CN105084386B - A kind of surface Silicon-rich small crystal grain Y-shaped molecular sieve and preparation method thereof - Google Patents
A kind of surface Silicon-rich small crystal grain Y-shaped molecular sieve and preparation method thereof Download PDFInfo
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Abstract
A kind of small crystal grain Y-shaped molecular sieve of surface Silicon-rich, it is characterised in that molecular sieve body phase skeleton SiO2/Al2O3Mol ratio is 5.0~6.0, surface SiO2/Al2O3Mol ratio is 8.0~13.0, and cell parameter is 2.46~2.468nm, and sodium oxide molybdena weight content≤0.1wt%, average grain diameter is 50~800nm.
Description
Technical field
The present invention relates to a kind of Y type molecular sieve and preparation method thereof, more particularly to a kind of small crystalline substance of surface Silicon-rich
The preparation method of grain Y type molecular sieve.
Background technology
The fifties end, Milton and Breck successfully synthesize Y type molecular sieve.Due in the structure of Y type molecular sieve
SiO2With Al2O3The ratio between be more than X-type molecular sieve so that heat endurance and hydrothermal stability are improved.Early seventies, Grace
Development of company directing agent method synthesis NaY molecular sieve, raw material instead of the Ludox of costliness with waterglass, and technique is simplified,
Growth cycle shortens, so that NaY molecular sieve is rapid and is widely applied to petrochemical industry especially cracking of oil catalytic field.
So far, in hundreds of molecular sieve developed, what industrially usage amount was maximum is Y type molecular sieve.At present, Y types
The synthesis of molecular sieve industrially mainly uses crystal seed glue method.Due to the use and improvement of crystal seed glue, make the synthesis of Y type molecular sieve
The time of crystallization greatly shortens, and is that the industrialization of Y type molecular sieve is laid a good foundation.
Industrial application and development proposes higher requirement to the synthesis of molecular sieve and products thereof performance, in turn
Promote the further investigation of Zeolite synthesis technology.Synthesizing small-grain is concentrated mainly on to the requirements at the higher level that Y type molecular sieve is synthesized
And ultra-fine grain zeolite product, improve the molecular sieve of silica alumina ratio and synthesizing high-silicon aluminum ratio ratio and little crystal grain and ultra-fine grain
Three aspects such as product.
The Y type molecular sieve of little crystallite size is due to larger external surface area and higher micropore diffusion speed, carrying
In terms of height conversion macromolecular ability, the secondary cracking for reducing product and reduction catalyst coking, show than conventional die chi
Very little Y type molecular sieve more superior performance, therefore the study on the synthesis of the Y type molecular sieve of little crystal grain turns into focus.In conventional manner
The Y type molecular sieve of synthesis typically has an about 1000nm crystallite dimension, and little crystal grain can even reach nanoscale (<100nm)
The synthesis report of crystallite dimension this respect is still less.
Y type molecular sieve is handled with hot crushing technology, although its grain size can be made to be reduced to 100nm, but this physics powder
The mode of broken processing not only expends large energy, and destroys the crystal structure of molecular sieve, is allowed to part amorphous.If
Can synthesizing small-grain Y type molecular sieve be directly then most simple and feasible method, therefore, it is necessary to will the conventional Y type molecular sieve of optimization
Synthesis condition, by improve and increase be oriented to dosage, improve feed intake the methods such as basicity reduce molecular sieve particle diameter, to obtain small crystalline substance
Grain Y type molecular sieve product and the commercialized optimum condition of suitable molecular sieve.
The optimization of synthesis condition generally include preparation such as crystal seed glue, the influence of ageing time, the preparation of silica-alumina gel and
The condition of hydrothermal crystallizing, including basicity, crystallization temperature and crystallization time etc..The general shadow by crystallization condition of composition of silica-alumina gel
Ring and cause molecular sieve different；Hydrothermal crystallizing condition more immediate influence the synthesis of molecular sieve, their both mutually restrictions, and phase
Mutually affect silica alumina ratio, crystallinity and the grain size of molecular sieve.The basicity of silica-alumina gel is one ten in sieve synthesis procedure
Divide crucial factor, Microsize NaY Zeolite can be prepared by improving the basicity of synthetic system.Due to industrial mostly using containing many
The waterglass of poly- state silicon is silicon source, improves system basicity, can not only increase the depolymerization of poly state silicon, and be conducive to sial to coagulate
More nucleus are formed in glue, so that crystallite dimension reduces.Schhoeman etc. (Sehoeman B J, Sterte J,
Chemical Communications, 1993:994~99) using high alkalinity, the method for high silica alumina ratio, directly closed from liquid phase
It is less than 150nm NaY molecular sieve into crystallite dimension.But, with the increase of system basicity, the yield of synthetic product declines.
Bi-ZengZ et al. also found as synthetic system n (Na under study for action2O)/n(Al2O3)=6~15, and it is more than 3000r/ in rotating speed
Homogeneous, mobility Alusil is prepared under min high-speed stirred, Y type molecular sieve of the particle diameter in below 100nm, but silicon can be made
Aluminum ratio is generally less than 4.5 (Bi-Zeng Z, Mary A.W, Miehael L.Control of Particle size and
surface ProPertles of CrystaIs of NaX Zeolite,Chemistry of Materials,2002,14:
363-3642)。
In the synthetic method of Y type molecular sieve, include the directing agent method based on commercial synthesis and the clear liquid based on template
Synthetic method.In directing agent method based on commercial synthesis, lived by adding rare earth ion, aluminum complexing agent and surface into synthetic system
The additives such as property agent, it is possible to decrease the average grain diameter of NaY molecular sieve, but it has the disadvantage that particle diameter distribution is wider.Linder etc.
