CN105084387B - Synthetic method of small-crystal grain NaY molecular sieve - Google Patents
Synthetic method of small-crystal grain NaY molecular sieve Download PDFInfo
- Publication number
- CN105084387B CN105084387B CN201410199054.5A CN201410199054A CN105084387B CN 105084387 B CN105084387 B CN 105084387B CN 201410199054 A CN201410199054 A CN 201410199054A CN 105084387 B CN105084387 B CN 105084387B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- directed agents
- mixture
- nay molecular
- aluminium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a synthetic method of small-crystal grain NaY molecular sieve, and the method comprises the following steps: in the condition of synthesis of the NaY molecular sieve, a mixture A composed of a guiding agent, water, a silicon source and an aluminium source is crystallized by a hydrothermal method and recycled for obtaining a products, and the method is characterized in that the guiding agent is mixed from sodium meta aluminate and soluble glass, so that the mole concentration of the aluminium element in the soluble glass is gradually increased from zero in order to form a mixture B with a mole ratio (6-25)Na2O:Al2O3:(6-25)SiO2, dynamic aging and standing aging are carried out in order, and water is added for obtaining the product, wherein the mixture A is obtained by adding the guiding agent, the silicon source, the aluminium source and water in order into a material mixing pot. According to the method, the synthesized small-crystal grain NaY molecular sieve whose relative crystallinity is higher than 90% and silica-alumina ratio is middle or high has a conveniently adjusted crystal grain size.
Description
Technical field
The present invention relates to a kind of synthetic method of small crystal grain NaY molecular sieve, furtherly the present invention relates to high in one kind
The direct synthesis method of silicon aluminium ratio small crystal NaY 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 widely applied to petrochemical industry especially cracking of oil catalytic field rapidly.
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 propose requirement higher to the synthesis of molecular sieve and products thereof performance, in turn
Promote the further investigation of Zeolite synthesis technology.Requirements at the higher level to Y type molecular sieve synthesis are concentrated mainly on synthesizing small-grain
And the molecular sieve of the zeolite product, raising silica alumina ratio and synthesizing high-silicon aluminum ratio ratio and little crystal grain and ultra-fine grain of 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 micropore diffusion speed higher, carrying
The aspects such as height conversion macromolecular ability, the secondary cracking for reducing product and reduction catalyst coking, show than conventional die chi
The more superior performance of very little Y type molecular sieve, 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 the synthesis typically crystallite dimension with about 1000nm, 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 processed with hot crushing technology, although its grain size can be made to be reduced to 100nm, but this physics powder
The mode of broken treatment not only expends large energy, and destroys the crystal structure of molecular sieve, is allowed to part amorphous.If
It is then most simple and feasible method that small crystal grain Y-shaped molecular sieve can be directly synthesized, therefore, it is necessary to will the conventional Y type molecular sieve of optimization
Synthesis condition, by improve and increase be oriented to dosage, raising feed intake the methods such as basicity reduction 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, the basicity for improving synthetic system can prepare Microsize NaY Zeolite.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 is 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
NaY molecular sieve into crystallite dimension less than 150nm.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 the high-speed stirred of min, Y type molecular sieve of the particle diameter in below 100nm, but silicon can be obtained
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, the directing agent method based on commercial synthesis and the clear liquid based on template are included
Synthetic method.In directing agent method based on commercial synthesis, lived by addition rare earth ion, aluminum complexing agent and surface in 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：Faujasite is synthesized in research mineralizer 196-206)
Found during influence, to a small amount of organic complexing agent that stable comple can be formed with aluminium is added in synthetic system, can typically promoted
Enter the growth of the nucleation and crystal of molecular sieve, 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 intensification crystallization steps, to adding a small amount of organic solvent miscible with water, such as two in synthetic system
MSM, DMF, tetrahydrofuran, methyl alcohol, 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 intensification, 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 kind is based on the clear liquid synthetic method of template, the method can obtain nano level NaY molecular sieve, and with 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+Concentration with anion controls Y type molecular sieve crystallite dimension and receipts
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,
Silica alumina ratio molecular sieve higher 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.Therefore, it can by being directly synthesized
Or the silica alumina ratio of different type molecular sieve is obtained by the method (i.e. secondary synthesis) being modified, 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 silicon Y high more than 6.0 by silica alumina ratio
Type molecular sieve.The conventional method for obtaining high-Si Y-type molecular sieve has two kinds：A kind of is the method being directly synthesized, another kind 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 shortcoming 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 being 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 obtained, otherwise the preparation condition of silica alumina ratio more high request is harsher, it is more difficult to synthesize preferable sample.
In the method being directly synthesized, the conventional approach for improving silica alumina ratio mainly has following several：A kind of approach is extension crystallization time,
But, after silica alumina ratio is more than 5.5, exponentially form declines crystallization velocity the approach, makes synthesis uncomfortable because of time-consuming, high cost
For industrial production；Another approach be use organic amine (US5116590, US4965059, CN96105159.7,
CN97196899) or inorganic salts (US4333859, US4309313) are used as template, but this equally exists high cost, crystallization
The problems such as time is long, silicon utilization rate is relatively low, meanwhile, the silicon waste liquid of a large amount of high concentrations is discharged, and has both wasted and has also polluted environment.
