CN104588122A - Hydrocracking catalyst carrier and preparation method thereof - Google Patents

Abstract

The invention discloses a hydrocracking catalyst carrier and a preparation method thereof. The catalyst carrier comprises small-grain Y-type molecular sieve, alumina, and amorphous silica-alumina. According to the preparation method, the small-grain Y-type molecular sieve with high dealumination depth, good crystallinity maintenance and developed secondary pores is adopted as an acidic component, and cooperates with amorphous silica-alumina in the hydrocracking catalyst. According to the invention, the catalyst has better activity, better stability, higher target product selectivity and better product quality.

Description

A kind of carrier of hydrocracking catalyst and preparation method thereof

technical field

The present invention relates to a kind of carrier of hydrocracking catalyst and preparation method thereof.

Background technology

Along with the demand of international refined products market to intermediate oil constantly increases, need from mink cell focus, to obtain intermediate oil more, and one of the important means of hydrocracking process light materialization of heavy oil just.Due to this technique, to have adaptability to raw material strong, good product quality, adjustment flexible operation, midbarrel product yield is high, the features such as product structure is flexible, the status of hydrocracking process is made to become more and more important, being faced with petroleum resources shortage, environmental requirement increasingly stringent and oil product structure at present for China is not suitable with the problems such as market especially, the application of hydrocracking technology, by becoming the effective technology measure improving petroleum product-quality, reduce environmental pollution, increase market adaptability to changes, has become the of paramount importance process unit in modernization refinery.These factors facilitate 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 for metal active constituent provides dispersion place, carrier itself also participates in reaction simultaneously, whole catalytic reaction has been worked in coordination with together with other active component, hydrocracking catalyst is a kind of bifunctional catalyst, and it is simultaneously containing acidic components and hydrogenation component.Hydrogenation activity is generally selected from VI B race in the periodic table of elements and group VIII metal provides; And its acidic components are mainly provided by zeolite and inorganic oxide, major part be with aluminium oxide or amorphous aluminum silicide for carrier, be equipped with a certain amount of molecular sieve.And the key component playing cracking in this type of catalyst is generally Y molecular sieve, the quality of Y molecular sieve performance, directly affects performance and the product quality of catalyst.

Y zeolite is cracking active component the most general in residual oil cracking field at present, crystal grain is generally about 1000nm, its crystal grain is larger, duct is relatively long, diffusional resistance is large, large molecule is difficult to enter inside, duct and reacts, and afterproduct is also more difficult diffuses out, so its cracking activity and the selective of object product receive restriction in reaction.Compared with conventional Y zeolite, small crystal grain Y-shaped molecular sieve has larger external surface area and Geng Duo outer surface activated centre, is conducive to improving large molecule hydrocarbon cracking capability, thus has more superior catalytic perfomance.Meanwhile, reduce Y zeolite crystallite dimension and can also improve inner surface active sites utilization rate.In general, the diffusion of reactant molecule in molecular sieve endoporus duct is called micropore diffusion.Make molecular sieve inner surface all be used to carry out catalyzed conversion, micropore diffusion speed must be made to be greater than endoporus catalyzed conversion speed.Shortening diffusion path is the best way.The effective way overcoming micropore diffusion restriction reduces zeolite crystal size.This not only can increase the external surface area of zeolite crystal, and shortens diffusion length simultaneously.EP0204236 compares small crystal grain NaY molecular sieve and large grain size NaY molecular sieve, and result shows, the former has higher activity and selective preferably to RFCC.

Small crystal grain NaY molecular sieve does not possess acidity, needs to carry out modification, to meet the performance requirement of Cracking catalyst.CN1382632A discloses a kind of super stabilizing method of small-grain Y-type zeolite, the method uses dry gas and the fine grain NaY zeolitic contact of silicon tetrachloride, obtain after washing, due to the heat of its raw material self and hydrothermal stability just poor, the method is the mode process molecular sieve adopting gas phase dealumination complement silicon simultaneously, this make the heat of product and hydrothermal stability poorer, active low.Especially to heat endurance and the poor fine grain NaY zeolite of hydrothermal stability, sial skeleton structure less stable in zeolite, be easy to cause removing of framework aluminum in modifying process, simultaneously also some framework silicon also along with removing, part skeleton is caused to occur the phenomenon of caving in, make the crystallization reservation degree of product lower, the activity of zeolite is not high.

CN200910188140.5 discloses a kind of hydrocracking catalyst and preparation method thereof.This catalyst comprises the carrier of hydrogenation active metals component and small-grain Y molecular sieve, amorphous aluminum silicide and aluminium oxide composition, and wherein said small crystal grain Y-shaped molecular sieve is the small crystal grain Y-shaped molecular sieve after adopting hydrothermal treatment consists.Raw materials used small crystal grain NaY molecular sieve is prepared for method disclosed in CN101722023A, i.e. SiO ₂/ Al ₂o ₃mol ratio is 4.0 ~ 6.0, and average grain diameter, at 100 ~ 700nm, successively by the mixed aqueous solution process of successive modified i.e. ammonium exchange, ammonium hexafluorosilicate dealumination complement silicon, hydrothermal treatment consists, aluminium salt and acid, obtains small-grain Y molecular sieve.In the method, need first to raw material with after the process of ammonium hexafluorosilicate dealumination complement silicon, then carry out the process such as hydrothermal treatment consists, could reduce caving in of the skeleton structure of molecular sieve like this, improve crystallization the reservations degree of molecular sieve, but the method is due to after first using the process of ammonium hexafluorosilicate dealumination complement silicon, due to generation sial same order elements, molecular sieve silica constructed of aluminium is more complete, carry out hydrothermal treatment consists again, the secondary pore of formation is few, and secondary pore proportion is low, divide as catalyst molecule screen banks, middle oily yield is low.

Existing method fine grain NaY type molecular sieve is in preparation process, and Silicified breccias easily runs off, and silicon utilization rate is low, and silicon, aluminium distributing inhomogeneity, easy appearance is reunited, and therefore still cannot to prepare silica alumina ratio high for existing method, and the fine grain NaY type molecular sieve that heat endurance and hydrothermal stability are good again.Through successive modified, can not obtain structural integrity, degree of crystallinity is high and have the small crystal grain Y-shaped molecular sieve of more secondary pore, and as the cracking component of catalyst, middle oily yield is low.

Summary of the invention

For weak point of the prior art, the invention provides good carrier of hydrocracking catalyst of a kind of catalytic performance and preparation method thereof.This carrier of hydrocracking catalyst adopts that a kind of high silica alumina ratio, high-crystallinity, secondary pore are many, the small crystal grain Y-shaped molecular sieve of bigger serface as acidic components, be conducive to improving the active and middle distillates oil selectivity of hydrocracking catalyst and improve product property.

