CN105084386A - Small-particle Y-type molecular sieve with silicon-enriched surface and preparation method thereof - Google Patents
Small-particle Y-type molecular sieve with silicon-enriched surface and preparation method thereof Download PDFInfo
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Abstract
The invention provides a small-particle Y-type molecular sieve with a silicon-enriched surface. The molecular sieve is characterized in that the molar ratio of SiO2/Al2O3 of a phase skeleton of the molecular sieve body is 5.0-6.0, the molar ratio of SiO2/Al2O3 of the surface is 8.0-13.0, the cell parameter is 2.46-2.468nm, the weight content of sodium oxide is less than or equal to 0.1 wt%, and the average diameter of crystal grains is 50-800nm.
Description
Technical field
The present invention relates to a kind of Y zeolite and preparation method thereof, more particularly relate to a kind of preparation method of rich surface silicon small grain Y zeolite.
Background technology
The fifties end, Milton and Breck successfully synthesizes Y zeolite.Due to SiO in the structure of Y zeolite
2with Al
2o
3ratio be greater than X-type molecular sieve, thus thermostability and hydrothermal stability improve.Early seventies, Grace development of company directing agent method synthesis NaY molecular sieve, raw material instead of expensive silicon sol with water glass, and technique is simplified, growth cycle shortens, thus makes NaY molecular sieve be widely applied to petrochemical complex especially cracking of oil catalytic field rapidly.Up to now, in hundreds of molecular sieve developed, what industrially usage quantity was maximum is Y zeolite.At present, the synthesis of Y zeolite industrially mainly adopts crystal seed glue method.Due to the Application and improvement of crystal seed glue, greatly shortened, for the industrialization of Y zeolite is laid a good foundation the time of the synthesis crystallization of Y zeolite.
Industrial application and development is had higher requirement to the synthesis of molecular sieve and products thereof performance, also promotes the further investigation of Zeolite synthesis technology conversely.To the requirements at the higher level of Y zeolite synthesis mainly concentrate on synthesizing small-grain and ultra-fine grain zeolite product, improve silica alumina ratio and synthesizing high-silicon aluminum ratio ratio and three aspects such as the zeolite product of little crystal grain and ultra-fine grain.
The Y zeolite of little grain-size is owing to having larger outer surface area and higher micropore diffusion speed, improving in conversion macromole ability, the secondary cracking reducing product and the coking of reduction catalyzer etc., show the performance more more superior than conventional die size Y zeolite, therefore the study on the synthesis of the Y zeolite of little crystal grain becomes focus.The Y zeolite synthesized in conventional manner generally has the grain-size of about 1000nm, and the synthesis report that little crystal grain even can reach nano level (<100nm) grain-size this respect is still less.
With hot crushing technology process Y zeolite, although its grain fineness number can be made to be reduced to 100nm, the mode of this physical pulverization process not only expends comparatively macro-energy, and destroys the crystalline structure of molecular sieve, makes it part amorphous.If can direct synthesizing small-grain Y zeolite, it be the most simple and feasible method, therefore, must will optimize the synthesis condition of conventional Y zeolite, by improving and increase guiding dosage, improving the method reduction molecular sieve particle diameters such as the basicity that feeds intake, to obtain small crystal grain Y-shaped molecular sieve product and the business-like top condition of applicable molecular sieve.
The optimization of synthesis condition generally includes the condition as the preparation of crystal seed glue, the impact of digestion time, the preparation of silica-alumina gel and hydrothermal crystallizing, comprises basicity, crystallization temperature and crystallization time etc.The composition of silica-alumina gel generally causes molecular sieve different by the impact of crystallization condition; Hydrothermal crystallizing condition more immediate influence the synthesis of molecular sieve, and they both restricted mutually, the silica alumina ratio of the molecular sieve that influences each other again, degree of crystallinity and grain fineness number.The basicity of silica-alumina gel is a very crucial factor in sieve synthesis procedure, and the basicity improving synthetic system can prepare Microsize NaY Zeolite.The water glass containing poly state silicon due to industrial most employing is silicon source, improves system basicity, not only can increase the depolymerization of poly state silicon, and be conducive to forming more nucleus in silica-alumina gel, thus grain-size is reduced.Schhoeman etc. (SehoemanBJ, SterteJ, ChemicalCommunications, 1993:994 ~ 99) adopt the method for high alkalinity, high silica alumina ratio, have directly synthesized the NaY molecular sieve that grain-size is less than 150nm from liquid phase.But along with the increase of system basicity, the yield of synthetic product declines.The people such as Bi-ZengZ also find under study for action as synthetic system n (Na
2o)/n (Al
2o
3)=6 ~ 15, and be greater than the high-speed stirring of 3000r/min at rotating speed under, prepare homogeneous phase, mobility alumino silica gel, the Y zeolite of particle diameter at below 100nm can be obtained, but silica alumina ratio is generally less than 4.5 (Bi-ZengZ, MaryA.W, MiehaelL.ControlofParticlesizeandsurfaceProPertlesofCrys taIsofNaXZeolite, ChemistryofMaterials, 2002,14:363-3642).
In the synthetic method of Y zeolite, include the directing agent method based on commercial synthesis and the clear liquid synthesis method based on template.Based in the directing agent method of commercial synthesis, by adding the additives such as rare earth ion, aluminum complexing agent and tensio-active agent in synthetic system, the median size of NaY molecular sieve can be reduced, but its shortcoming to be size distribution wider.(the LindnerT. such as Linder, LechertH., Zeolites, 1996,16:196-206) study mineralizer on faujusite synthesize affect time find, in synthetic system, add a small amount of can form the organic complexing agent of stable comple with aluminium, generally can promote the nucleation of molecular sieve and the growth of crystal, thus make the grain-size of molecular sieve reduce, narrow particle size distribution, and framework of molecular sieve silica alumina ratio can not be reduced.Maher etc. disclose a kind of method of synthetic faujasites type molecular sieve in US3516786, before synthetic system intensification crystallization steps, add in synthetic system on a small quantity can be miscible with water organic solvent, as dimethyl sulfone, N, dinethylformamide, tetrahydrofuran (THF), methyl alcohol, ethanol, acetone etc., final zeolite crystal is of a size of 0.01 ~ 0.1 μm.Ambs etc. in order to reduce the volatilization of the organic solvent brought because of intensification, employ glucose in US4372931, and final grain-size is 0.035 ~ 0.069 μm.But, after adding organic solvent, the skeleton SiO of molecular sieve
2/ Al
2o
3lower, generally lower than 2.5.And another kind is based on the clear liquid synthesis method of template, this method can obtain nano level NaY molecular sieve, and has the advantage of crystal particle diameter narrow distribution, but its product yield is very low, and cost is very high.Holmberg etc. by adding 4 bromide and Tetramethylammonium hydroxide double template, by optimize TMA
+y zeolite grain-size and yield is controlled with the concentration of negatively charged ion, finally synthesize the Y zeolite that granularity is 37nm, but the very low and very high (HolmbergB.A. of cost of its product yield, WangH., ControllingsizeandyieldofzeoliteYnanocrystalsUsingtetram ethylammoniumbromide, MicroPorousandMesoPorousMaterial, 2003,59:13-28).