(Lindner T., Lech ert H., Zeolites, 1996,16：196-206) faujasite is synthesized in research mineralizer
Found during influence, a small amount of organic complexing agent that can be with aluminium formation stable comple is added into synthetic system, can typically be promoted
Enter the nucleation of molecular sieve and the growth of crystal, so that the crystallite dimension of molecular sieve reduces, narrow particle size distribution, and will not
Reduce framework of molecular sieve silica alumina ratio.Maher etc. discloses a kind of side of synthetic faujasites type molecular sieve in US3516786
Method, before synthetic system heating crystallization steps, a small amount of organic solvent miscible with water, such as two are added into synthetic system
MSM, DMF, tetrahydrofuran, methanol, ethanol, acetone etc., final zeolite crystal size are 0.01~0.1
μm.Ambs etc., in order to reduce the volatilization of the organic solvent brought by heating, has used glucose, finally in US4372931
Crystallite dimension is 0.035~0.069 μm.But, after addition organic solvent, the skeleton SiO of molecular sieve2/Al2O3Than relatively low, typically
Less than 2.5.And another clear liquid synthetic method based on template, the method can obtain nano level NaY molecular sieve, and have crystalline substance
The narrower advantage of body particle diameter distribution, but its product yield is very low, and cost is very high.Holmberg etc. is by adding 4 bromide
With TMAH double template, by optimizing TMA+Y type molecular sieve crystallite dimension and receipts are controlled with the concentration of anion
Rate, finally synthesizes the Y type molecular sieve that granularity is 37nm, but its product yield is very low and cost it is very high (Holmberg B.A.,
Wang H., Controlling size and yield of zeolite Y nanocrystals Using
Tetramethyl ammonium bromide, MicroPorous and MesoPorous Material, 2003,59:13-
28)。
The height of framework si-al ratio and its structures shape in the duct main character and function of molecular sieve.In general,
The higher molecular sieve of silica alumina ratio often has stronger heat-resisting, resistance to vapor and capacity antacid；In addition, different types of molecular sieve
To some catalytic reactions, different specific regularity are also shown with the change of its silica alumina ratio.It therefore, it can by directly synthesizing
Or the silica alumina ratio of different type molecular sieve is obtained by modified method (i.e. secondary synthesis), so as to regulate and control its property and function.
The silica alumina ratio of the Y type molecular sieve synthesized with conventional method is less than 5.0, is typically high silicon Y more than 6.0 by silica alumina ratio
Type molecular sieve.Obtaining the conventional method of high-Si Y-type molecular sieve has two kinds：A kind of is the method directly synthesized, it is another be
On the basis of single sintering, product is reprocessed using specific route, i.e., skeleton is improved by the method for secondary synthesis
Silica alumina ratio.At present, two-step fabrication mainly has：High temperature hydro-thermal method (US3449370), high temperature gas-phase reaction method (US4701313),
Ammonium fluosilicate liquid phase reactor method (US4093560) etc., the shortcomings of these methods is that preparation process is numerous and diverse, zeolite crystallinity loss compared with
Greatly, preparation technology process CIMS is complicated, yield is low and environmental pollution is larger etc..
And need to consider more factor in the method directly synthesized, for example：The composition of reactant mixture, preparation side
Formula, reactant source, the preparation of directed agents, whether stir, gel acid-base value and crystallization condition etc..Usual silica alumina ratio is lower
Y type molecular sieve is easier to be made, otherwise the preparation condition of silica alumina ratio more high request is harsher, it is more difficult to synthesize preferable sample.
In the method directly synthesized, the conventional approach for improving silica alumina ratio mainly has following several：A kind of approach is extension crystallization time,
But, the approach is after silica alumina ratio is more than 5.5, and exponentially form declines crystallization velocity, makes synthesis uncomfortable because of time-consuming, cost height
For industrial production；Another approach be using organic amine (US5116590, US4965059, CN96105159.7,
CN97196899) or inorganic salts (US4333859, US4309313) are as template, but this equally exists that cost is high, crystallization
The problems such as time length, relatively low utilization rate of silicon, meanwhile, the silicon waste liquid of a large amount of high concentrations is discharged, and has both been wasted and has also been polluted environment.
It is always the focus and difficulty of research using non-template agent method in the method for direct synthesizing high-silicon aluminum ratio Y type molecular sieve
Point.CN102198950A discloses a kind of preparation method of high silica alumina ratio NaY molecular sieve；Silicon source, silicon source and deionized water are mixed
Close, directed agents, waterglass, acid aluminium salt and the sodium aluminate solution of two kinds of different mol ratios are taken according to following gel masses mol ratios
It is well mixed that two kinds of gels, difference crystallization are made；Gel masses mol ratio is：(1.0~6.5) Na2O:Al2O3:(5.0~18)
SiO2:(100~280) H2O, wherein directed agents Al2O3Account for Al2O3The 0.01~15% of gross weight；Two kinds of gels are according to quality
Than for 1：(0.1~10) is uniformly mixed, and mixed gel is made；By obtained mixed gel, crystallization 2~50 is small at 80~120 DEG C
When, NaY molecular sieve is made.In molar ratio under the same conditions, this method can prepare high silicon within the shorter time
The NaY molecular sieve of aluminum ratio.Method disclosed in CN1785807A and CN1785808A is the stirring ageing 0.5 at 15~60 DEG C in advance
~48 hours obtained directed agents, are then directed to agent, water, silicon source, silicon source and reactant mixture are made, after stirring will reaction it is mixed
Compound crystallization, first step dynamic crystallization, second step static crystallization in two steps, eventually pass filter, washing, dry, relative knot is made
It is SiO that brilliant degree, which is more than 80%, framework si-al ratio,2/Al2O3Mol ratio is between 6.0~7.0, and average crystal grain is in 300~800nm
Between high silicon aluminium ratio small crystal NaY molecular sieve.High silica alumina ratio, the preparation of the NaY molecular sieve of little crystal grain disclosed in CN1789125
Method, is to synthesize NaY molecular sieve directed agents first, is then made solidifying with waterglass, directed agents, acid aluminium salt and sodium metaaluminate
Glue, after 0~70h of crystallization, silicon source, then continuation 0.5~50h of crystallization at 90~120 DEG C are added by gel at 50~100 DEG C,
Eventually pass filter, washing, dry, it is the NaY molecular sieve that 5.2~7.0, crystal grain is 100~400nm to obtain silica alumina ratio.
Y type molecular sieve will be modified processing before application to it, obtain with different SiO2/Al2O3Than, it is acid and
The molecular sieve of pore structure.The modification of molecular sieve is realized typically by the content of aluminium is changed, wherein sour dealuminzation is Y types point
A modified important method of son sieve.The condition of acid treatment is typically relatively gentleer, can not saboteur's sieve structure, selective is de-
Except the non-framework aluminum in molecular sieve.But for the non-framework aluminum of the difficult removing in part, using general acid treatment can not by it effectively,
Uniform removing, if by improving acid concentration, the removing of part framework aluminum can be caused so that modified molecular sieve structure is broken
Bad, crystallinity declines, sour irrational distribution, so as to directly result in the decline of catalytic performance.It is another with salicide processes molecular sieve
A kind of method of modifying.CN1382632A discloses a kind of super stabilizing method of small-grain Y-type zeolite, and this method is to use silicon tetrachloride
Dry gas and fine grain NaY zeolitic contact, obtained after washing, due to its raw material itself heat and hydrothermal stability just compared with
Difference, while the inventive method is to handle molecular sieve by the way of gas phase dealumination complement silicon, this causes the heat and hydrothermally stable of product
Property it is worse, activity it is low；There is small in batches, the shortcomings of consuming energy higher in the industrial production in other this gas phase treatment method.