Carrier of hydrocracking catalyst of the present invention, comprises small-grain Y molecular sieve, aluminium oxide and amorphous aluminum silicide, and wherein said small-grain Y molecular sieve, its character is as follows: SiO ₂/ A1 ₂o ₃mol ratio is 40 ~ 120, and average grain diameter is 200 ~ 700nm, preferably 300 ~ 500nm, and relative crystallinity, more than 100%, is preferably 100% ~ 120%, lattice constant 2.425 ~ 2.450nm, and be preferably 2.425 ~ 2.440, specific area is 850 ~ 1000m ²/ g, pore volume is the pore volume shared by secondary pore of 0.40 ~ 0.60mL/g, 1.7 ~ 10nm is more than 50% of total pore volume, is preferably 50% ~ 80%, more preferably 55% ~ 75%, Na ₂o content≤0.15wt%.

Carrier of hydrocracking catalyst character of the present invention is as follows: specific area is 450 ~ 650 m ²/ g, pore volume is 0.5 ~ 0.80 mL/g, and the pore volume of aperture 4 ~ 10nm accounts for 55% ~ 90% of total pore volume, is preferably 65% ~ 80%.

In described carrier of hydrocracking catalyst, with the weight of carrier for benchmark, its composition comprises: the content of small crystal grain Y-shaped molecular sieve is 5wt% ~ 40wt%, be preferably 10wt% ~ 25wt%, the content of amorphous aluminum silicide is 20wt% ~ 65wt%, be preferably 30wt% ~ 60wt%, the content of aluminium oxide is 10wt% ~ 40 wt%, is preferably 15wt% ~ 30wt%.

The preparation method of carrier of hydrocracking catalyst of the present invention, comprising: by small crystal grain Y-shaped molecular sieve, amorphous aluminum silicide and the adhesive mixing made from aluminium oxide, extruded moulding, then drying and roasting, make carrier.

Small-grain Y molecular sieve described in catalyst carrier of the present invention, comprises following preparation process:

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

(2) fine grain NaY type molecular sieve is become Na ₂the little crystal grain NH of O content≤2.5wt% ₄naY;

(3) little crystal grain NH is obtained to step (2) ₄naY molecular sieve carries out hydrothermal treatment consists;

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

(5) molecular sieve step (4) obtained is with containing NH ₄ ⁺and H ⁺mixed solution process, then washing and dry, obtains small crystal grain Y-shaped molecular sieve.

Small crystal grain NaY molecular sieve described in step (1), its character is as follows: SiO ₂/ Al ₂o ₃mol ratio is greater than 6.0 and not higher than 9.0, and preferably 6.5 ~ 9.0, more preferably 7.0 ~ 8.0, average grain diameter is 200 ~ 700nm, preferably 300 ~ 500nm; Specific area is 800 ~ 1000 m ²/ g, is preferably 850 ~ 950 m ²/ g, pore volume 0.30/ ~ 0.45mL/g, relative crystallinity is 90% ~ 130%, cell parameter is 2.460 ~ 2.470nm, through roasting in 650 DEG C of air after 3 hours relative crystallinity be more than 90%, be generally 90% ~ 110%, be preferably 90% ~ 105%, through 700 DEG C of water vapour hydrothermal treatment consists after 2 hours relative crystallinity be more than 90%, be generally 90% ~ 110%, be preferably 90% ~ 105%.

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

I, preparation directed agents: silicon source, aluminium source, alkali source and water are fed intake according to following proportioning: (6 ~ 30) Na ₂o:Al ₂o ₃: (6 ~ 30) SiO ₂: (100 ~ 460) H ₂o, after stirring, stirs ageing 0.5 ~ 24 hour obtained directed agents at 0 ~ 20 DEG C by mixture;

II, employing preparing amorphous silicon alumnium using carbonization predecessor, with the weight of the butt of amorphous aluminum silicide predecessor for benchmark, silicon for 40wt% ~ 75wt%, is preferably 55 wt% ~ 70wt% in the content of silica; Its preparation process comprises:

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

B, to step a preparation sodium aluminate solution in add step a preparation part sodium silicate solution, then pass into CO ₂gas, controlling reaction temperature is 10 ~ 40 DEG C, is preferably 15 ~ 35 DEG C, and the pH value controlling cemented into bundles is 8 ~ 11; Wherein as the CO passed into ₂gas flow accounts for 60% ~ 100% of total intake, when being preferably 80% ~ 100%, add remainder sodium silicate solution, wherein in step b, remainder sodium silicate solution accounts for step b in silica and adds sodium silicate solution total amount in the 5wt% ~ 85wt% of silica, is preferably 30wt% ~ 70wt%;

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

III, prepare silica-alumina gel

By (0.5 ~ 6) Na ₂o:Al ₂o ₃: (8 ~ 15) SiO ₂: (100 ~ 460) H ₂total molar ratio of O, under the condition of 0 ~ 40 DEG C of rapid stirring, add water, silicon source, directed agents and alkali source in the amorphous aluminum silicide predecessor of step (2) gained, and control ph is 9.5 ~ 12.0, uniform stirring, obtains silica-alumina gel; Wherein directed agents addition accounts for 1% ~ 20% of silica-alumina gel weight,

The reactant mixture of IV, Step II I gained is through two step dynamic crystallizations, more after filtration, washing, drying, obtains small crystal grain NaY molecular sieve.

In the present invention, in step I and III, silicon source, alkali source are selected from sodium metasilicate and NaOH respectively.In step I, aluminium source is selected from sodium metaaluminate.

In Step II, the concentration of the sodium aluminate solution that step a is used is for being preferably 15 ~ 55g Al ₂o ₃/ l, the concentration of sodium silicate solution is 50 ~ 150 gSiO ₂/ l, step b CO used ₂the concentration of gas is 30v% ~ 60v%.

In Step II I, control reaction temperature 0 ~ 40 DEG C, 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 wherein to carry out the condition of dynamic crystallization as follows for the first step: temperature controls at 50 ~ 90 DEG C, and crystallization time is 0.5 ~ 18 hour; The condition that second step carries out dynamic crystallization is as follows: temperature controls at 80 ~ 140 DEG C, and crystallization time is 3 ~ 10 hours, after crystallization completes, more after filtration, washing, dry, obtained 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 hour; Second step: temperature controls at 80 ~ 120 DEG C, crystallization time is 5 ~ 10 hours.