The main character of the height of framework si-al ratio and the structures shape in duct thereof molecular sieve and function.In general, the molecular sieve that silica alumina ratio is higher often has stronger heat-resisting, resistance to water vapour and capacity antacid; In addition, dissimilar molecular sieve is to some catalyzed reaction, and the change with its silica alumina ratio also shows different specific regularity.Therefore, by directly synthesizing or obtained by the method (i.e. secondary synthesis) of modification the silica alumina ratio of dissimilar molecular sieve, thus its character and function can be regulated and controled.
Be less than 5.0 with the silica alumina ratio of Y zeolite of ordinary method synthesis, generally silica alumina ratio is greater than 6.0 be high-Si Y-type molecular sieve.The conventional method obtaining high-Si Y-type molecular sieve has two kinds: a kind of is the method for directly synthesizing, and another kind is on the basis of single sintering, is adopted by product specific route to reprocess, and namely improves framework si-al ratio by the method for secondary synthesis.At present, two-step fabrication mainly contains: high temperature hydrothermal method (US3449370), high temperature gas-phase reaction method (US4701313), ammonium silicofluoride liquid phase reaction method (US4093560) etc., the shortcoming of these methods be that preparation process is numerous and diverse, zeolite crystallinity loss is comparatively large, preparation technology's process CIMS is complicated, yield is low and environmental pollution larger etc.
And need to consider more factor in the method for directly synthesizing, such as: the preparation of the composition of reaction mixture, preparation method, reactant source, directed agents, whether stir, gel potential of hydrogen and crystallization condition etc.The Y zeolite that usual silica alumina ratio is lower more easily obtains, otherwise the preparation condition of silica alumina ratio more high request is harsher, more difficultly synthesizes desirable sample.In the method for directly synthesis, the conventional approach improving silica alumina ratio mainly contains following several: a kind of approach extends crystallization time, but this approach is after silica alumina ratio is greater than 5.5, crystallization velocity exponentially form decline, make synthesis because of consuming time, cost is high and be not suitable for industrial production; Another kind of approach uses organic amine (US5116590, US4965059, CN96105159.7, or inorganic salt (US4333859 CN97196899), US4309313) as template, but the problem such as this exists equally that cost is high, crystallization time long, the utilization ratio of silicon is on the low side, simultaneously, the silicon waste liquid of a large amount of high density is discharged, and has both wasted also contaminate environment.
In the method for direct synthesizing high-silicon aluminum ratio Y zeolite, adopt non-template agent method to be the focus and difficult point studied always.CN102198950A discloses a kind of preparation method of high silica alumina ratio NaY molecular sieve; By silicon source, aluminium source and deionized water mixing, get the directed agents of two kinds of different mol ratio, water glass, acid aluminium salt and sodium aluminate solution according to following gel masses mol ratio and mix obtained two kinds of gels, respectively crystallization; Gel masses mol ratio is: (1.0 ~ 6.5) Na
2o:Al
2o
3: (5.0 ~ 18) SiO
2: (100 ~ 280) H
2o, the wherein Al of directed agents
2o
3account for Al
2o
30.01 ~ 15% of gross weight; Two kinds of gels are 1:(0.1 ~ 10 according to mass ratio) Homogeneous phase mixing, obtained mixed gel; By obtained mixed gel crystallization 2 ~ 50 hours at 80 ~ 120 DEG C, obtained NaY molecular sieve.Under the condition that molar ratio is identical, the method can prepare the NaY molecular sieve of high silica alumina ratio within the shorter time.Method disclosed in CN1785807A and CN1785808A is at 15 ~ 60 DEG C, stir ageing 0.5 ~ 48 hour obtained directed agents in advance, then reaction mixture is made in directed agents, water, silicon source, aluminium source, by reaction mixture crystallization in two steps after stirring, the first step dynamic crystallization, second step static crystallization, finally by filtration, washing, dry, obtained relative crystallinity is greater than 80%, framework si-al ratio and SiO
2/ Al
2o
3mol ratio is between 6.0 ~ 7.0, and the high silicon aluminium ratio small crystal NaY molecular sieve of average crystal grain between 300 ~ 800nm.The preparation method of the NaY molecular sieve of high silica alumina ratio, little crystal grain disclosed in CN1789125, first synthesize NaY molecular sieve directed agents, then gel is obtained with water glass, directed agents, acid aluminium salt and sodium metaaluminate, by gel at 50 ~ 100 DEG C after crystallization 0 ~ 70h, add silicon source, at 90 ~ 120 DEG C, continue crystallization 0.5 ~ 50h again, finally by filtration, washing, dry, obtain that silica alumina ratio is 5.2 ~ 7.0, crystal grain is the NaY molecular sieve of 100 ~ 400nm.
Y zeolite will carry out modification to it before application, obtained having different SiO
2/ Al
2o
3the molecular sieve of ratio, acidity and pore structure.Content normally by changing aluminium realizes the modification of molecular sieve, and wherein sour dealuminzation is an important method of Y zeolite modification.Acid-treated condition is general gentleer, can not saboteur's sieve structure, optionally removes the non-framework aluminum in molecular sieve.But for the difficult non-framework aluminum removed of part, adopt general acid treatment it effectively, uniformly can not be removed, if by improving acid concentration, then can cause removing of part framework aluminum, make modified molecular sieve structure destruction, degree of crystallinity declines, sour irrational distribution, thus directly cause the decline of catalytic performance.Another kind of method of modifying with salicide processes molecular sieve.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, this inventive 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; To there is batch in the industrial production little for this gas phase treatment method in addition, and the shortcoming such as consume energy higher.