The content of the invention
In terms of disclosed document, there is not report skeleton SiO also2/Al2O3Mol ratio is between 5.0~6.0, and average crystal grain
It can be adjusted between 50~200nm, 200~500nm, 500~800nm, the middle high silicon aluminium ratio small crystal NaY that particle diameter distribution is narrow divides
Son sieve.Inventor has found the temperature and time, the temperature and time of directed agents static burn in, directed agents of directed agents dynamic aging
Constitute and addition, the composition of reactant mixture, crystallization temperature and these influence factors of crystallization time are equal in the reactive mixture
The silica alumina ratio and average grain diameter of synthesized molecular sieve can be influenceed, by optimizing above-mentioned influence factor simultaneously, accurate tune is can reach
The average grain diameter of whole product and the purpose of silica alumina ratio, can obtain the Y type molecular sieve of more little crystal grain, 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 surface Silicon-rich, and the second purpose is to provide one
Plant and be different from prior art, the simple non-template agent method of with low cost, technique prepares the small crystal grain Y-shaped molecular sieve of surface Silicon-rich
Method.
The small crystal grain Y-shaped molecular sieve for the surface Silicon-rich that the present invention is provided, it is characterised in that molecular sieve body phase skeleton SiO2/
Al2O3Mol ratio is 5.0~6.0, surface SiO2/Al2O3Mol ratio is 8.0~13.0, and cell parameter is 2.46~2.468nm,
Sodium oxide molybdena weight content≤0.1wt%, average grain diameter is 50~800nm.
The small crystal grain Y-shaped molecular sieve for the surface Silicon-rich that the present invention is provided, the silicon atom of framework of molecular sieve and rubbing for aluminium atom
You compare, i.e. body phase skeleton SiO2/Al2O3Mol ratio is 5.0~6.0.Determined using NMR methods；The silicon of zeolite crystal outer surface
The mol ratio of atom and aluminium atom, i.e. surface SiO2/Al2O3Mol ratio is 8.0~13.0, is determined using XPS methods.
The small crystal grain Y-shaped molecular sieve for the surface Silicon-rich that the present invention is provided, it crystallizes reservation degree and is more than 90%, described crystallization
Reservation degree is defined：With the Y types point of little crystal grain used before the small crystal grain Y-shaped molecular sieve of surface Silicon-rich and the processing of surface Silicon-rich
The percentage of the ratio of the peak height sum of 5 characteristic peaks in the X-ray diffracting spectrum of son sieve, 5 described characteristic peaks are respectively that 2 θ are
15.8th, the characteristic peak corresponding to 20.7,24.0,27.4 and 31.8 peak positions.The small-grain Y-type for the surface Silicon-rich that the present invention is provided point
Son sieve, its average grain diameter can between 50~800nm modulation, as needed, its average grain diameter can for 50~
200nm, can be either 200~500nm or can be 500~800nm.Its BET is 700~800cm than surface2/g。
Present invention also offers the corresponding preparation method of small crystal grain Y-shaped molecular sieve of above-mentioned surface Silicon-rich, it is characterised in that
Drop sodium, hydro-thermal process and dealumination complement silicon process are handed in synthesis including small crystal grain NaY molecular sieve, ammonium, the conjunction of described NaY molecular sieve
Into being included under conditions of synthesis NaY molecular sieve, the mixture A for being directed to agent, water, silicon source and silicon source composition carries out hydrothermal crystallizing
And obtained product is reclaimed, wherein described directed agents are to mix sodium metaaluminate with waterglass, make aluminium element in waterglass
It is (6~25) Na that molar concentration is edged up to mol ratio is formed by zero2O:A12O3:(6~25) SiO2Mixture B, then order
By dynamic ageing, still aging, then add what water was obtained, wherein described mixture A is according to directed agents, silicon source, silicon source
Sequentially add what is obtained after mixing tank with the order of water.
The present invention is having found directed agents raw material contact condition, dynamic aging, static burn in, the composition of directed agents and reacted
The factor such as addition in mixture, the raw material addition sequence of reactant mixture and crystallization temperature and time can influence synthesized
On the basis of the silica alumina ratio and average grain diameter of molecular sieve, by optimizing above-mentioned influence factor simultaneously, accurate adjustment product can reach
Average grain diameter and silica alumina ratio purpose.And the synthetic method of existing Y type molecular sieve can only synthesize grain size in 900-
1300nm、SiO2/Al2O3Product of the mol ratio between 4.8~5.3.
In the preparation method of the present invention, described small crystal grain Y-shaped molecular sieve is obtained using direct synthesis technique：First prepare and lead
To agent, then prepare reactant mixture, most afterwards through crystallization, filtering, washing, dry and obtain middle high silicon aluminium ratio small crystal NaY molecule
Sieve.Any template or additive are added without in described reactant mixture, the molecular sieve that synthesis is obtained need not also be carried out
Chemically or physically method carry out dealuminzation, or dealumination complement silicon is secondary synthesis to improve silica alumina ratio.It is raw materials used it is inexpensive, be easy to get,
It is simple for process, advantageously reduce manufacturing cost.
Wherein, the preparation of described directed agents is different from the preparation process that conventional method synthesizes NaY molecular sieve directed agents, conventional
Method can be mixed silicon source and silicon source with any order, aging under quiescent conditions after being well mixed；Also different from patent
The preparation method of directed agents in CN1785807, CN1785808, stirs the obtained directed agents of aging at 15~60 DEG C.Present invention side
The preparation of directed agents in method is to mix sodium metaaluminate with waterglass, the molar concentration of aluminium element in waterglass is edged up by zero
It is (6~25) Na to mol ratio is formed2O:A12O3:(6~25) SiO2Mixture B, then sequentially pass through dynamic ageing, standing
Ageing, then add what water was obtained.More specifically preparation process comprises the following steps：(1) in 15~60 DEG C of temperature and stirring condition
Under, sodium metaaluminate is added into waterglass, mol ratio is formed for (6~25) Na2O:A12O3:(6~25) SiO2It is described
Mixture B；(2) mixture B is dynamically aged 5~48 hours at 15~60 DEG C, then still aging 5~48 at 15~60 DEG C
Hour；(3) after ageing is finished, water is added under conditions of stirring, the final mol ratio for making directed agents is (6~25) Na2O:
A12O3:(6~25) SiO2:(200~400) H2O。
After directed agents are obtained, the preparation method further step of described small crystal grain NaY molecular sieve is：At room temperature
Add water, silicon source, silicon source, directed agents and obtain mixture A, mixture A mol ratio is (2~6) Na2O:A12O3:(8~20)
SiO2:(200~400) H2O, the addition of directed agents accounts for the 3 of total aluminium element molal quantity according to the molal quantity of aluminium element in directed agents
~30% calculates.Described mixture A is sequentially added and obtained after mixing tank according to the order of directed agents, silicon source, silicon source and water
's.