In step (3), the condition of described hydrothermal treatment consists is as follows: treatment temperature controls at 500 ~ 750 DEG C, preferably controls at 600 ~ 700 DEG C, and pressure is 0.01 ~ 0.50MPa, and be preferably 0.05 ~ 0.30MPa, the processing time is 1.0 ~ 4.0 hours.

In step (4), in aqueous medium, add little crystal grain NH ₄naY molecular sieve (solid-liquid weight ratio 1:4 ~ 1:8), stirs and is warmed up to 90 ~ 120 DEG C, being then added dropwise to hexafluorosilicic acid aqueous ammonium, and after dropwising, constant temperature stirs 1 ~ 2 hour, isolated molecule sieve and accessory substance, and filter, dry.Concentration 10wt% ~ the 40wt% of hexafluorosilicic acid aqueous ammonium, ammonium hexafluorosilicate addition is little crystal grain NH ₄10wt% ~ the 50wt% of NaY molecular sieve

In step (5), by the molecular sieve after hydrothermal treatment consists with acid with containing NH ₄ ⁺the mixed solution contact of salt composition, exchange the Na in molecular sieve ⁺with the part non-framework aluminum removed in molecular sieve, acid wherein can be one or more in hydrochloric acid, carbonic acid, nitric acid, sulfuric acid, containing NH ₄ ⁺salt be containing above acid group ammonium salt in one or more; H in mixed solution ⁺concentration be 0.05 ~ 0.6mol/L, NH ₄ ⁺concentration be 0.5 ~ 3.0mol/L, exchange temperature is 70 ~ 120 DEG C, and the concentration exchanging slurries Middle molecule sieve is 0.1 ~ 0.5g/mL, and swap time is 0.5 ~ 3.0 hour, and exchange step can repeat 1 ~ 4 time.Then remove mother liquor, wash with water, dry.

Other operating procedure in modified Y molecular sieve preparation method of the present invention, as ammonium salt exchanges method of operating and the condition that can adopt this area routine, specific as follows: to take NaY molecular sieve as raw material, with the aqueous solution of solubility ammonium salt as ammonium chloride, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate etc., the concentration of ammonium salt solution is 0.5 ~ 5.0mol/L.At 70 ~ 120 DEG C, preferably exchange 0.5 ~ 3.0 hour at 80 ~ 100 DEG C, Y molecular sieve is 0.05 ~ 0.50g/mL exchanging the concentration in slurries, repeated exchanged l ~ 5 time, elimination mother liquor, and washing is dry.

Adhesive therefor of the present invention is made up of little porous aluminum oxide and inorganic acid and/or organic acid.Aperture aluminium oxide pore volume used is 0.3 ~ 0.5 mL/g, and specific area is 200 ~ 400m ²/ g.

Amorphous aluminum silicide used in catalyst carrier of the present invention can be prepared by coprecipitation or grafting copolymerization process, prepares by conventional method in document.SiO in obtained amorphous aluminum silicide ₂weight content be 20% ~ 60%, be preferably 25% ~ 40%, the pore volume of amorphous aluminum silicide is 0.6 ~ 1.1 mL/g, be preferably 0.8 ~ 1.0 mL/g, specific area is 300 ~ 500 m ²/ g, is preferably 350 ~ 500 m ²/ g.

Catalyst of the present invention can carry out shaping according to actual needs, and shape can be cylindrical bars, clover etc.In shaping of catalyst process, shaping assistant can also be added, as peptization acid, extrusion aid etc.Catalyst carrier of the present invention adopted conventional method to carry out drying and roasting, specific as follows: through 80 ~ 150 DEG C of dryings 3 ~ 10 hours, 500 ~ 600 DEG C of roastings 3 ~ 6 hours.

When catalyst carrier of the present invention is for the preparation of hydrocracking catalyst, carrying method conventional in prior art can be adopted, preferred infusion process, can be saturated leaching, excessive leaching or complexing leaching, namely with the solution impregnated catalyst carrier containing required active component, carrier after dipping, after super-dry, roasting, obtains final hydrocracking catalyst.

Carrier of hydrocracking catalyst of the present invention is owing to adopting small crystal grain Y-shaped molecular sieve as acidic components, this molecular sieve has that high silica alumina ratio, high-crystallinity, secondary pore are many, the feature of bigger serface, match with amorphous aluminum silicide, be particularly suitable as middle oil type hydrocracking catalyst carrier.

In carrier of hydrocracking catalyst preparation method of the present invention, small-grain Y molecular sieve used, the silica alumina ratio of its NaY type Molecular sieve raw material is higher, degree of crystallinity is high, good stability, so in follow-up modification process, especially before dealumination complement silicon, just hydrothermal treatment consists is carried out, be conducive to the ratio shared by secondary pore improving molecular sieve like this, and make molecular sieve still keep good stability through hydrothermal treatment consists due to the particularity of raw material, also be conducive to follow-up dealumination complement silicon, acid-treatedly carry out, and do not affect the stability of final molecular sieve.The small crystal grain Y-shaped molecular sieve prepared by method provided by the invention is obtaining higher SiO ₂/ A1 ₂o ₃while mol ratio, the ratio shared by secondary pore is higher, and maintains the stability of Y zeolite, and molecular sieve has higher specific area and higher degree of crystallinity.Small crystal grain Y-shaped molecular sieve of the present invention is as Cracking Component, be conducive to improving the large molecule diffusion rate in the catalyst in raw material, the performance of molecular sieve as acid cracking center can be played better, avoid second pyrolysis, reduce carbon deposit, thus catalyst can be made to have the product property of good activity, middle distillates oil selectivity and excellence.

Small crystal grain molecular sieve is adopted to be Cracking Component in addition in carrier of the present invention, there is larger external surface area and Geng Duo outer surface activated centre, be conducive to improving large molecule hydrocarbon cracking capability, the activity that can to make by this molecular sieve be the hydrocracking catalyst of active component increases, simultaneously can the performance of promoting catalyst Hydrogenation better.

Detailed description of the invention

In order to better the present invention is described, further illustrate the present invention below in conjunction with embodiment and comparative example.But scope of the present invention is not only limited to the scope of these embodiments.Analytical method of the present invention: specific area, pore volume adopt low temperature liquid nitrogen physisorphtion, relative crystallinity and cell parameter adopt x-ray diffraction method, silica alumina ratio adopts chemical method, and the grain size of molecular sieve adopts the mode of SEM (SEM) to measure.Wt% is mass fraction.

Embodiment 1

The present embodiment is raw materials fine grain NaY type molecular sieve

The preparation of NY-1

(1) preparation of directed agents: get 8g sodium hydrate solid and be dissolved in 80g water, adds sodium metaaluminate 2.5 g (Al ₂o ₃content is 45wt%, Na ₂o content is 41wt%), and then add 40g waterglass (SiO ₂content is 28wt%, Na ₂o content is 8 wt%), stir ageing 4 hours obtained directed agents at 18 DEG C after mixing.