Summary of the invention
From disclosed document, also there is not report skeleton SiO
2/ Al
2o
3mol ratio is between 5.0 ~ 6.0, and average crystal grain can adjust between 50 ~ 200nm, 200 ~ 500nm, 500 ~ 800nm, high silicon aluminium ratio small crystal NaY molecular sieve in narrow diameter distribution.Contriver finds the temperature and time of directed agents dynamic aging, the temperature and time of directed agents static-aging, the composition of directed agents and the composition of add-on, reaction mixture, crystallization temperature and these influence factors of crystallization time all can affect silica alumina ratio and the median size of synthesized molecular sieve in the reactive mixture, by optimizing above-mentioned influence factor simultaneously, accurately the adjustment median size of product and the object of silica alumina ratio can be reached, the Y zeolite of less crystal grain can be obtained, based on this, form the present invention.
An object of the present invention is to provide a kind of small crystal grain Y-shaped molecular sieve of surperficial Silicon-rich, and two of object is to provide a kind of prior art that is different from, and with low cost, technique simple non-template agent legal system is for the method for the small crystal grain Y-shaped molecular sieve of surperficial Silicon-rich.
The small crystal grain Y-shaped molecular sieve of surperficial Silicon-rich provided by the invention, is characterized in that, molecular sieve phase skeleton SiO
2/ Al
2o
3mol ratio is 5.0 ~ 6.0, surperficial SiO
2/ Al
2o
3mol ratio is 8.0 ~ 13.0, and unit cell parameters is 2.46 ~ 2.468nm, sodium oxide weight content≤0.1wt%, and average grain diameter is 50 ~ 800nm.
The small crystal grain Y-shaped molecular sieve of surperficial Silicon-rich provided by the invention, the Siliciumatom of framework of molecular sieve and the mol ratio of aluminium atom, i.e. body phase skeleton SiO
2/ Al
2o
3mol ratio is 5.0 ~ 6.0.NMR method is adopted to measure; The Siliciumatom of zeolite crystal outside surface and the mol ratio of aluminium atom, i.e. surperficial SiO
2/ Al
2o
3mol ratio is 8.0 ~ 13.0, adopts XPS method to measure.
The small crystal grain Y-shaped molecular sieve of surperficial Silicon-rich provided by the invention, its crystallization reservation degree is greater than 90%, the definition of said crystallization reservation degree is: with the peak height of 5 characteristic peaks in the X-ray diffracting spectrum of the Y zeolite of little crystal grain used before the small crystal grain Y-shaped molecular sieve of surperficial Silicon-rich and surperficial Silicon-rich process and the percentage ratio of ratio, said 5 characteristic peaks be respectively 2 θ be 15.8,20.7,24.0, characteristic peak corresponding to 27.4 and 31.8 peak positions.The small crystal grain Y-shaped molecular sieve of surperficial Silicon-rich provided by the invention, its average grain diameter can between 50 ~ 800nm modulation, as required, its average grain diameter can be 50 ~ 200nm, or can be 200 ~ 500nm, or can be 500 ~ 800nm.Its BET specific surface is 700 ~ 800cm
2/ g.
Present invention also offers the corresponding preparation method of small crystal grain Y-shaped molecular sieve of above-mentioned surperficial Silicon-rich, it is characterized in that the synthesis comprising small crystal grain NaY molecular sieve, ammonium is handed over and is fallen sodium, hydrothermal treatment consists and dealumination complement silicon process, under the synthesis of said NaY molecular sieve is included in the condition of synthesis NaY molecular sieve, by directed agents, water, the mixture A of silicon source and aluminium source composition carries out hydrothermal crystallizing and also reclaims the product obtained, wherein said directed agents is mixed with water glass by sodium metaaluminate, the volumetric molar concentration of aluminium element in water glass is edged up to forming mol ratio for (6 ~ 25) Na by zero
2o:A1
2o
3: (6 ~ 25) SiO
2mixture B, then sequentially pass through dynamic ageing, still aging, then add that water obtains, wherein said mixture A obtains after adding mixing tank successively according to the order of directed agents, silicon source, aluminium source and water.
The present invention find directed agents contact raw state, dynamic aging, static-aging, directed agents composition and the raw material addition sequence of add-on, reaction mixture and the factor such as crystallization temperature and time all can affect on the silica alumina ratio of synthesized molecular sieve and the basis of median size in the reactive mixture, by optimizing above-mentioned influence factor simultaneously, accurately the adjustment median size of product and the object of silica alumina ratio can be reached.And the synthetic method of existing Y zeolite can only synthesize grain size at 900-1300nm, SiO
2/ Al
2o
3the product of mol ratio between 4.8 ~ 5.3.
In preparation method of the present invention, said small crystal grain Y-shaped molecular sieve uses direct synthesis technique to obtain: first prepare directed agents, then preparation feedback mixture, finally by crystallization, filtration, washing, drying and obtain middle high silicon aluminium ratio small crystal NaY molecular sieve.In said reaction mixture, do not add any template or additive, also need not to synthesize the molecular sieve that obtain carry out chemistry or physical method carry out dealuminzation, or dealumination complement silicon and secondary synthesis improve silica alumina ratio.Raw materials used inexpensive, be easy to get, simple for process, be conducive to reduce manufacturing cost.
Wherein, the preparation of said directed agents is different from the preparation process of conventional method synthesis NaY molecular sieve directed agents, and silicon source and aluminium source can mix with any order by ordinary method, aging under quiescent conditions after mixing; Also be different from the preparation method of directed agents in patent CN1785807, CN1785808, at 15 ~ 60 DEG C, stir aging obtained directed agents.The preparation of the directed agents in the inventive method is mixed with water glass by sodium metaaluminate, and the volumetric molar concentration of aluminium element in water glass is edged up to forming mol ratio for (6 ~ 25) Na by zero
2o:A1
2o
3: (6 ~ 25) SiO
2mixture B, then sequentially pass through dynamic ageing, still aging, then add that water obtains.Preparation process comprises the following steps more specifically: sodium metaaluminate, at 15 ~ 60 DEG C of temperature and agitation condition, adds by (1) in water glass, and forming mol ratio is (6 ~ 25) Na
2o:A1
2o
3: (6 ~ 25) SiO
2said mixture B; (2) by mixture B dynamic ageing 5 ~ 48 hours at 15 ~ 60 DEG C, then at 15 ~ 60 DEG C still aging 5 ~ 48 hours; (3) after ageing, under the condition stirred, add water, make the final mol ratio of directed agents for (6 ~ 25) Na
2o:A1
2o
3: (6 ~ 25) SiO
2: (200 ~ 400) H
2o.