Described water is deionized water or distilled water, and silicon source can be one in waterglass, Ludox, silica gel and white carbon
Plant or a variety of mixtures, described silicon source is sodium metaaluminate, aluminum sulfate, aluminium chloride, aluminum nitrate, aluminium hydroxide and intends thin water aluminium
One or more mixtures in stone.
Described mixture A hydrothermal crystallizing is carried out 15-48 hours in closed reactor at 90-100 DEG C.
In the preparation method of the present invention, after the NaY molecular sieve of little crystal grain is obtained, drop sodium is also handed over by ammonium, at hydro-thermal
Reason and the process of dealumination complement silicon can just obtain the small crystal grain Y-shaped molecular sieve of the surface Silicon-rich of the present invention.
Wherein, described ammonium hands over the process of drop sodium to be that the content of sodium oxide molybdena in molecular sieve is reduced into 2.5~5.0 weights
Measure %.The process that described ammonium hands over the process of drop sodium to carry out one or many, described ammoniums friendship drop sodium includes dense using ammonium ion
The ammonium salt solution for 0.1~1.0mol/L is spent, is 8~15 in 50~100 DEG C of temperature, solvent and solute weight ratio：Under conditions of 1, constant temperature
Processing 0.5~1.5 hour.Described ammonium salt is the one or more in ammonium nitrate, ammonium sulfate, ammonium chloride and ammonium acetate.
Wherein, the process of described hydro-thermal process is in 100% vapor, 0.1~0.2MPa of gauge pressure, temperature 500~650
Handled 1~3 hour at DEG C.
Wherein, the process of described dealumination complement silicon is that the molecular sieve for obtaining the process of hydrothermal treatment is beaten in aqueous
It is 3~10 that slurry, which obtains solvent and solute weight ratio,：1 slurry, at a temperature of 80~120 DEG C, according to every 100 gram molecule sieve add 10~
60 grams of inventory, by (NH4)2SiF6Add in described slurry and stir, then recovery product.Described stirring is in temperature
Spend at 80-120 DEG C, preferably to stir 0.5-5 hours in constant temperature constant speed.The process of described recovery product includes filtering and dry
It is dry.
The method of the present invention, the process of hydro-thermal process and the dealumination complement silicon combination of use, makes the silicon master in ammonium hexafluorosilicate
Y molecular sieve surface is added to, removing silicon when filling up hydrothermal aging, aluminium and the lattice vacancy produced have increased considerably Y molecules
The surface silica alumina ratio of sieve, and overall framework si-al ratio is to be increased slightly.Final Y molecular sieve structure cell only has minimal shrink, phase
It is 100%-130% to crystallinity, cell parameter is 2.460-2.468nm, sodium oxide content≤0.1wt%.
Embodiment
The following examples are used to the present invention is described in more detail, but the scope of the present invention is not limited solely to these embodiments
Scope.
In each embodiment and comparative example, the measure than surface uses low temperature liquid nitrogen physisorphtion；Relative crystallinity
X-ray diffraction method is used with cell parameter；Body phase skeleton SiO2/Al2O3Mol ratio is determined using NMR methods；Surface SiO2/Al2O3
Mol ratio is determined using XPS methods；The grain size of molecular sieve is determined by the way of SEM (SEM), by
JSM-5610LV type ESEMs instrument is observed.
Embodiment 1
This example demonstrates that the building-up process of small crystal grain NaY molecular sieve.
By 50.39g high alkali deflection aluminium acid sodiums solution, (sinopec limited company catalyst Chang Ling branch company provides, Al2O3
Content is 40.2g/L, Na2O content is 255g/L, and proportion is 1.324) to be added to 65.56g waterglass (sinopec share is limited
Company's catalyst Chang Ling branch company provides, SiO2Content is 260.6g/L, Na2O content is 81.6g/L, and proportion is 1.2655, mould
Is ageing 48 hours in 3.3), is stirred at room temperature in number, then static ageing 5 hours at a temperature of 60 DEG C, finally in stirring
Under the conditions of add 15g deionized waters, the obtained final mol ratio of directed agents be 15Na2O:A12O3:15SiO2:320H2O。
Obtained directed agents are completely used for the preparation of following reactant mixtures, the addition of directed agents, according to aluminium in directed agents
The molal quantity of element accounts for 3% calculating of total aluminium element molal quantity.
Under conditions of room temperature and high-speed stirred according to directed agents (abovementioned steps preparation), 1682.6g waterglass (ibid),
(sinopec limited company catalyst Chang Ling branch company provides 134.19g low alkali aluminium acid sodium solutions, Al2O3Content is
194g/L, Na2O content is 286.2g/L, proportion be 1.413), 448.02g aluminum sulfate (sinopec limited company catalyst
Chang Ling branch company provides, Al2O3Content is 88.9g/L, and proportion is that the order 1.2829) with 150.4g water sequentially adds mixing tank
In, total molar ratio of reactant mixture is 3Na2O:A12O3:12SiO2:209H2O.After stirring, it is loaded into stainless
In steel reactor, in 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, which measures its silica alumina ratio, and relative crystallinity is 93.7%, and electromicroscopic photograph shows average grain size
For 300nm.
Comparative example 1
This comparative example explanation changes directed agents aging condition, only with still aging and anti-during synthesis directed agents
The situation for answering the feeding sequence of mixture to change.
Each raw material sources be the same as Example 1.
50.39g high alkali deflection aluminium acid sodium solution is added in 65.56g waterglass, still aging 28 hours at room temperature,
It is 15Na to add the final mol ratio of directed agents that 15g deionized waters obtain2O:A12O3:15SiO2:320H2O。
Obtained directed agents are completely used for the preparation of following reactant mixtures, the addition of directed agents, according to aluminium in directed agents
The molal quantity of element accounts for 3% calculating of total aluminium element molal quantity.
1682.6g waterglass is first added in mixing tank under conditions of room temperature and high-speed stirred, is sequentially added
150.4g water, 134.19g low alkali aluminium acid sodium solutions, directed agents (abovementioned steps preparation) and 448.02g aluminum sulfate, reaction mixing
Total molar ratio of thing is 3Na2O:A12O3:12SiO2:209H2O.After stirring, it is loaded into stainless steel cauldron,
In 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, which measures silica alumina ratio, and relative crystallinity is 88.7%, and electromicroscopic photograph shows that average grain size is
1000nm。
Embodiment 2
This example demonstrates that the building-up process of small crystal grain NaY molecular sieve.