(2) preparation of amorphous aluminum silicide predecessor

Solid sodium aluminate being mixed with 0.3L concentration is 100g A1 ₂o ₃/ L sodium aluminate working solution (a).Concentrated ammonia liquor is added appropriate distilled water diluting into about 10wt% weak aqua ammonia (b).Get containing SiO ₂the sodium silicate solution of 28wt%, then to be diluted to 0.5L concentration be 140g SiO ₂/ L sodium metasilicate working solution (c).Get the steel retort of one 5 liters, 0.5 liter of distilled water is added and after being heated with stirring to 70 DEG C in tank, open the valve having (a) and (b) and (c) Sulfur capacity device respectively simultaneously, control the flow of (a) and (c) to make the neutralization reaction time at 40 minutes, and the flow of adjustment (b) rapidly makes the pH value of system remain on 7 ~ 8, and the temperature of the hierarchy of control is at about 60 DEG C.After reacting aluminum sulfate completes, stop adding (b), the addition of (c) is 0.17L, after the silicon-aluminum sol of generation stablizes 20 minutes, continue to add (c) 0.33L, add in 10 minutes, start the ageing process of system, keep pH value 8.0, temperature 60 C, aging 30 minutes.

(3) preparation of gel

1L H is added in the slurries that step (2) obtains ₂o, 140g SiO ₂directed agents 100g prepared by/L sodium metasilicate working solution 0.6L and step (1), the pH value of gel is 11.5, and control reaction temperature 15 DEG C, uniform stirring 30 minutes, staticizes 2.5 hours.

(4) crystallization

The gel that step (2) obtains is poured in stainless steel cauldron, stirs crystallization 5 hours at 75 DEG C, be then warming up to 110 DEG C, stir crystallization 7 hours, then filter, wash, dry NaY molecular sieve product NY-1, character lists in table l.

The preparation of NY-2

(1) preparation of directed agents: get 10 g sodium hydrate solids and be dissolved in 90g water, adds sodium metaaluminate 3 g (Al ₂o ₃content is 45wt%, Na ₂o content is 41wt%), and then add 50g waterglass (SiO ₂content is 28wt%, Na ₂o content is 8wt%), stir ageing 4 hours obtained directed agents at 20 DEG C after mixing.

(2) preparation of amorphous aluminum silicide predecessor

Solid aluminum sulfate being mixed with 0.5L concentration is 80g A1 ₂o ₃/ L aluminum sulfate working solution (a).Concentrated ammonia liquor is added appropriate distilled water diluting into about 10wt% weak aqua ammonia (b).Get containing SiO ₂the sodium silicate solution of 28wt%, then to be diluted to 0.4L concentration be 150g SiO ₂/ L sodium metasilicate working solution (c).Get the steel retort of one 5 liters, 0.5 liter of distilled water is added and after being heated with stirring to 70 DEG C in tank, open the valve having (a) and (b) and (c) container respectively simultaneously, control the flow of (a) and (c) to make the neutralization reaction time at 40 minutes, and the flow of adjustment (b) rapidly makes the pH value of system remain on 7 ~ 8, and the temperature of the hierarchy of control is at about 60 DEG C.After reacting aluminum sulfate completes, stop adding (b), the addition of (c) is 0.2L, after the silicon-aluminum sol of generation stablizes 20 minutes, continue to add (c) 0.2L, add in 10 minutes, start the ageing process of system, keep pH value 8.0, temperature 60 C, aging 30 minutes.

(3) preparation of gel

1.2L H is added in the slurries that step (2) obtains ₂o, 150g SiO ₂directed agents 120g prepared by/L sodium metasilicate working solution 0.8L and step (1), the pH value of gel is 12, and control reaction temperature 30 DEG C, uniform stirring 30 minutes, staticizes 3 hours.

(4) crystallization

The gel that step (2) obtains is poured in stainless steel cauldron, stirs crystallization 6 hours at 80 DEG C, be then warming up to 120 DEG C, stir crystallization 5 hours, then filter, wash, dry NaY molecular sieve product NY-2, character lists in table l.

Embodiment 2

First ammonium exchange is carried out to raw material small crystal grain NaY molecular sieve NY-1.Compound concentration is 0.5mol/L aqueous ammonium nitrate solution 10 liters.Take small crystal grain NaY molecular sieve 1000 grams, join in 10 liters of aqueous ammonium nitrate solutions prepared, speed of agitator is 300rpm, and at 90 DEG C, constant temperature stirs l hour, then filtering molecular sieve, and stays sample, analyzes Na ₂o content; Repeat aforesaid operations, until Na in molecular sieve ₂o content reach 2.5wt%, obtaining dried sample number into spectrum is NNY-1.

Embodiment 3

First ammonium exchange is carried out to raw material small crystal grain NaY molecular sieve NY-2.Compound concentration is 0.8mol/L aqueous ammonium nitrate solution 10 liters.Take small crystal grain NaY molecular sieve 1000 grams, join in 10 liters of aqueous ammonium nitrate solutions prepared, speed of agitator is 300rpm, and at 95 DEG C, constant temperature stirs l hour, then filtering molecular sieve, and stays sample, analyzes Na ₂o content; Repeat aforesaid operations, until Na in molecular sieve ₂the content of O reaches 2.5wt%, and obtaining dried sample number into spectrum is NNY-2.

Embodiment 4

Get 100 grams of NNY-1 and be placed in heat-treatment furnace, control the heating rate of 500 DEG C/h, temperature is risen to 600 DEG C, the water vapor pressure simultaneously maintaining system is 0.15MPa, processes 2 hours, and sample is taken out in cooling; Sample deionized water is pulled an oar, and stir condition under rapid temperature increases to 95 DEG C, then in 2 hours, the aqueous solution configured by 25 grams of ammonium hexafluorosilicate and 150m1 deionized water is dripped with uniform speed, add rear slurry constant temperature 2 hours under 95 DEG C of stirring conditions, leave standstill 10 minutes, through 3 washings, filter; Filter cake 500mL is contained NH ₄ ⁺and H ⁺the concentration mixed solution (ammonium chloride and hydrochloric acid) that is respectively 0.6mol/L and 0.1mol/L process, remove the non-framework aluminum in sample, dealuminzation condition is 80 DEG C of process 2 hours, and use hot deionized water washing leaching cake, with the pH value of cleaning solution close to stopping the 120 DEG C of dryings 5 hours in an oven of washing, filter cake after 7, obtain the physico-chemical property of modification small-grain Y-1, Y-1 in table 1.