After obtaining directed agents, preparation method's further step of said small crystal grain NaY molecular sieve is: at room temperature add water, silicon source, aluminium source, directed agents obtain mixture A, the mol ratio of mixture A is (2 ~ 6) Na
2o:A1
2o
3: (8 ~ 20) SiO
2: (200 ~ 400) H
2o, the add-on of directed agents accounts for 3 ~ 30% calculating of total aluminium element mole number according to the mole number of aluminium element in directed agents.Said mixture A obtains after adding mixing tank successively according to the order of directed agents, silicon source, aluminium source and water.
Said water is deionized water or distilled water, silicon source can be one or more the mixture in water glass, silicon sol, silica gel and white carbon black, and said aluminium source is one or more the mixture in sodium metaaluminate, Tai-Ace S 150, aluminum chloride, aluminum nitrate, aluminium hydroxide and pseudo-boehmite.
The hydrothermal crystallizing of said mixture A carries out 15-48 hour in closed reactor at 90-100 DEG C.
In preparation method of the present invention, after the NaY molecular sieve obtaining little crystal grain, also the process of falling sodium, hydrothermal treatment consists and dealumination complement silicon to be handed over just to obtain the small crystal grain Y-shaped molecular sieve of surperficial Silicon-rich of the present invention through ammonium.
Wherein, said ammonium hands over the process of falling sodium to be the content of sodium oxide in molecular sieve will be reduced to 2.5 ~ 5.0 % by weight.Said ammonium hands over the process of falling sodium to carry out one or many, it is the ammonium salt solution of 0.1 ~ 1.0mol/L that said ammonium hands over the process of falling sodium to comprise employing ammonium concentration, under temperature 50 ~ 100 DEG C, solvent and solute weight ratio are the condition of 8 ~ 15:1, constant temperature process 0.5 ~ 1.5 hour.Said ammonium salt is one or more in ammonium nitrate, ammonium sulfate, ammonium chloride and ammonium acetate.
Wherein, the process of said hydrothermal treatment consists processes 1 ~ 3 hour at 100% water vapour, gauge pressure 0.1 ~ 0.2MPa, temperature 500 ~ 650 DEG C.
Wherein, the process of said dealumination complement silicon is that the molecular sieve process through hydrothermal treatment consists obtained is pulled an oar in aqueous and obtained the slurry that solvent and solute weight ratio is 3 ~ 10:1, again at 80 ~ 120 DEG C of temperature, add the charging capacity of 10 ~ 60 grams according to every 100 mol sieves, by (NH
4)
2siF
6to add in said slurry and to stir, then reclaiming product.Said stirring is at temperature is 80-120 DEG C, preferably stirs 0.5-5 hour in constant temperature constant speed.The process of said recovery product comprises filters and drying.
Method of the present invention, the process that the hydrothermal treatment consists adopted and dealumination complement silicon combine, the silicon in ammonium hexafluorosilicate is made mainly to add to Y molecular sieve surface, silicon, aluminium and the lattice vacancy produced is removed when filling up hydrothermal aging, increased considerably the surface silicon aluminum ratio of Y molecular sieve, and the framework si-al ratio of entirety just slightly increases.Final Y molecular sieve structure cell only has minimal shrink, and relative crystallinity is 100%-130%, and unit cell parameters is 2.460-2.468nm, sodium oxide content≤0.1wt%.
Embodiment
The following examples are used for illustrating in greater detail the present invention, but scope of the present invention is not only limited to the scope of these embodiments.
In each embodiment and comparative example, the mensuration of specific surface adopts low temperature liquid nitrogen physisorphtion; Relative crystallinity and unit cell parameters adopt x-ray diffraction method; Body phase skeleton SiO
2/ Al
2o
3mol ratio adopts NMR method to measure; Surface SiO
2/ Al
2o
3mol ratio adopts XPS method to measure; The grain size of molecular sieve adopts the mode of SEM (scanning electronic microscope) to measure, and is observed by JSM-5610LV type scanning electron microscope instrument.
Embodiment 1
The present embodiment illustrates the building-up process of small crystal grain NaY molecular sieve.
By 50.39g high alkali deflection aluminium acid sodium solution, (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, Al
2o
3content is 40.2g/L, Na
2o content is 255g/L, and proportion is 1.324) (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, SiO to join 65.56g water glass
2content is 260.6g/L, Na
2o content is 81.6g/L, and proportion is 1.2655, and modulus is 3.3) in, at room temperature stir ageing 48 hours, then static ageing 5 hours at 60 DEG C of temperature, finally under the condition stirred, add 15g deionized water, the final mol ratio of the directed agents obtained is 15Na
2o:A1
2o
3: 15SiO
2: 320H
2o.
Obtained directed agents is all for the preparation of following reaction mixture, and the add-on of directed agents, accounts for 3% of total aluminium element mole number according to the mole number of aluminium element in directed agents and calculate.
Under the condition of room temperature and high-speed stirring, according to directed agents (abovementioned steps preparation), 1682.6g water glass (the same), 134.19g low alkali aluminium acid sodium solution, (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, Al
2o
3content is 194g/L, Na
2o content is 286.2g/L, and proportion is 1.413), (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides 448.02g Tai-Ace S 150, Al
2o
3content is 88.9g/L, and proportion is 1.2829) and the order of 150.4g water add successively in mixing tank, total molar ratio of reaction mixture is 3Na
2o:A1
2o
3: 12SiO
2: 209H
2o.After stirring, loaded in stainless steel cauldron, 100 DEG C of static crystallizations 24 hours, then filter, wash, dry NaY molecular sieve product, numbering A1.
It is 5.8 that XRD spectra records its silica alumina ratio, and relative crystallinity is 93.7%, and electromicroscopic photograph display average grain size is 300nm.
Comparative example 1
This comparative example illustrates is synthesizing in directed agents process the situation changing directed agents aging condition, only adopt feeding sequence that is still aging and reaction mixture to change.
Each raw material sources are with embodiment 1.
50.39g high alkali deflection aluminium acid sodium solution is joined in 65.56g water glass, at room temperature still aging 28 hours, then to add the final mol ratio of directed agents that 15g deionized water obtains be 15Na
2o:A1
2o
3: 15SiO
2: 320H
2o.
Obtained directed agents is all for the preparation of following reaction mixture, and the add-on of directed agents, accounts for 3% of total aluminium element mole number according to the mole number of aluminium element in directed agents and calculate.