By 50.39g high alkali deflection aluminium acid sodiums solution, (sinopec limited company catalyst Chang Ling branch company provides, Al2O3
Content is 40.2g/L, Na2O content is 255g/L, and proportion is 1.324) to be added to 65.56g waterglass (sinopec share is limited
Company's catalyst Chang Ling branch company provides, SiO2Content is 260.6g/L, Na2O content is 81.6g/L, and proportion is 1.2655, mould
Number is in 3.3), stirring ageing 5 hours at a temperature of 60 DEG C, then static ageing 5 hours at a temperature of 60 DEG C, finally in stirring
Under the conditions of add 15g deionized waters, the obtained final mol ratio of directed agents be 15Na2O:A12O3:15SiO2:320H2O。
Obtained directed agents are completely used for the preparation of following reactant mixtures, the addition of directed agents, according to aluminium in directed agents
The molal quantity of element accounts for 3% calculating of total aluminium element molal quantity.
Under conditions of room temperature and high-speed stirred according to directed agents (abovementioned steps preparation), 1682.6g waterglass (ibid),
(sinopec limited company catalyst Chang Ling branch company provides 134.19g low alkali aluminium acid sodium solutions, Al2O3Content is
194g/L, Na2O content is 286.2g/L, proportion be 1.413), 448.02g aluminum sulfate (sinopec limited company catalyst
Chang Ling branch company provides, Al2O3Content is 88.9g/L, and proportion is that the order 1.2829) with 1419.4g water sequentially adds mixing tank
In, total molar ratio of reactant mixture is 3Na2O:A12O3:12SiO2:350H2O.After stirring, it is loaded into stainless
In steel reactor, in 100 DEG C of static crystallizations 32 hours, then filter, wash, dry NaY molecular sieve product, numbering A2.
It is 5.9 that XRD, which measures its silica alumina ratio, and relative crystallinity is 90.6%, and electromicroscopic photograph shows that average grain size is
800nm。
Comparative example 2
This comparative example illustrates to change silicon source, the situation of the charging sequence of silicon source in prepared by directed agents.
Each raw material sources be the same as Example 2.
65.56g waterglass is added in 50.39g high alkali deflection aluminium acid sodium solution, stirring ageing 5 hours at a temperature of 60 DEG C,
Then static ageing 5 hours at a temperature of 60 DEG C, finally add 15g deionized waters, obtained directed agents under conditions of stirring
Final mol ratio is 15Na2O:A12O3:15SiO2:320H2O。
Obtained directed agents are completely used for the preparation of following reactant mixtures, the addition of directed agents, according to aluminium in directed agents
The molal quantity of element accounts for 3% calculating of total aluminium element molal quantity.
Under conditions of room temperature and high-speed stirred according to directed agents (abovementioned steps preparation), 1682.6g waterglass,
The order of 134.19g low alkali aluminium acid sodium solutions, 448.02g aluminum sulfate and 1419.4g water is sequentially added in mixing tank, and reaction is mixed
Total molar ratio of compound is 3Na2O:A12O3:12SiO2:350H2O.After stirring, stainless steel cauldron is loaded into
In, in 100 DEG C of static crystallizations 32 hours, then filter, wash, dry NaY molecular sieve product, numbering D2.
It is 5.0 that XRD, which measures its silica alumina ratio, and relative crystallinity is 87%, and electromicroscopic photograph shows that average grain size is
1000nm。
Embodiment 3
This example demonstrates that the building-up process of small crystal grain NaY molecular sieve.
By 164.54g high alkali deflection aluminium acid sodiums solution, (sinopec limited company catalyst Chang Ling branch company provides, Al2O3
Content is 40.2g/L, Na2O content is 340g/L, and proportion is 1.297) to be added to 291.37g waterglass (sinopec share is limited
Company's catalyst Chang Ling branch company provides, SiO2Content is 260.6g/L, Na2O content is 81.6g/L, and proportion is 1.2655, mould
Number is in 3.3), stirring ageing 20 hours at a temperature of 30 DEG C, then static ageing 15 hours at a temperature of 40 DEG C, finally in stirring
Under conditions of add 60g deionized waters.The obtained final mol ratio of directed agents is 20Na2O:A12O3:20SiO2:380H2O。
Obtained directed agents are completely used for the preparation of following reactant mixtures, the addition of directed agents, according to aluminium in directed agents
The molal quantity of element accounts for 10% calculating of total aluminium element molal quantity.
It is (same according to directed agents (abovementioned steps preparation), 1092.62g waterglass under conditions of room temperature and high-speed stirred
On), 166.31 low alkali aluminium acid sodium solutions (sinopec limited company catalyst Chang Ling branch company provide, Al2O3Content is
194g/L, Na2O content is 286.2g/L, proportion be 1.413), 332.87g aluminum sulfate (sinopec limited company catalyst
Chang Ling branch company provides, Al2O3Content is 88.9g/L, and proportion is that the order 1.2829) with 479.4g water sequentially adds mixing tank
In, total molar ratio of reactant mixture is 4Na2O:A12O3:9SiO2:220H2O.After stirring, stainless steel is loaded into
In reactor, in 95 DEG C of static crystallizations 24 hours, then filter, wash, dry NaY molecular sieve product, numbering A3.
It is 5.2 that XRD, which measures its silica alumina ratio, and relative crystallinity is 95.1%, and electromicroscopic photograph shows that average grain size is
300nm。
Comparative example 3
This comparative example explanation changes directed agents aging condition during synthesis directed agents, only with the feelings of dynamic ageing
Condition.
Raw material sources be the same as Example 3.
164.54g high alkali deflection aluminium acid sodium solution is added in 291.37g waterglass, stirring ageing 20 is small at a temperature of 30 DEG C
When, 60g deionized waters are finally added under conditions of stirring, the obtained final mol ratio of directed agents is 20Na2O:A12O3:
20SiO2:380H2O。
Obtained directed agents are completely used for the preparation of following reactant mixtures, the addition of directed agents, according to aluminium in directed agents
The molal quantity of element accounts for 10% calculating of total aluminium element molal quantity.
Under conditions of room temperature and high-speed stirred according to directed agents (abovementioned steps preparation), 1092.62g waterglass,
The order of 166.31 low alkali aluminium acid sodium solutions, 332.87g aluminum sulfate and 479.4g water is sequentially added in mixing tank, reaction mixing
Total molar ratio of thing is 4Na2O:A12O3:9SiO2:220H2O.After stirring, it is loaded into 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, which measures its silica alumina ratio, and relative crystallinity is 55.1%, and electromicroscopic photograph shows that average grain size is
1000nm。
Embodiment 4
This example demonstrates that the building-up process of small crystal grain NaY molecular sieve.