Embodiment 5

Get 100 grams of NNY-1 molecular sieves and be placed in heat-treatment furnace, control the heating rate of 400 DEG C/h, 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 deionized water is pulled an oar, and stir condition under rapid temperature increases to 90 DEG C, then in 2 hours, the aqueous solution configured by 30 grams of ammonium hexafluorosilicate and 150m1 deionized water is dripped with uniform speed, add rear slurry constant temperature 2 hours under 90 DEG C of stirring conditions, leave standstill 10 minutes, through 3 washings, filter; Filter cake 400mL is contained NH ₄ ⁺and H ⁺the concentration mixed solution (ammonium nitrate and nitric acid) that is respectively 0.8mol/L and 0.2mol/L process, remove the non-framework aluminum in sample, dealuminzation condition is process 3 hours at 70 DEG C, filter, and use hot deionized water washing leaching cake, with the pH value of cleaning solution close to stopping the 120 DEG C of dryings 5 hours in an oven of washing, filter cake after 7, obtain the physico-chemical property of modification small-grain Y-2, Y-2 in table 1.

Embodiment 6

Get 100 grams of NNY-2 molecular sieves and be placed in heat-treatment furnace, control the heating rate of 400 DEG C/h, 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 deionized water is pulled an oar, and stir condition under rapid temperature increases to 100 DEG C, then in 2 hours, the aqueous solution configured by 20 grams of ammonium hexafluorosilicate and 150m1 deionized water is dripped with uniform speed, add rear slurry constant temperature 2 hours under 100 DEG C of stirring conditions, leave standstill 10 minutes, through 3 washings, filter; Filter cake 400mL is contained NH ₄ ⁺and H ⁺the concentration mixed solution (ammonium chloride and hydrochloric acid) that is respectively 1.0mol/L and 0.2mol/L process, remove the non-framework aluminum in sample, dealuminzation condition is at 75 DEG C, process 3 hours filter, and use hot deionized water washing leaching cake, with the pH value of cleaning solution close to stopping the 120 DEG C of dryings 6 hours in an oven of washing, filter cake after 7, obtain modification small-grain Y-3.The physico-chemical property of Y-3 is in table 1.

Embodiment 7

By 25 grams of Y-1 molecular sieves (butt 90wt%), 106.5 grams of amorphous aluminum silicides (pore volume 0.9ml/g, than

Surface area 350m ²/ g, butt 70wt%), 120 grams of adhesive (butt 20wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.25) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier TCAT-1, character is in table 2.

Embodiment 8

By 30 grams of Y-2 molecular sieves (butt 90wt%), 100 grams of amorphous aluminum silicides (pore volume 0.9ml/g, than

Surface area 350m ²/ g, butt 70wt%), 120 grams of adhesive (butt 20wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.25) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier TCAT-2, character is in table 2.

Embodiment 9

By 40 grams of Y-3 molecular sieves (butt 90wt%), 90 grams of amorphous aluminum silicides (pore volume 0.9ml/g, specific area 350m ²/ g, butt 70wt%), 120 grams of adhesives (butt 20wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.25) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier TCAT-3.

The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, temperature programming 500 DEG C of roastings 4 hours, obtain catalyst CAT-3, and carrier and corresponding catalyst character are in table 2.

Comparative example 1

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

Feedstock property used in this comparative example is as follows: low alkali sodium metaaluminate: Na ₂o content 120g/L, Al ₂o ₃content 40g/L; Waterglass: SiO ₂content 250g/L; Aluminum sulfate: Al ₂o ₃content 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, 59.4mL aluminum sulfate, the low sodium metaaluminate of 62.7mL and 42.2mL directed agents is added successively in the waterglass of 208mL, then constant temperature constant speed stirs 1.5 hours, then by the synthesis liquid that obtains static aging 8 hours at the temperature disclosed above, gel is obtained.

(3) crystallization: under agitation, was raised to 50 DEG C by the gel in synthesis reactor in 20 minutes, and constant temperature stirs crystallization 7 hours; After low temperature crystallized end, in 20 minutes, the temperature in synthesis reactor is brought up to 120 DEG C, then constant temperature stirs 6 hours.After filtration, wash and drying, obtain the little crystal grain CNY-l of product.

2, carry out ammonium exchange to raw material small crystal grain NaY molecular sieve, treatment conditions are with embodiment 2, and obtaining dried sample number into spectrum is CNNY-1.

3, carry out subsequent treatment to CNNY-1, processing mode and condition, with embodiment 4, obtain Reference Product CY-1.The physico-chemical property of CY-1 is in table 1.

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

Surface area 350m ²/ g, butt 70wt%), 120 grams of adhesive (butt 20wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.25) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, carrier TCCAT-1 is obtained.

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

Comparative example 2

1, fine grain NaY is with reference to CN1785807A preparation.

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

Be positioned in beaker by 14.21g water, controlling fluid temperature in beaker is 60 DEG C, adds the A1 of 12.79g50wt% under rapid stirring simultaneously ₂(SO ₄) ₃) solution and 31.91g waterglass.After stirring, add above-mentioned directed agents 1.90g, the pH value of gel is 12.5, after stirring, loaded in stainless steel cauldron, stirred crystallization 6 hours at 60 DEG C, then be warming up to 100 DEG C of static crystallizations 60 hours, then filter, wash, dry CNY-2 molecular sieve.

2, carry out ammonium exchange to raw material small crystal grain NaY molecular sieve, treatment conditions are with embodiment 2, and obtaining dried sample number into spectrum is CNNY-2.

3, carry out subsequent treatment to CNNY-2, processing mode and condition, with embodiment 4, obtain Reference Product CY-2.The physico-chemical property of CY-2 is in table 2.

4, by 30 grams of CY-2 molecular sieves (butt 90wt%), 100 grams of amorphous aluminum silicides (pore volume 0.9ml/g, specific area 350m ²/ g, butt 70wt%), 120 grams of adhesive (butt 20wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.25) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier TCCAT-2, character is in table 2.

Comparative example 3

1, fine grain NaY preparation.

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

(2) preparation of amorphous aluminum silicide predecessor.

Solid sodium aluminate being mixed with concentration is 40gAl ₂o ₃/ L sodium aluminate working solution, gets containing SiO ₂the sodium silicate solution of 28wt%, then to be diluted to concentration be 100g SiO ₂/ L sodium metasilicate working solution.Get 1L sodium aluminate working solution and be placed in plastic cans, then add 0.6L sodium metasilicate working solution, control reaction temperature 20 DEG C, pass into the CO that concentration is 50v% ₂gas, stops logical CO when pH value reaches 10.0 ₂, then ventilate and stablize 20 minutes.