In mixing tank, 1682.6g water glass is first added under the condition of room temperature and high-speed stirring, add 150.4g water, 134.19g low alkali aluminium acid sodium solution, directed agents (abovementioned steps preparation) and 448.02g Tai-Ace S 150 more successively, total molar ratio of reaction mixture is 3Na
2o:A1
2o
3: 12SiO
2: 209H
2o.After stirring, loaded in stainless steel cauldron, 100 DEG C of static crystallizations 24 hours, then filter, wash, dry NaY molecular sieve product, numbering D1.
It is 4.8 that XRD spectra records silica alumina ratio, and relative crystallinity is 88.7%, and electromicroscopic photograph display average grain size is 1000nm.
Embodiment 2
The present embodiment illustrates the building-up process of small crystal grain NaY molecular sieve.
By 50.39g high alkali deflection aluminium acid sodium solution, (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, Al
2o
3content is 40.2g/L, Na
2o content is 255g/L, and proportion is 1.324) (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, SiO to join 65.56g water glass
2content is 260.6g/L, Na
2o content is 81.6g/L, and proportion is 1.2655, and modulus is 3.3) in, ageing 5 hours is stirred at 60 DEG C of temperature, then static ageing 5 hours at 60 DEG C of temperature, finally under the condition stirred, add 15g deionized water, the final mol ratio of the directed agents obtained is 15Na
2o:A1
2o
3: 15SiO
2: 320H
2o.
Obtained directed agents is all for the preparation of following reaction mixture, and the add-on of directed agents, accounts for 3% of total aluminium element mole number according to the mole number of aluminium element in directed agents and calculate.
Under the condition of room temperature and high-speed stirring, according to directed agents (abovementioned steps preparation), 1682.6g water glass (the same), 134.19g low alkali aluminium acid sodium solution, (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, Al
2o
3content is 194g/L, Na
2o content is 286.2g/L, and proportion is 1.413), (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides 448.02g Tai-Ace S 150, Al
2o
3content is 88.9g/L, and proportion is 1.2829) and the order of 1419.4g water add successively in mixing tank, total molar ratio of reaction mixture is 3Na
2o:A1
2o
3: 12SiO
2: 350H
2o.After stirring, loaded in stainless steel cauldron, 100 DEG C of static crystallizations 32 hours, then filter, wash, dry NaY molecular sieve product, numbering A2.
It is 5.9 that XRD records its silica alumina ratio, and relative crystallinity is 90.6%, and electromicroscopic photograph display average grain size is 800nm.
Comparative example 2
This comparative example illustrates the situation of the order of addition(of ingredients) changing silicon source, aluminium source in directed agents preparation.
Each raw material sources are with embodiment 2.
65.56g water glass is joined in 50.39g high alkali deflection aluminium acid sodium solution, ageing 5 hours is stirred at 60 DEG C of temperature, then static ageing 5 hours at 60 DEG C of temperature, finally under the condition stirred, add 15g deionized water, the final mol ratio of the directed agents obtained is 15Na
2o:A1
2o
3: 15SiO
2: 320H
2o.
Obtained directed agents is all for the preparation of following reaction mixture, and the add-on of directed agents, accounts for 3% of total aluminium element mole number according to the mole number of aluminium element in directed agents and calculate.
Add successively in mixing tank according to the order of directed agents (abovementioned steps preparation), 1682.6g water glass, 134.19g low alkali aluminium acid sodium solution, 448.02g Tai-Ace S 150 and 1419.4g water under the condition of room temperature and high-speed stirring, total molar ratio of reaction mixture is 3Na
2o:A1
2o
3: 12SiO
2: 350H
2o.After stirring, loaded in stainless steel cauldron, 100 DEG C of static crystallizations 32 hours, then filter, wash, dry NaY molecular sieve product, numbering D2.
It is 5.0 that XRD records its silica alumina ratio, and relative crystallinity is 87%, and electromicroscopic photograph display average grain size is 1000nm.
Embodiment 3
The present embodiment illustrates the building-up process of small crystal grain NaY molecular sieve.
By 164.54g high alkali deflection aluminium acid sodium solution, (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, Al
2o
3content is 40.2g/L, Na
2o content is 340g/L, and proportion is 1.297) (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, SiO to join 291.37g water glass
2content is 260.6g/L, Na
2o content is 81.6g/L, and proportion is 1.2655, and modulus is 3.3) in, stir ageing 20 hours at 30 DEG C of temperature, then static ageing 15 hours at 40 DEG C of temperature, finally under the condition stirred, add 60g deionized water.The final mol ratio of the directed agents obtained is 20Na
2o:A1
2o
3: 20SiO
2: 380H
2o.
Obtained directed agents is all for the preparation of following reaction mixture, and the add-on of directed agents, accounts for 10% of total aluminium element mole number according to the mole number of aluminium element in directed agents and calculate.
Under the condition of room temperature and high-speed stirring, according to directed agents (abovementioned steps preparation), 1092.62g water glass (the same), 166.31 low alkali aluminium acid sodium solutions, (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, Al
2o
3content is 194g/L, Na
2o content is 286.2g/L, and proportion is 1.413), (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides 332.87g Tai-Ace S 150, Al
2o
3content is 88.9g/L, and proportion is 1.2829) and the order of 479.4g water add successively in mixing tank, total molar ratio of reaction mixture is 4Na
2o:A1
2o
3: 9SiO
2: 220H
2o.After stirring, loaded in stainless steel cauldron, 95 DEG C of static crystallizations 24 hours, then filter, wash, dry NaY molecular sieve product, numbering A3.
It is 5.2 that XRD records its silica alumina ratio, and relative crystallinity is 95.1%, and electromicroscopic photograph display average grain size is 300nm.
Comparative example 3
The explanation of this comparative example changes directed agents aging condition in synthesis directed agents process, only adopts the situation of dynamic ageing.
Raw material sources are with embodiment 3.
Join in 291.37g water glass by 164.54g high alkali deflection aluminium acid sodium solution, stir ageing 20 hours at 30 DEG C of temperature, finally under the condition stirred, add 60g deionized water, the final mol ratio of the directed agents obtained is 20Na
2o:A1
2o
3: 20SiO
2: 380H
2o.
Obtained directed agents is all for the preparation of following reaction mixture, and the add-on of directed agents, accounts for 10% of total aluminium element mole number according to the mole number of aluminium element in directed agents and calculate.