By 251.76g high alkali deflection aluminium acid sodiums solution, (sinopec limited company catalyst Chang Ling branch company provides, Al2O3
Content is 40.2g/L, Na2O content is 270g/L, and proportion is 1.323) to be added to 349.64g waterglass (sinopec share is limited
Company's catalyst Chang Ling branch company provides, SiO2Content is 260.6g/L, Na2O content is 81.6g/L, and proportion is 1.2655, mould
Number is in 3.3), stirring ageing 15 hours at a temperature of 40 DEG C, then static ageing 20 hours at a temperature of 15 DEG C, finally in stirring
Under conditions of add 78g deionized waters.The obtained final mol ratio of directed agents is 16Na2O:A12O3:16SiO2:290H2O。
Obtained directed agents are completely used for the preparation of following reactant mixtures.The addition of directed agents, according to aluminium in directed agents
The molal quantity of element accounts for 15% calculating of total aluminium element molal quantity.
It is (same according to directed agents (abovementioned steps preparation), 1129.04g waterglass under conditions of room temperature and high-speed stirred
On), 55.90g low alkali aluminium acid sodium solutions (sinopec limited company catalyst Chang Ling branch company provide, Al2O3Content is
194g/L, Na2O content is 286.2g/L, proportion be 1.413), 514.81g aluminum sulfate (sinopec limited company catalyst
Chang Ling branch company provides, Al2O3Content is 88.9g/L, and proportion is that the order 1.2829) with 489.2g water sequentially adds mixing tank
In, total molar ratio of reactant mixture is 3Na2O:A12O3:10SiO2:250H2O.After stirring, it is loaded into stainless
In steel reactor, in 95 DEG C of static crystallizations 36 hours, then filter, wash, dry NaY molecular sieve product, numbering A4.
It is 5.8 that XRD, which measures its silica alumina ratio, and relative crystallinity is 97.6%, and electromicroscopic photograph shows that average grain size is
100nm。
Comparative example 4
This comparative example explanation is during reactant mixture is prepared, the situation of the addition sequence change of raw material.
Each raw material sources be the same as Example 4.
251.76g high alkali deflection aluminium acid sodium solution is added in 349.64g waterglass, stirring ageing 15 is small at a temperature of 40 DEG C
When, then static ageing 20 hours at a temperature of 15 DEG C, finally add 78g deionized waters under conditions of stirring.What is obtained leads
It is 16Na to the final mol ratio of agent2O:A12O3:16SiO2:290H2O。
Obtained directed agents are completely used for the preparation of following reactant mixtures, the addition of directed agents, according to aluminium in directed agents
The molal quantity of element accounts for 15% calculating of total aluminium element molal quantity.
Under conditions of room temperature and high-speed stirred according to 55.90g low alkali aluminium acid sodium solutions, 514.81g aluminum sulfate,
1129.04g waterglass, directed agents (abovementioned steps preparation) and the order of 489.2g water are sequentially added in mixing tank, reaction mixing
Total molar ratio of thing is 3Na2O:A12O3:10SiO2:250H2O.After stirring, it is loaded into stainless steel cauldron,
In 95 DEG C of static crystallizations 36 hours, then filter, wash, dry NaY molecular sieve product, numbering D4.
It is 5.0 that XRD, which measures its silica alumina ratio, and relative crystallinity is 87%, and electromicroscopic photograph shows that average grain size is
1000nm。
Embodiment 5
This example demonstrates that the building-up process of small crystal grain NaY molecular sieve.
By 335.69g high alkali deflection aluminium acid sodiums solution, (sinopec limited company catalyst Chang Ling branch company provides, Al2O3
Content is 40.2g/L, Na2O content is 270g/L, and proportion is 1.323) to be added to 466.18g waterglass (sinopec share is limited
Company's catalyst Chang Ling branch company provides, SiO2Content is 260.6g/L, Na2O content is 81.6g/L, and proportion is 1.2655, mould
Number is in 3.3), stirring ageing 10 hours at a temperature of 50 DEG C, then static ageing 36 hours at a temperature of 20 DEG C, finally in stirring
Under conditions of add 104g deionized waters.The obtained final mol ratio of directed agents is 16Na2O:A12O3:16SiO2:290H2O。
Obtained directed agents are completely used for the preparation of following reactant mixtures, the addition of directed agents, according to aluminium in directed agents
The molal quantity of element accounts for 20% calculating of total aluminium element molal quantity.
Under conditions of room temperature and high-speed stirred according to directed agents (abovementioned steps preparation), 815.83g waterglass (ibid),
(sinopec limited company catalyst Chang Ling branch company provides 15.29g low alkali aluminium acid sodium solutions, Al2O3Content is 194g/
L, Na2O content is 286.2g/L, proportion be 1.413), 558.48g aluminum sulfate (sinopec limited company catalyst Chang Ling
Branch company provides, Al2O3Content is 88.9g/L, and proportion is that the order 1.2829) with 528.7g water is sequentially added in mixing tank, instead
The total molar ratio for answering mixture is 2.7Na2O:A12O3:8.6SiO2:250H2O.After stirring, stainless steel is loaded into
In reactor, in 90 DEG C of static crystallizations 48 hours, then filter, wash, dry NaY molecular sieve product, numbering A5.
It is 5.6 that XRD, which measures its silica alumina ratio, and relative crystallinity is 92.5%, and electromicroscopic photograph shows that average grain size is
100nm。
Comparative example 5
This comparative example illustrates process of the preparation of directed agents according to the present invention, but the raw material of reactant mixture is added simultaneously
Situation.
Each raw material sources be the same as Example 5
335.69g high alkali deflection aluminium acid sodium solution is added in 466.18g waterglass, stirring ageing 10 is small at a temperature of 50 DEG C
When, then static ageing 36 hours at a temperature of 20 DEG C, finally add 104g deionized waters, what is obtained leads under conditions of stirring
It is 16Na to the final mol ratio of agent2O:A12O3:16SiO2:290H2O。
Obtained directed agents are completely used for the preparation of following reactant mixtures, the addition of directed agents, according to aluminium in directed agents
The molal quantity of element accounts for 20% calculating of total aluminium element molal quantity.
Under conditions of room temperature and high-speed stirred, in mixing tank simultaneously add directed agents (abovementioned steps preparation),
815.83g waterglass, 15.29g low alkali aluminium acid sodium solutions, 558.48g aluminum sulfate and 528.7g water, total throwing of reactant mixture
Material mol ratio is 2.7Na2O:A12O3:8.6SiO2:250H2O.After stirring, it is loaded into stainless steel cauldron, at 90 DEG C
Static crystallization 48 hours, then filters, washs, dry NaY molecular sieve product, numbering D5.
It is 5.0 that XRD, which measures its silica alumina ratio, and relative crystallinity is 88%, and electromicroscopic photograph shows that average grain size is
1000nm。
Embodiment 6
This example demonstrates that the small crystal grain NaY molecular sieve sample A1 obtained to embodiment 1 using ammonium exchange, hydro-thermal process and
Aluminium-eliminating and silicon-replenishing process obtains the surface Silicon-rich small crystal grain Y-shaped molecular sieve of the present invention.