(3) preparation of gel is with embodiment 1.

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

2, carry out ammonium exchange to raw material small crystal grain NaY molecular sieve, treatment conditions are with embodiment 2, and obtaining dried sample number into spectrum is CNNY-3.

3, carry out subsequent treatment to CNNY-3, processing mode and condition, with embodiment 4, obtain Reference Product CY-3.The physico-chemical property of CY-3 is in table 2.

4, by 40 grams of CY-3 molecular sieves (butt 90wt%), 90 grams of amorphous aluminum silicides (pore volume 0.9ml/g, specific area 350m ²/ g, butt 70wt%), 120 grams of adhesive (butt 20wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.25) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier TCCAT-3, character is in table 2.

Comparative example 4

1, with comparative example 1 prepare CNNY-1 for raw material, then the method modification of CN200910165116.X is adopted, specific as follows: to get 100 grams of CNNY-1 100mL deionized water making beating, and stir condition under rapid temperature increases to 95 DEG C, then in 2 hours, the aqueous solution configured by 25 grams of ammonium hexafluorosilicate and 150m1 deionized water is dripped with uniform speed, add rear slurry constant temperature 2 hours under 95 DEG C of stirring conditions, leave standstill 10 minutes, through 3 washings, filter, dry; Sample after above-mentioned drying is placed in heat-treatment furnace, and control the heating rate of 500 DEG C/h, temperature is risen to 600 DEG C, the water vapor pressure simultaneously maintaining system is 0.15MPa, processes 2 hours, and sample is taken out in cooling; Final sample 400mL contains Al ³⁺and H ⁺the concentration mixed solution (aluminum nitrate and nitric acid) that is respectively 1.0mol/L and 0.5mol/L remove non-framework aluminum in sample, dealuminzation condition is 80 DEG C of process 2 hours, and use hot deionized water washing leaching cake, with the pH value of cleaning solution close to stopping the 120 DEG C of dryings 5 hours in an oven of washing, filter cake after 7, obtain CY-4.The physico-chemical property of CY-4 is in table 1.

2, by 40 grams of CY-4 molecular sieves (butt 90wt%), 90 grams of amorphous aluminum silicides (pore volume 0.9ml/g, specific area 350m ²/ g, butt 70wt%), 120 grams of adhesive (butt 20wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.25) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, carrier TCCAT-4 is obtained.

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

Comparative example 5

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

The feedstock property that in this comparative example, NaY is used is as follows: low alkali sodium metaaluminate: Na ₂o content 120g/L, Al ₂o ₃content 40g/L; Waterglass: SiO ₂content 250g/L; Aluminum sulfate: Al ₂o ₃content 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 adding 60mL aluminum sulfate, 60mL in the waterglass of 220mL successively, then constant temperature constant speed stirs 0.5 hour, obtained silica-alumina gel.

(3) crystallization: under agitation, was raised to 140 DEG C by the gel in synthesis reactor in 30 minutes, and constant temperature stirs crystallization 2 hours; Add 35mL directed agents, mixing and stirring, then continue crystallization 15 hours at 100 DEG C, after filtration, wash and drying, obtain products C NY-5, product property is in table 1.

2, carry out ammonium exchange to raw material small crystal grain NaY molecular sieve CNY-5, treatment conditions are with embodiment 2, and obtaining dried sample number into spectrum is CNNY-5.

3, carry out subsequent treatment to CNNY-5, processing mode and condition, with embodiment 4, obtain Reference Product CY-5.The physico-chemical property of CY-5 is in table 1.

4, by 30 grams of CY-5 molecular sieves (butt 90wt%), 100 grams of amorphous aluminum silicides (pore volume 0.9ml/g, specific area 350m ²/ g, butt 70wt%), 120 grams of adhesive (butt 20wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.25) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier TCCAT-5, carrier and corresponding catalyst character are in table 2.

 

Comparative example 6

1, get 100gNNY-1, NNY-1 of the present invention is adopted to the method modification of CN200910165116.X, concrete method of modifying, with comparative example 4, obtains Reference Product CY-6.The physico-chemical property of CY-6 is in table 1.

2, by 40 grams of CY-6 molecular sieves (butt 90wt%), 90 grams of amorphous aluminum silicides (pore volume 0.9ml/g, specific area 350m ²/ g, butt 70wt%), 120 grams of adhesive (butt 20wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.25) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, carrier TCCAT-6 is obtained.

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

 

The character of table 1 Y zeolite

Production code member	NY-1	NY-2	Y-1	Y-2	Y-3	CY-1	CY-2	CY-3	CY-4	CY-5	CY-6
												Feed intake SiO 2/Al 2O 3Mol ratio	9.1	10.1
SiO 2/Al 2O 3Mol ratio	7.5	8.4	66	84	105	50	25	28	63	24	65
												Specific area, m 2/g	916	898	950	990	1020	892	780	805	921	711	935
Pore volume, mL/g	0.39	0.38	0.53	0.58	0.62	0.33	0.32	0.34	0.48	0.30	0.51
												Secondary pore (1.7-10nm), %			62.1	66.4	71.1	37.1	27.5	35.2	42.1	25.2	46.0
External surface area, m 2/g	191	182	2161	249	240	170	159	190	189	145	209
												Lattice constant, nm	2.461	2.462	2.436	2.432	2.430	2.441	2.450	2.443	2.436	2.449	2.436
Relative crystallinity, %	101	110	115	118	116	95	80	85	116	78	117
												Average crystallite size, nm	380	430	380	380	430	400	450	400	400	450	400

The physico-chemical property of table 2 carrier and catalyst

Bearer number	TCAT-1	TCAT-2	TCAT-3	TCCAT-1	TCCAT-2	TCCAT-3	TCCAT-4	TCCAT-5	TCCAT-6
										Small-grain Y molecular sieve, wt%	18	22	29	29	29	22	22	29	22
Amorphous aluminum silicide, wt%	62	58	51	51	51	58	58	51	58
										Aluminium oxide, wt%	20	20	20	20	20	20	20	20	20
Specific area, m 2/g	493	500	516	435	418	420	460	382	478
										Pore volume, mL/g	0.59	0.60	0.62	0.50	0.46	0.44	0.53	0.42	0.55
Pore size distribution (4-10nm), %	64	65	72	45	43	40	50	38	52
										Catalyst is numbered			CAT-2	CCAT-1			CCAT-4		CCAT-6
Specific area, m 2/g			425	318			346		395
										Pore volume, mL/g			0.56	0.44			0.47		0.50
Pore size distribution (4-10nm), %			67	42			47		49

The invention described above catalyst CAT-3 and comparative example catalyst CCAT-1, CCAT-4, CCAT-6 are carried out active evaluation test.Test is carried out on 200ml small hydrogenation device, and adopt one-stage serial technological process, raw materials used oil nature is 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 μ g/g.Catalyst Activating Test the results are shown in Table 4.