Add successively in mixing tank according to the order of directed agents (abovementioned steps preparation), 1092.62g water glass, 166.31 low alkali aluminium acid sodium solutions, 332.87g Tai-Ace S 150 and 479.4g water under the condition of room temperature and high-speed stirring, total molar ratio of reaction mixture is 4Na
2o:A1
2o
3: 9SiO
2: 220H
2o.After stirring, loaded in stainless steel cauldron, 95 DEG C of static crystallizations 24 hours, then filter, wash, dry NaY molecular sieve product, numbering D3.
It is 5.0 that XRD records its silica alumina ratio, and relative crystallinity is 55.1%, and electromicroscopic photograph display average grain size is 1000nm.
Embodiment 4
The present embodiment illustrates the building-up process of small crystal grain NaY molecular sieve.
By 251.76g high alkali deflection aluminium acid sodium solution, (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, Al
2o
3content is 40.2g/L, Na
2o content is 270g/L, and proportion is 1.323) (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, SiO to join 349.64g water glass
2content is 260.6g/L, Na
2o content is 81.6g/L, and proportion is 1.2655, and modulus is 3.3) in, stir ageing 15 hours at 40 DEG C of temperature, then static ageing 20 hours at 15 DEG C of temperature, finally under the condition stirred, add 78g deionized water.The final mol ratio of the directed agents obtained is 16Na
2o:A1
2o
3: 16SiO
2: 290H
2o.
Obtained directed agents is all for the preparation of following reaction mixture.The add-on of directed agents, accounts for 15% of total aluminium element mole number according to the mole number of aluminium element in directed agents and calculates.
Under the condition of room temperature and high-speed stirring, according to directed agents (abovementioned steps preparation), 1129.04g water glass (the same), 55.90g low alkali aluminium acid sodium solution, (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, Al
2o
3content is 194g/L, Na
2o content is 286.2g/L, and proportion is 1.413), (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides 514.81g Tai-Ace S 150, Al
2o
3content is 88.9g/L, and proportion is 1.2829) and the order of 489.2g water add successively in mixing tank, total molar ratio of reaction mixture is 3Na
2o:A1
2o
3: 10SiO
2: 250H
2o.After stirring, loaded in stainless steel cauldron, 95 DEG C of static crystallizations 36 hours, then filter, wash, dry NaY molecular sieve product, numbering A4.
It is 5.8 that XRD records its silica alumina ratio, and relative crystallinity is 97.6%, and electromicroscopic photograph display average grain size is 100nm.
Comparative example 4
This comparative example illustrates in preparation feedback mixture process, the situation of the addition sequence change of raw material.
Each raw material sources are with embodiment 4.
251.76g high alkali deflection aluminium acid sodium solution is joined in 349.64g water glass, at 40 DEG C of temperature, stirs ageing 15 hours, then static ageing 20 hours at 15 DEG C of temperature, finally under the condition stirred, add 78g deionized water.The final mol ratio of the directed agents obtained is 16Na
2o:A1
2o
3: 16SiO
2: 290H
2o.
Obtained directed agents is all for the preparation of following reaction mixture, and the add-on of directed agents, accounts for 15% of total aluminium element mole number according to the mole number of aluminium element in directed agents and calculate.
Add successively in mixing tank according to 55.90g low alkali aluminium acid sodium solution, 514.81g Tai-Ace S 150,1129.04g water glass, directed agents (abovementioned steps preparation) and the order of 489.2g water under the condition of room temperature and high-speed stirring, total molar ratio of reaction mixture is 3Na
2o:A1
2o
3: 10SiO
2: 250H
2o.After stirring, loaded in stainless steel cauldron, 95 DEG C of static crystallizations 36 hours, then filter, wash, dry NaY molecular sieve product, numbering D4.
It is 5.0 that XRD records its silica alumina ratio, and relative crystallinity is 87%, and electromicroscopic photograph display average grain size is 1000nm.
Embodiment 5
The present embodiment illustrates the building-up process of small crystal grain NaY molecular sieve.
By 335.69g high alkali deflection aluminium acid sodium solution, (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, Al
2o
3content is 40.2g/L, Na
2o content is 270g/L, and proportion is 1.323) (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, SiO to join 466.18g water glass
2content is 260.6g/L, Na
2o content is 81.6g/L, and proportion is 1.2655, and modulus is 3.3) in, stir ageing 10 hours at 50 DEG C of temperature, then static ageing 36 hours at 20 DEG C of temperature, finally under the condition stirred, add 104g deionized water.The final mol ratio of the directed agents obtained is 16Na
2o:A1
2o
3: 16SiO
2: 290H
2o.
Obtained directed agents is all for the preparation of following reaction mixture, and the add-on of directed agents, accounts for 20% of total aluminium element mole number according to the mole number of aluminium element in directed agents and calculate.
Under the condition of room temperature and high-speed stirring, according to directed agents (abovementioned steps preparation), 815.83g water glass (the same), 15.29g low alkali aluminium acid sodium solution, (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, Al
2o
3content is 194g/L, Na
2o content is 286.2g/L, and proportion is 1.413), (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides 558.48g Tai-Ace S 150, Al
2o
3content is 88.9g/L, and proportion is 1.2829) and the order of 528.7g water add successively in mixing tank, total molar ratio of reaction mixture is 2.7Na
2o:A1
2o
3: 8.6SiO
2: 250H
2o.After stirring, loaded in stainless steel cauldron, 90 DEG C of static crystallizations 48 hours, then filter, wash, dry NaY molecular sieve product, numbering A5.
It is 5.6 that XRD records its silica alumina ratio, and relative crystallinity is 92.5%, and electromicroscopic photograph display average grain size is 100nm.
Comparative example 5
This comparative example illustrates that the preparation of directed agents is according to process of the present invention, but the situation that the raw material of reaction mixture adds simultaneously.
Each raw material sources are with embodiment 5
335.69g high alkali deflection aluminium acid sodium solution is joined in 466.18g water glass, ageing 10 hours is stirred at 50 DEG C of temperature, then static ageing 36 hours at 20 DEG C of temperature, finally under the condition stirred, add 104g deionized water, the final mol ratio of the directed agents obtained is 16Na
2o:A1
2o
3: 16SiO
2: 290H
2o.
Obtained directed agents is all for the preparation of following reaction mixture, and the add-on of directed agents, accounts for 20% of total aluminium element mole number according to the mole number of aluminium element in directed agents and calculate.