Ammonium exchange is carried out to raw material small crystal grain NaY molecular sieve A1 first.Compound concentration is 0.5mol/L aqueous ammonium nitrate solutions
10 liters.A11000 grams of small crystal grain NaY molecular sieve is weighed, is dissolved in 10 liters of aqueous ammonium nitrate solutions prepared, speed of agitator is
300rpm, at 90 DEG C constant temperature stir 1 hour, then filtering molecular sieve repeat aforesaid operations, until Na in molecular sieve2O content
Reach 2.5-5wt%.Obtain dried sample hydro-thermal process under conditions of 500 DEG C, 100% vapor gauge pressure 0.1MPa
1.5h.Measure 1 liter of water purification and 200 grams of above-mentioned samples are dissolved in water purification, be rapidly heated stirring, temperature is 95 DEG C, speed of agitator
For 300rpm.Hexafluorosilicic acid aqueous ammonium is quickly added into molecular sieve slurry, 50 grams of ammonium hexafluorosilicates are added altogether, then constant temperature
Constant speed is stirred 2 hours, is filtered, and is dried, is obtained production code member NY-1, property is listed in table 1.
Comparative example 6
This comparative example be the same as Example 6, difference is the small crystal grain NaY molecular sieve sample D1 using comparative example 1.Contrasted
Production code member DB-1, property is listed in table 1.
Embodiment 7
This example demonstrates that the small crystal grain NaY molecular sieve A2 obtained to embodiment 2 is using ammonium exchange, hydro-thermal process and takes out aluminium
Mend the surface Silicon-rich small crystal grain Y-shaped molecular sieve that silicon process obtains the present invention.
Ammonium exchange is carried out to raw material small crystal grain NaY molecular sieve A2 first.Compound concentration is 0.2mol/L ammonium sulfate solutions
10 liters.1000 grams of small crystal grain NaY molecular sieve is weighed, is dissolved in 10 liters of aqueous ammonium nitrate solutions prepared, speed of agitator is
300rpm, at 90 DEG C constant temperature stir 1 hour, then filtering molecular sieve repeat aforesaid operations, until Na in molecular sieve2O content
Reach 2.5-5wt%.Obtain dried sample hydro-thermal process under conditions of 570 DEG C, 100% vapor gauge pressure 0.2MPa
2.0h.Measure 1 liter of water purification and the sample obtained by 300 grams of abovementioned steps is dissolved in water purification, be rapidly heated stirring, and temperature is 80
DEG C, speed of agitator is 300rpm.Hexafluorosilicic acid aqueous ammonium is added into molecular sieve slurry rapidly, 50 grams of hexafluorosilicic acids are added altogether
Ammonium, then constant temperature constant speed stirring 2 hours, is filtered, and is dried, is obtained production code member NY-2, property is listed in table 1.
Comparative example 7
This comparative example be the same as Example 7, difference is the small crystal grain NaY molecular sieve sample D2 using comparative example 2.Contrasted
Production code member DB-2, property is listed in table 1.
Embodiment 8
This example demonstrates that the small crystal grain NaY molecular sieve A3 obtained to embodiment 3 is using ammonium exchange, hydro-thermal process and takes out aluminium
Mend the surface Silicon-rich small crystal grain Y-shaped molecular sieve that silicon process obtains the present invention.
Ammonium exchange is carried out to raw material small crystal grain NaY molecular sieve A3 first.Compound concentration is 0.5mol/L aqueous ammonium chloride solutions
10 liters.1000 grams of small crystal grain NaY molecular sieve is weighed, is dissolved in 10 liters of aqueous ammonium nitrate solutions prepared, speed of agitator is
300rpm, at 90 DEG C constant temperature stir 1 hour, then filtering molecular sieve.Aforesaid operations are repeated, until Na in molecular sieve2O content
Reach 2.5-5wt%.Obtain dried sample hydro-thermal process under conditions of 550 DEG C, 100% vapor gauge pressure 0.2MPa
2.5h.Measure 1 liter of water purification and the sample obtained by above-mentioned experiment is dissolved in water purification, be rapidly heated stirring, temperature is 95 DEG C, stirring
Rotating speed is 300rpm.Hexafluorosilicic acid aqueous ammonium is added into molecular sieve slurry rapidly, 60 grams of ammonium hexafluorosilicates are added altogether, then
Constant temperature constant speed is stirred 2 hours, is filtered, and is dried, is obtained production code member NY-3, property is listed in table 1.
Comparative example 8
This comparative example be the same as Example 8, difference is the small crystal grain NaY molecular sieve sample D3 using comparative example 3.Contrasted
Production code member DB-3, property is listed in table 1.
Embodiment 9
This example demonstrates that the small crystal grain NaY molecular sieve A4 obtained to embodiment 4 is using ammonium exchange, hydro-thermal process and takes out aluminium
Mend the surface Silicon-rich small crystal grain Y-shaped molecular sieve that silicon process obtains the present invention.
Compound concentration is 10 liters of 0.7mol/l aqueous ammonium nitrate solutions.A41000 grams of small crystal grain NaY molecular sieve sample is weighed, it is molten
Speed of agitator is 300rpm in 10 liters of aqueous ammonium nitrate solutions prepared, and constant temperature is stirred 1 hour at 90 DEG C, then filtering point
Son sieve, repeats aforesaid operations, until Na in molecular sieve2O content reaches 2.5-5wt%.Dried sample is obtained 600
DEG C, hydro-thermal process 1.0h under conditions of 100% vapor gauge pressure 0.1MPa.Measure 1 liter of water purification and by the sample obtained by above-mentioned experiment
200 grams of product are dissolved in water purification, and be rapidly heated stirring, and temperature is 95 DEG C, and speed of agitator is 300rpm.Rapidly into molecular sieve slurry
Hexafluorosilicic acid aqueous ammonium is added, 50 grams of ammonium hexafluorosilicates are added altogether, then constant temperature constant speed is stirred 2 hours, is filtered, dries, obtains
To production code member NY-4, property is listed in table 1.
Comparative example 9
This comparative example be the same as Example 9, difference is the small crystal grain NaY molecular sieve sample D4 using comparative example 4.Contrasted
Production code member DB-4, property is listed in table 1.
Embodiment 10
This example demonstrates that the small crystal grain NaY molecular sieve A5 obtained to embodiment 5 is using ammonium exchange, hydro-thermal process and takes out aluminium
Mend the surface Silicon-rich small crystal grain Y-shaped molecular sieve that silicon process obtains the present invention.
Compound concentration is 10 liters of 0.7mol/l aqueous ammonium nitrate solutions.Weigh small crystal grain NaY molecular sieve sample
A51000 grams, it is 300rpm, the constant temperature at 90 DEG C to be dissolved in speed of agitator in 10 liters of aqueous ammonium nitrate solutions prepared
Stirring 1 hour, then filtering molecular sieve, repeats aforesaid operations, until Na in molecular sieve2O content reaches 2.5-5wt%.