Table 3 feedstock oil character

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

Table 4 catalyst activity evaluation result

Catalyst is numbered	CAT-3	CCAT-1	CCAT-4	CCAT-6
					Reaction temperature, DEG C	378	383	382	381
< 370 DEG C of conversion ratios, wt%	65.0	64.8	64.5	65.2
					Middle distillates oil selectivity, %(132 ~ 370 DEG C)	86.9	81.1	83.5	84.5
Major product character
					Jet fuel (132 ~ 282 DEG C)
Freezing point, DEG C	<－60	<－60	<－60	<－60
					Aromatic hydrocarbons, wt%	3.3	4.2	4.0	3.9
Smoke point, mm	27	26	26	26
					Diesel oil (282 ~ 370 DEG C)
Cetane number	64	59	60	61
					Condensation point, DEG C	-7	-1	-3	-3

Can be found out by the evaluation result of table 4 catalyst, the catalyst prepared by the present invention is on the basis of greater activity, and have well selective, product property is good.

Claims (30)

1. a carrier of hydrocracking catalyst, comprises small-grain Y molecular sieve, aluminium oxide and amorphous aluminum silicide, and wherein said small-grain Y molecular sieve, its character is as follows: SiO ₂/ A1 ₂o ₃mol ratio is 40 ~ 120, and average grain diameter is 200 ~ 700nm, and relative crystallinity is more than 100%, and lattice constant 2.425 ~ 2.450nm, specific area is 850 ~ 1000m ²/ g, pore volume is that the pore volume shared by secondary pore of 0.40 ~ 0.60mL/g, 1.7 ~ 10nm accounts for more than 50%, Na of total pore volume ₂o content≤0.15wt%.

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

3., according to catalyst carrier according to claim 1, it is characterized in that in described small crystal grain Y-shaped molecular sieve, the pore volume shared by secondary pore of 1.7 ~ 10nm account for 50% ~ 80% of total pore volume.

4., according to catalyst carrier according to claim 1, it is characterized in that in described small crystal grain Y-shaped molecular sieve, the pore volume shared by secondary pore of 1.7 ~ 10nm account for 55% ~ 75% of total pore volume.

5., according to catalyst carrier according to claim 1, it is characterized in that the lattice constant of described small crystal grain Y-shaped molecular sieve is 2.425 ~ 2.440.

6. according to catalyst carrier according to claim 1, it is characterized in that described catalyst support properties is as follows: specific area is 450 ~ 650 m ²/ g, pore volume is 0.5 ~ 0.80 mL/g, and the pore volume of aperture 4 ~ 10nm accounts for 55% ~ 90% of total pore volume.

7. according to catalyst carrier according to claim 1, it is characterized in that in described carrier of hydrocracking catalyst, with the weight of carrier for benchmark, its composition comprises: the content of small crystal grain Y-shaped molecular sieve is 5wt% ~ 40wt%, the content of amorphous aluminum silicide is 20wt% ~ 65wt%, and the content of aluminium oxide is 10wt% ~ 40wt%.

8. according to catalyst carrier according to claim 1, it is characterized in that in described carrier of hydrocracking catalyst, with the weight of carrier for benchmark, the content of small crystal grain Y-shaped molecular sieve is 10wt% ~ 25wt%, the content of amorphous aluminum silicide is 30wt% ~ 60wt%, and the content of aluminium oxide is 15wt% ~ 30wt%.

9. the preparation method of the arbitrary described catalyst carrier of claim 1 ~ 8, comprising: by small crystal grain Y-shaped molecular sieve, amorphous aluminum silicide and the adhesive mixing made from aluminium oxide, extruded moulding, then drying and roasting, make carrier.

10. in accordance with the method for claim 9, it is characterized in that the preparation method of described small crystal grain Y-shaped molecular sieve, comprising:

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

(2) fine grain NaY type molecular sieve is become Na ₂the little crystal grain NH of O content≤2.5wt% ₄naY;

(3) little crystal grain NH is obtained to step (2) ₄naY molecular sieve carries out hydrothermal treatment consists;

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

(5) molecular sieve step (4) obtained is with containing NH ₄ ⁺and H ⁺mixed solution process, then washing and dry, obtains small crystal grain Y-shaped molecular sieve,

The small crystal grain NaY molecular sieve that wherein step (1) is used, its character is as follows: SiO ₂/ Al ₂o ₃mol ratio is greater than 6.0 and not higher than 9.0, average grain diameter is 200 ~ 700nm, specific surface 800 ~ 1000 m ²/ g, pore volume 0.30/ ~ 0.45mL/g, relative crystallinity is 90% ~ 130%, and cell parameter is 2.460 ~ 2.470nm, through roasting in 650 DEG C of air after 3 hours relative crystallinity be more than 90%, through 700 DEG C of water vapour hydrothermal treatment consists after 2 hours relative crystallinity be more than 90%.

11. in accordance with the method for claim 10, it is characterized in that: the SiO of small crystal grain NaY molecular sieve used ₂/ Al ₂o ₃mol ratio is 6.5 ~ 9.0.

12. in accordance with the method for claim 10, it is characterized in that: the SiO of small crystal grain NaY molecular sieve used ₂/ Al ₂o ₃mol ratio is 7.0 ~ 8.0.

13. in accordance with the method for claim 10, it is characterized in that: the average grain diameter of small crystal grain NaY molecular sieve used is 300 ~ 500nm.

14. in accordance with the method for claim 10, it is characterized in that: small crystal grain NaY molecular sieve used through roasting in 650 DEG C of air after 3 hours relative crystallinity be 90% ~ 110%, through 700 DEG C of water vapour hydrothermal treatment consists after 2 hours relative crystallinity be 90% ~ 110%.