Under the condition of room temperature and high-speed stirring, in mixing tank, add directed agents (abovementioned steps preparation), 815.83g water glass, 15.29g low alkali aluminium acid sodium solution, 558.48g Tai-Ace S 150 and 528.7g water, total molar ratio of reaction mixture is 2.7Na simultaneously
2o:A1
2o
3: 8.6SiO
2: 250H
2o.After stirring, loaded in stainless steel cauldron, 90 DEG C of static crystallizations 48 hours, then filter, wash, dry NaY molecular sieve product, numbering D5.
It is 5.0 that XRD records its silica alumina ratio, and relative crystallinity is 88%, and electromicroscopic photograph display average grain size is 1000nm.
Embodiment 6
The present embodiment illustrates that the small crystal grain NaY molecular sieve sample A1 obtained embodiment 1 adopts ammonium exchange, hydrothermal treatment consists and aluminium-eliminating and silicon-replenishing process to obtain rich surface silicon small grain Y zeolite of the present invention.
First ammonium exchange is carried out to raw material small crystal grain NaY molecular sieve A1.Compound concentration is 0.5mol/L aqueous ammonium nitrate solution 10 liters.Take small crystal grain NaY molecular sieve A11000 gram, be dissolved in 10 liters of aqueous ammonium nitrate solutions prepared, mixing speed is 300rpm, and at 90 DEG C, constant temperature stirs 1 hour, then filtering molecular sieve. repeat aforesaid operations, until Na in molecular sieve
2o content reach 2.5-5wt%.Obtain dried sample at 500 DEG C, the Water Under thermal treatment 1.5h of 100% water vapour gauge pressure 0.1MPa.Measure 1 liter of water purification and be dissolved in water purification by 200 grams of above-mentioned samples, be rapidly heated stirring, and temperature is 95 DEG C, and mixing speed is 300rpm.In molecular sieve slurry, add hexafluorosilicic acid aqueous ammonium fast, add 50 grams of ammonium hexafluorosilicate altogether, then constant temperature constant speed stirs 2 hours, filters, and dry, obtain production code member NY-1, character lists in table 1.
Comparative example 6
This comparative example is with embodiment 6, and difference is the small crystal grain NaY molecular sieve sample D1 adopting comparative example 1.Obtain contrast product numbering DB-1, character lists in table 1.
Embodiment 7
The present embodiment illustrates that the small crystal grain NaY molecular sieve A2 obtained embodiment 2 adopts ammonium exchange, hydrothermal treatment consists and aluminium-eliminating and silicon-replenishing process to obtain rich surface silicon small grain Y zeolite of the present invention.
First ammonium exchange is carried out to raw material small crystal grain NaY molecular sieve A2.Compound concentration is 0.2mol/L ammonium sulfate solution 10 liters.Take small crystal grain NaY molecular sieve 1000 grams, be dissolved in 10 liters of aqueous ammonium nitrate solutions prepared, mixing speed is 300rpm, and at 90 DEG C, constant temperature stirs 1 hour, then filtering molecular sieve. repeat aforesaid operations, until Na in molecular sieve
2o content reach 2.5-5wt%.Obtain dried sample at 570 DEG C, the Water Under thermal treatment 2.0h of 100% water vapour gauge pressure 0.2MPa.Measure 1 liter of water purification and be dissolved in water purification by the sample of 300 grams of abovementioned steps gained, be rapidly heated stirring, and temperature is 80 DEG C, and mixing speed is 300rpm.Be rapidly in molecular sieve slurry and add hexafluorosilicic acid aqueous ammonium, add 50 grams of ammonium hexafluorosilicate altogether, then constant temperature constant speed stirs 2 hours, filters, and dry, obtain production code member NY-2, character lists in table 1.
Comparative example 7
This comparative example is with embodiment 7, and difference is the small crystal grain NaY molecular sieve sample D2 adopting comparative example 2.Obtain contrast product numbering DB-2, character lists in table 1.
Embodiment 8
The present embodiment illustrates that the small crystal grain NaY molecular sieve A3 obtained embodiment 3 adopts ammonium exchange, hydrothermal treatment consists and aluminium-eliminating and silicon-replenishing process to obtain rich surface silicon small grain Y zeolite of the present invention.
First ammonium exchange is carried out to raw material small crystal grain NaY molecular sieve A3.Compound concentration is 0.5mol/L aqueous ammonium chloride solution 10 liters.Take small crystal grain NaY molecular sieve 1000 grams, be dissolved in 10 liters of aqueous ammonium nitrate solutions prepared, mixing speed is 300rpm, and at 90 DEG C, constant temperature stirs 1 hour, then filtering molecular sieve.Repeat aforesaid operations, until Na in molecular sieve
2o content reach 2.5-5wt%.Obtain dried sample at 550 DEG C, the Water Under thermal treatment 2.5h of 100% water vapour gauge pressure 0.2MPa.Measure 1 liter of water purification and be dissolved in water purification by the sample of above-mentioned experiment gained, be rapidly heated stirring, and temperature is 95 DEG C, and mixing speed is 300rpm.Be rapidly in molecular sieve slurry and add hexafluorosilicic acid aqueous ammonium, add 60 grams of ammonium hexafluorosilicate altogether, then constant temperature constant speed stirs 2 hours, filters, and dry, obtain production code member NY-3, character lists in table 1.
Comparative example 8
This comparative example is with embodiment 8, and difference is the small crystal grain NaY molecular sieve sample D3 adopting comparative example 3.Obtain contrast product numbering DB-3, character lists in table 1.
Embodiment 9
The present embodiment illustrates that the small crystal grain NaY molecular sieve A4 obtained embodiment 4 adopts ammonium exchange, hydrothermal treatment consists and aluminium-eliminating and silicon-replenishing process to obtain rich surface silicon small grain Y zeolite of the present invention.
Compound concentration is 0.7mol/l aqueous ammonium nitrate solution 10 liters.Take small crystal grain NaY molecular sieve sample A41000 gram, being dissolved in mixing speed in 10 liters of aqueous ammonium nitrate solutions prepared is 300rpm, and at 90 DEG C, constant temperature stirs 1 hour, and then filtering molecular sieve, repeats aforesaid operations, until Na in molecular sieve
2o content reach 2.5-5wt%.Obtain dried sample at 600 DEG C, the Water Under thermal treatment 1.0h of 100% water vapour gauge pressure 0.1MPa.Measure 1 liter of water purification and be dissolved in water purification by 200 grams, the sample of above-mentioned experiment gained, be rapidly heated stirring, and temperature is 95 DEG C, and mixing speed is 300rpm.Be rapidly in molecular sieve slurry and add hexafluorosilicic acid aqueous ammonium, add 50 grams of ammonium hexafluorosilicate altogether, then constant temperature constant speed stirs 2 hours, filters, and dry, obtain production code member NY-4, character lists in table 1.