To dried sample under conditions of 600 DEG C, 100% vapor gauge pressure 0.1MPa hydro-thermal process 1.0h.Measure 1 liter of water purification simultaneously
200 grams of above-mentioned molecular sieves are dissolved in water purification, be rapidly heated stirring, temperature is 95 DEG C, and speed of agitator is 300rpm.It is rapid to point
Hexafluorosilicic acid aqueous ammonium is added in sub- screening the pulp material, 60 grams of ammonium hexafluorosilicates are added altogether, then constant temperature constant speed is stirred 2 hours, mistake
Filter, dries, obtains production code member NY-5, property is listed in table 1.
Comparative example 10
This comparative example be the same as Example 10, difference is the small crystal grain NaY molecular sieve sample D5 using comparative example 5.Obtain pair
Than production code member DB-5, property is listed in table 1.
Claims (15)
1. a kind of small crystal grain Y-shaped molecular sieve of surface Silicon-rich, it is characterised in that molecular sieve body phase skeleton SiO2/Al2O3Mol ratio
For 5.0~6.0, surface SiO2/Al2O3Mol ratio is 8.0~13.0, and cell parameter is 2.460~2.468nm, sodium oxide content
≤ 0.1wt%, average grain diameter is 50~800nm.
2. according to the Y type molecular sieve of claim 1, wherein, described average grain diameter is 50~200nm.
3. according to the Y type molecular sieve of claim 1, wherein, described average grain diameter is 200~500nm.
4. according to the Y type molecular sieve of claim 1, wherein, described average grain diameter is 500~800nm.
5. according to the Y type molecular sieve of claim 1, it is characterised in that crystallization reservation degree is more than 90%.
6. according to the Y type molecular sieve of claim 1, it is characterised in that its BET is 700~800cm than surface2/g。
7. the preparation method of the small crystal grain Y-shaped molecular sieve of the surface Silicon-rich of claim 1, it is characterised in that including fine grain NaY
Drop sodium, hydro-thermal process and dealumination complement silicon process are handed in the synthesis of molecular sieve, ammonium, and the synthesis of described NaY molecular sieve is included in synthesis
Under conditions of NaY molecular sieve, the mixture A for being directed to agent, water, silicon source and silicon source composition carries out hydrothermal crystallizing and reclaims what is obtained
Product, wherein described directed agents is at 15~60 DEG C of temperature and stirring condition, sodium metaaluminate is added into waterglass, made
It is (6~25) Na that the molar concentration of aluminium element is edged up to mol ratio is formed by zero in waterglass2O:Al2O3:(6~25) SiO2
Mixture B, by mixture B in stirring, carry out 5~48 hours dynamics at 15~60 DEG C and be aged, then stood at 15~60 DEG C
Ageing is carried out 5~48 hours, and after ageing is finished, water is added under conditions of stirring, and it is (6~25) to make final mol ratio
Na2O:Al2O3:(6~25) SiO2:(200~400) H2What O was obtained；Wherein described mixture A be according to directed agents, silicon source,
Silicon source and the order of water sequentially add what is obtained after mixing tank.
8. according to the preparation method of claim 7, wherein, described mixture A mol ratio is (2~6) Na2O:Al2O3:
(8~20) SiO2:(200~400) H2O。
9. according to the preparation method of claim 7, wherein, the molal quantity of aluminium element accounts for total aluminium element in mixture A in directed agents
The 3~30% of molal quantity.
10. according to the preparation method of claim 7, wherein, described hydrothermal crystallizing is that progress 15~48 is small at 90~100 DEG C
When.
11. according to the preparation method of claim 7, wherein, described ammonium is handed over after the process of drop sodium, sodium oxide molybdena in molecular sieve
Content is 2.5~5.0 weight %.
12. according to the preparation method of claim 7 or 11, wherein, described ammonium hands over the process of drop sodium to carry out one or many, institute
The ammonium said hands over the process of drop sodium to include using ammonium concentration for 0.1~1.0mol/L ammonium salt solution, in temperature 50~100
DEG C, solvent and solute weight ratio be 8~15：Under conditions of 1, constant temperature is handled 0.5~1.5 hour.
13. according to the preparation method of claim 12, wherein, described ammonium salt is ammonium nitrate, ammonium sulfate, ammonium chloride and ammonium acetate
In one or more.
14. according to the preparation method of claim 7, wherein, the process of described hydro-thermal process is in 100% vapor, gauge pressure
Handled 1~10 hour at 0.1~0.2MPa, 500~650 DEG C of temperature.
15. according to the preparation method of claim 7, wherein, the process of described dealumination complement silicon is by the process of hydrothermal treatment
It is 3~10 that obtained molecular sieve, which is beaten obtains solvent and solute weight ratio in aqueous,：1 slurry, at a temperature of 80~120 DEG C,
The inventory of 10~60 grams of addition is sieved according to every 100 gram molecule, by (NH4)2SiF6Add in described slurry and stir, then
Recovery product.
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| CN1785807A (en) * | 2004-12-09 | 2006-06-14 | 中国石油天然气股份有限公司 | High silicon aluminium ratio small crystal NaY molecular sieve |
| CN1789125A (en) * | 2004-12-15 | 2006-06-21 | 中国石油化工股份有限公司 | Small crystal grain molecular sieve preparation method |
| CN101723401A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | ZSM-5/ZSM-5 core-shell type zeolite molecular sieve |
| CN101723400A (en) * | 2008-10-29 | 2010-06-09 | 中国石油化工股份有限公司 | Small crystal grain Y-shaped molecular sieve and preparation method thereof |
| CN102049306A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Small crystal particle Y-shaped molecular sieve-containing hydrocracking catalyst carrier and preparation method thereof |
| CN102198950A (en) * | 2010-03-26 | 2011-09-28 | 中国石油天然气股份有限公司 | Method for preparing NaY molecular sieve with high aluminum-silicon ratio |
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| CN1785807A (en) * | 2004-12-09 | 2006-06-14 | 中国石油天然气股份有限公司 | High silicon aluminium ratio small crystal NaY molecular sieve |
| CN1789125A (en) * | 2004-12-15 | 2006-06-21 | 中国石油化工股份有限公司 | Small crystal grain molecular sieve preparation method |
| CN101723401A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | ZSM-5/ZSM-5 core-shell type zeolite molecular sieve |
| CN101723400A (en) * | 2008-10-29 | 2010-06-09 | 中国石油化工股份有限公司 | Small crystal grain Y-shaped molecular sieve and preparation method thereof |
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| CN102198950A (en) * | 2010-03-26 | 2011-09-28 | 中国石油天然气股份有限公司 | Method for preparing NaY molecular sieve with high aluminum-silicon ratio |
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