported on carriers hydrogenation active metals component, drying and roasting, make catalyst.

13. in accordance with the method for claim 12 it is characterised in that the preparation method of described small crystal grain Y-shaped molecular sieve, including：

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

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

（3）By step（2）The fine grain NaY type molecular sieve obtaining is prepared into Na₂Little crystal grain NH of O content≤2.5wt%₄NaY；

（4）To step（3）Obtain little crystal grain NH₄NaY molecular sieve carries out hydro-thermal process；

（5）By step（4）The molecular sieve obtaining is with containing NH₄ ⁺And H⁺Mixed solution process, scrubbed and be dried, obtain little crystalline substance Grain Y type molecular sieve；

Wherein step（1）Described small crystal grain NaY molecular sieve, its property is as follows： SiO₂/Al₂O₃Mol ratio is not more than 6.0 and high In 9.0, average grain diameter is 200～700nm, specific surface 800～1000 m²/ g, pore volume 0.30～0.45mL/g, tie relatively Brilliant degree is 90%～130%, and cell parameter is 2.460～2.470nm, through relative crystallinity after 650 DEG C of in the air roastings 3 hours For more than 90%, it is more than 90% through relative crystallinity after 700 DEG C of water vapour hydro-thermal process 2 hours.

14. in accordance with the method for claim 13 it is characterised in that：The SiO of described small crystal grain NaY molecular sieve₂/Al₂O₃Rub That ratio is 6.5～9.0.

15. in accordance with the method for claim 13 it is characterised in that：The SiO of described small crystal grain NaY molecular sieve₂/Al₂O₃Rub That ratio is 7.0～8.0.

16. in accordance with the method for claim 13 it is characterised in that：Described small crystal grain NaY molecular sieve is through 650 DEG C of in the airs After roasting 3 hours, relative crystallinity is 90%～110%, through relative crystallinity after 700 DEG C of water vapour hydro-thermal process 2 hours is 90%～110%.

17. in accordance with the method for claim 13 it is characterised in that step（1）The preparation of described small crystal grain NaY molecular sieve Method, including：

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 is stirred at 0～20 DEG C ageing 0.5～24 hour and is obtained and lead To agent；

II, adopt 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 silica as 40wt%～75wt%；Its preparation process includes：

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

The part sodium silicate solution 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 controlling cemented into bundles is 8 ~ 11；Wherein as the CO being passed through₂Gas flow accounts 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 silica Meter accounts for step b and adds 5wt% ~ 85wt% in terms of silica for the sodium silicate solution total amount；

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

III, prepare silica-alumina gel：Press (0.5～6) Na₂O：Al₂O₃：(8～15) SiO₂：(100～460) H₂O always feeds intake mole Than, 0～40 DEG C quick stir under conditions of to the amorphous silica-alumina predecessor of step II gained in add water, silicon source, guiding 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,

IV, the reactant mixture of step III gained are through two step dynamic crystallizations, then through filtering, wash, and are dried, obtain little crystal grain NaY molecular sieve.

18. in accordance with the method for claim 17 it is characterised in that in step II, amorphous silica-alumina predecessor, with amorphous On the basis of the weight of the butt of sial predecessor, the content that silicon is counted with silica is for 55 wt%～70wt%.

19. in accordance with the method for claim 17 it is characterised in that：Step b controlling reaction temperature is 15～35 DEG C.

20. in accordance with the method for claim 17 it is characterised in that：In step b, as the CO being passed through₂Gas flow accounts for total intake 80% ~ 100% when, add remainder sodium silicate solution.

21. in accordance with the method for claim 17 it is characterised in that：In step b, remainder sodium silicate solution is with titanium dioxide Silicon meter accounts for step b and adds 30wt% ~ 70wt% in terms of silica for the sodium silicate solution total amount.

22. in accordance with the method for claim 17 it is characterised in that in step I and III, silicon source, alkali source are respectively selected from silicic acid Sodium and NaOH, in step I, silicon source is selected from sodium metaaluminate.

23. in accordance with the method for claim 17 it is characterised in that in step III, 10 ~ 30 DEG C of controlling reaction temperature, pH value 10～11.

24. in accordance with the method for claim 17 it is characterised in that step IV adopts two step dynamic crystallizations, the wherein 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.

25. in accordance with the method for claim 17 it is characterised in that step IV adopts two step dynamic crystallizations, the wherein 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 changed is as follows：At 80～120 DEG C, crystallization time is 5～10 hours to temperature control.

26. in accordance with the method for claim 13 it is characterised in that step（2）In, by the water of small crystal grain NaY molecular sieve and alkali Solution making beating mixes, and maintains stir process 1～4h under 60～120 DEG C of temperature conditionss；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 in slurries, the concentration of molecular sieve is 0.05～1.0g/mL.

27. in accordance with the method for claim 13 it is characterised in that step（4）In, the condition of described hydro-thermal process is as follows： Treatment temperature controls at 500～750 DEG C, and pressure is 0.01～0.50MPa, and process time is 1.0～4.0 hours.

28. in accordance with the method for claim 13 it is characterised in that step（4）In, the condition of described hydro-thermal process is as follows： Treatment temperature controls at 600～700 DEG C, and pressure is 0.05～0.30MPa, and process time is 1.0～4.0 hours.

29. in accordance with the method for claim 13 it is characterised in that step（5）In, by the molecular sieve after hydro-thermal process and acid With containing NH₄ ⁺Salt composition mixed solution contact, acid therein is one or more of hydrochloric acid, carbonic acid, nitric acid, sulfuric acid, contains NH₄ ⁺Salt be one or more of 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 slurries in molecular sieve concentration be 0.1～ 0.5g/mL, swap time is 0.5～3.0 hour, and exchange step repeats 1～4 time.

30. in accordance with the method for claim 13 it is characterised in that：Step（3）The method being exchanged using ammonium salt, process is such as Under：With NaY molecular sieve as raw material, exchanged 0.5～3.0 hour at 70～120 DEG C with the aqueous solution of soluble ammonium salt, molecular sieve Concentration in exchanging slurries is 0.05～0.50g/mL, repeated exchanged l～5 time, filters off mother liquor, washing, is dried；Ammonium salt is chlorine Change one or more of ammonium, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate, the concentration of ammonium salt solution For 0.5～5.0mol/L.

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