Comparative example 9
This comparative example is with embodiment 9, and difference is the small crystal grain NaY molecular sieve sample D4 adopting comparative example 4.Obtain contrast product numbering DB-4, character lists in table 1.
Embodiment 10
The present embodiment illustrates that the small crystal grain NaY molecular sieve A5 obtained embodiment 5 adopts ammonium exchange, hydrothermal treatment consists and aluminium-eliminating and silicon-replenishing process to obtain rich surface silicon small grain Y zeolite of the present invention.
Compound concentration is 0.7mol/l aqueous ammonium nitrate solution 10 liters.Take small crystal grain NaY molecular sieve sample
A51000 gram, being dissolved in mixing speed in 10 liters of aqueous ammonium nitrate solutions prepared is 300rpm, and at 90 DEG C, constant temperature stirs 1 hour, and then filtering molecular sieve, repeats aforesaid operations, until Na in molecular sieve
2o content reach 2.5-5wt%.Obtain dried sample at 600 DEG C, the Water Under thermal treatment 1.0h of 100% water vapour gauge pressure 0.1MPa.Measure 1 liter of water purification and be dissolved in water purification by 200 grams of above-mentioned molecular sieves, be rapidly heated stirring, and temperature is 95 DEG C, and mixing speed is 300rpm.Be rapidly in molecular sieve slurry and add hexafluorosilicic acid aqueous ammonium, add 60 grams of ammonium hexafluorosilicate altogether, then constant temperature constant speed stirs 2 hours, filters, and dry, obtain production code member NY-5, character lists in table 1.
Comparative example 10
This comparative example is with embodiment 10, and difference is the small crystal grain NaY molecular sieve sample D5 adopting comparative example 5.Obtain contrast product numbering DB-5, character lists in table 1.
Claims (17)
1. a small crystal grain Y-shaped molecular sieve for surperficial Silicon-rich, is characterized in that, molecular sieve phase skeleton SiO
2/ Al
2o
3mol ratio is 5.0 ~ 6.0, surperficial SiO
2/ Al
2o
3mol ratio is 8.0 ~ 13.0, and unit cell parameters is 2.460 ~ 2.468nm, sodium oxide content≤0.1wt%, and average grain diameter is 50 ~ 800nm.
2. according to the Y zeolite of claim 1, wherein, said average grain diameter is 50 ~ 200nm.
3. according to the Y zeolite of claim 1, wherein, said average grain diameter is 200 ~ 500nm.
4. according to the Y zeolite of claim 1, wherein, said average grain diameter is 500 ~ 800nm.
5., according to the Y zeolite of claim 1, it is characterized in that crystallization reservation degree is greater than 90%.
6., according to the Y zeolite of claim 1, it is characterized in that its BET specific surface is 700 ~ 800cm
2/ g.
7. the preparation method of the small crystal grain Y-shaped molecular sieve of the surperficial Silicon-rich of claim 1, it is characterized in that comprising the synthesis of small crystal grain NaY molecular sieve, ammonium hands over and fall sodium, hydrothermal treatment consists and dealumination complement silicon process, under the synthesis of said NaY molecular sieve is included in the condition of synthesis NaY molecular sieve, the mixture A that directed agents, water, silicon source and aluminium source form is carried out hydrothermal crystallizing and also reclaims the product obtained, wherein said directed agents is mixed with water glass by sodium metaaluminate, and the volumetric molar concentration of aluminium element in water glass is edged up to forming mol ratio for (6 ~ 25) Na by zero
2o:A1
2o
3: (6 ~ 25) SiO
2mixture B, then sequentially pass through dynamic ageing, still aging, then add that water obtains, wherein said mixture A obtains after adding mixing tank successively according to the order of directed agents, silicon source, aluminium source and water.
8. according to the preparation method of claim 7, wherein, said dynamic ageing carries out 5 ~ 48 hours at agitation condition, at 15 ~ 60 DEG C.
9. according to the preparation method of claim 7, wherein, said still aging, be carry out 5 ~ 48 hours at static conditions, at 15 ~ 60 DEG C.
10. according to the preparation method of claim 7, wherein, the mol ratio of said mixture A is (2 ~ 6) Na
2o:A1
2o
3: (8 ~ 20) SiO
2: (200 ~ 400) H
2o.
11. according to the preparation method of claim 7, and wherein, in directed agents, the mole number of aluminium element accounts for 3 ~ 30% of total aluminium element mole number in mixture A.
12. according to the preparation method of claim 7, and wherein, said hydrothermal crystallizing carries out 15 ~ 48 hours at 90 ~ 100 DEG C.
13. according to the preparation method of claim 7, and wherein, after said ammonium is handed over and fallen the process of sodium, in molecular sieve, the content of sodium oxide is 2.5 ~ 5.0 % by weight.
14. according to the preparation method of claim 7 or 13, wherein, said ammonium hands over the process of falling sodium to carry out one or many, it is the ammonium salt solution of 0.1 ~ 1.0mol/L that said ammonium hands over the process of falling sodium to comprise employing ammonium concentration, under temperature 50 ~ 100 DEG C, solvent and solute weight ratio are the condition of 8 ~ 15:1, constant temperature process 0.5 ~ 1.5 hour.
15. according to the preparation method of claim 14, and wherein, said ammonium salt is one or more in ammonium nitrate, ammonium sulfate, ammonium chloride and ammonium acetate.
16. according to the preparation method of claim 7, and wherein, the process of said hydrothermal treatment consists processes 1 ~ 10 hour at 100% water vapour, gauge pressure 0.1 ~ 0.2MPa, temperature 500 ~ 650 DEG C.
17. according to the preparation method of claim 7, wherein, the process of said dealumination complement silicon is that the molecular sieve process through hydrothermal treatment consists obtained is pulled an oar in aqueous and obtained the slurry that solvent and solute weight ratio is 3 ~ 10:1, again at 80 ~ 120 DEG C of temperature, the charging capacity of 10 ~ 60 grams is added, by (NH according to every 100 mol sieves
4)
2siF
6to add in said slurry and to stir, then reclaiming product.
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