15. in accordance with the method for claim 10, it is characterized in that: the preparation method of small crystal grain NaY molecular sieve used, comprising:

I, preparation directed agents: silicon source, aluminium source, alkali source and water are fed intake according to following proportioning: (6 ~ 30) Na ₂o:Al ₂o ₃: (6 ~ 30) SiO ₂: (100 ~ 460) H ₂o, after stirring, stirs ageing 0.5 ~ 24 hour obtained directed agents at 0 ~ 20 DEG C by mixture;

II, adopt preparing amorphous silicon alumnium using carbonization predecessor, with the weight of the butt of amorphous aluminum silicide predecessor for benchmark, silicon in the content of silica for 40wt% ~ 75wt%; Its preparation process comprises:

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

B, to step a preparation sodium aluminate solution in add step a preparation part sodium silicate solution, then pass into CO ₂gas, controlling reaction temperature is 10 ~ 40 DEG C, and the pH value controlling cemented into bundles is 8 ~ 11; Wherein as the CO passed into ₂when gas flow accounts for 60% ~ 100% of total intake, add remainder sodium silicate solution, wherein in step b, remainder sodium silicate solution accounts for step b in silica and adds sodium silicate solution total amount in the 5wt% ~ 85wt% of silica;

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

III, prepare silica-alumina gel: by (0.5 ~ 6) Na ₂o:Al ₂o ₃: (8 ~ 15) SiO ₂: (100 ~ 460) H ₂total molar ratio of O, under the condition of 0 ~ 40 DEG C of rapid stirring, add water, silicon source, directed agents and alkali source in the amorphous aluminum silicide predecessor of Step II gained, and control ph is 9.5 ~ 12.0, uniform stirring, obtains silica-alumina gel; Wherein directed agents addition accounts for 1% ~ 20% of silica-alumina gel weight,

The reactant mixture of IV, Step II I gained is through two step dynamic crystallizations, more after filtration, washing, drying, obtains small crystal grain NaY molecular sieve.

16. in accordance with the method for claim 15, it is characterized in that in Step II, amorphous aluminum silicide predecessor, and with the weight of the butt of amorphous aluminum silicide predecessor for benchmark, silicon is 55 wt% ~ 70wt% in the content of silica.

17. in accordance with the method for claim 15, it is characterized in that: it is 15 ~ 35 DEG C that step b controls reaction temperature.

18. in accordance with the method for claim 15, it is characterized in that: in step b, as the CO passed into ₂when gas flow accounts for 80% ~ 100% of total intake, add remainder sodium silicate solution.

19. in accordance with the method for claim 15, it is characterized in that: in step b, remainder sodium silicate solution accounts for step b in silica and adds sodium silicate solution total amount in the 30wt% ~ 70wt% of silica.

20. in accordance with the method for claim 15, and it is characterized in that, in step I and III, silicon source, alkali source are selected from sodium metasilicate and NaOH respectively, in step I, aluminium source is selected from sodium metaaluminate.

21. in accordance with the method for claim 15, it is characterized in that in Step II I, controls reaction temperature 10 ~ 30 DEG C, pH value 10 ~ 11.

22. in accordance with the method for claim 15, it is characterized in that step IV adopts two step dynamic crystallizations, and wherein to carry out the condition of dynamic crystallization as follows for the first step: temperature controls at 50 ~ 90 DEG C, and crystallization time is 0.5 ~ 18 hour; The condition that second step carries out dynamic crystallization is as follows: temperature controls at 80 ~ 140 DEG C, and crystallization time is 3 ~ 10 hours.

23. in accordance with the method for claim 15, it is characterized in that step IV adopts two step dynamic crystallizations, and wherein to carry out the condition of dynamic crystallization as follows for the first step: temperature controls at 60 ~ 80 DEG C, and crystallization time is 1 ~ 10 hour; The condition that second step carries out dynamic crystallization is as follows: temperature controls at 80 ~ 120 DEG C, and crystallization time is 5 ~ 10 hours.

24. in accordance with the method for claim 10, and it is characterized in that in step (3), the condition of described hydrothermal treatment consists is as follows: treatment temperature controls at 500 ~ 750 DEG C, pressure is 0.01 ~ 0.50MPa, and the processing time is 1.0 ~ 4.0 hours.

25. in accordance with the method for claim 10, and it is characterized in that in step (3), the condition of described hydrothermal treatment consists is as follows: treatment temperature controls at 600 ~ 700 DEG C, pressure is 0.05 ~ 0.30MPa, and the processing time is 1.0 ~ 4.0 hours.

26. in accordance with the method for claim 10, it is characterized in that, in step (4), in aqueous medium, adding little crystal grain NH by solid-liquid weight ratio 1:4 ~ 1:8 ₄naY molecular sieve, stirs and is warmed up to 90 ~ 120 DEG C, being then added dropwise to hexafluorosilicic acid aqueous ammonium, after dropwising, constant temperature stirs, isolated molecule sieve and accessory substance, and filter, dry, the wherein concentration 10wt% ~ 40wt% of hexafluorosilicic acid aqueous ammonium, ammonium hexafluorosilicate addition is little crystal grain NH ₄10wt% ~ the 50wt% of NaY molecular sieve.

27. in accordance with the method for claim 10, it is characterized in that in step (5), by the molecular sieve after hydrothermal treatment consists with acid with containing NH ₄ ⁺the mixed solution contact of salt composition, exchange the Na in molecular sieve ⁺with the part non-framework aluminum removed in molecular sieve, acid is wherein one or more in hydrochloric acid, carbonic acid, nitric acid, sulfuric acid, containing NH ₄ ⁺salt be containing above acid group ammonium salt in one or more; H in mixed solution ⁺concentration be 0.05 ~ 0.6mol/L, NH ₄ ⁺concentration be 0.5 ~ 3.0mol/L, exchange temperature is 70 ~ 120 DEG C, and the concentration exchanging slurries Middle molecule sieve is 0.1 ~ 0.5g/mL, and swap time is 0.5 ~ 3.0 hour, and exchange step repeats 1 ~ 4 time.

28. in accordance with the method for claim 10, it is characterized in that: the method that step (2) adopts ammonium salt to exchange, process is as follows: take NaY molecular sieve as raw material, at 70 ~ 120 DEG C, 0.5 ~ 3.0 hour is exchanged with the aqueous solution of solubility ammonium salt, molecular sieve is 0.05 ~ 0.50g/mL exchanging the concentration in slurries, repeated exchanged l ~ 5 time, elimination mother liquor, washing, dry; Ammonium salt is one or more in ammonium chloride, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate, and the concentration of ammonium salt solution is 0.5 ~ 5.0mol/L.

29. in accordance with the method for claim 9, it is characterized in that: SiO in described amorphous aluminum silicide ₂weight content be 20% ~ 60%, the pore volume of amorphous aluminum silicide is 0.6 ~ 1.1 mL/g, and specific area is 300 ~ 500 m ²/ g.

30. in accordance with the method for claim 9, it is characterized in that: drying and the roasting condition of carrier are as follows: through 80 ~ 150 DEG C of dryings 3 ~ 10 hours, 500 ~ 600 DEG C of roastings 3 ~ 6 hours.