It is directly synthesized in the method for high silica alumina ratio Y type molecular sieve, is always the focus and difficulty of research using non-template agent method
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, two kinds of directed agents of different mol ratio, waterglass, acid aluminium salt and sodium aluminate solutions are taken according to following gel masses mol ratios
It is well mixed that two kinds of gels, difference crystallization are obtained；Gel masses mol ratio is：(1.0~6.5) Na2O:Al2O3:(5.0~18)
SiO2:(100~280) H2The Al of O, wherein directed agents2O3Account for Al2O3The 0.01~15% of gross weight；Two kinds of gels are according to quality
Than being 1：(0.1~10) uniformly mixes, and mixed gel is obtained；By obtained mixed gel, crystallization 2~50 is small at 80~120 DEG C
When, NaY molecular sieve is obtained.Under the conditions of molar ratio identical, the method can prepare silicon high within the shorter time
The NaY molecular sieve of aluminum ratio.Method disclosed in CN1785807A and CN1785808A is to stir ageing 0.5 at 15~60 DEG C in advance
~48 hours prepared directed agents, are then directed to agent, water, silicon source, silicon source and are made reactant mixture, 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, and relative knot is obtained
Brilliant degree is SiO more than 80%, framework si-al ratio2/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 obtained with waterglass, directed agents, acid aluminium salt and sodium metaaluminate solidifying
Glue, by gel after 0~70h of crystallization at 50~100 DEG C, adds silicon source, then continues 0.5~50h of crystallization at 90~120 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.
The synthetic method of existing Y type molecular sieve can only synthesize grain size in 900-1300nm, SiO2/Al2O3Mol ratio exists
Product between 4.8~5.3, does not there is report skeleton SiO also2/Al2O3Mol ratio is between 5.0~6.0, and average crystal grain can be
50~800nm, and can be adjusted between 50~200nm, 200~500nm, 500~800nm, particle diameter distribution it is narrow in silicon high
The preparation method of aluminum ratio small crystal grain NaY molecular sieve.
The content of the invention
The present inventor has found to be oriented on the basis of the lot of experiments that non-template agent is directly synthesized Y type molecular sieve
Agent raw material contact condition, dynamic aging, static burn in, the composition of directed agents and addition, reaction mixing in the reactive mixture
The factor such as the raw material addition sequence and crystallization temperature of thing and time can influence the silica alumina ratio and average grain of synthesized molecular sieve
On the basis of footpath, by optimizing above-mentioned influence factor simultaneously, the average grain diameter and silica alumina ratio of product can be accurately adjusted.Based on this,
Form the present invention.
It is therefore an object of the present invention to providing a kind of non-template agent method for being different from prior art is directly synthesized middle sial high
Than the molecular sieve that the method and the method for small crystal grain NaY molecular sieve are obtained.
The synthetic method of the small crystal grain NaY molecular sieve that the present invention is provided, is included under conditions of synthesis NaY molecular sieve, will
The mixture A of directed agents, water, silicon source and silicon source composition carries out hydrothermal crystallizing and reclaims the product for obtaining, it is characterised in that wherein
Described directed agents are to mix sodium metaaluminate with waterglass, the molar concentration of aluminium element in waterglass is edged up to being formed by zero
Mol ratio is (6~25) Na2O:A12O3:(6~25) SiO2Mixture B, then sequentially pass through dynamic ageing, still aging,
Add what water was obtained again, wherein described mixture A is to sequentially add batch mixing according to the order of directed agents, silicon source, silicon source and water
Obtained after tank.
The method that the present invention is provided, is using the direct synthesis technique of non-template agent.The method first prepares directed agents, then prepares
Reactant mixture, most afterwards through crystallization, filtering, washing, dry and obtain middle high silicon aluminium ratio small crystal NaY molecular sieve.The method exists
Any template or additive are added without in reactant mixture, chemically or physically side need not be also carried out to the molecular sieve that synthesis is obtained
Method carries out dealuminzation or dealumination complement silicon i.e. secondary synthesis to improve silica alumina ratio, NaY molecular sieve average crystal grain can 50~800nm it
Between adjust, skeleton SiO2/Al2O3Mol ratio is between 5.0~6.0.
In the method for the present invention, the preparation of described directed agents synthesizes the system of NaY molecular sieve directed agents different from conventional method
Standby process, conventional method can be mixed silicon source and silicon source with any order, aging under quiescent conditions after being well mixed；
Different from the preparation method of directed agents in patent CN1785807, CN1785808, aging prepared guiding is stirred at 15~60 DEG C
Agent.The preparation of the directed agents in the inventive method is to mix sodium metaaluminate with waterglass, make aluminium element in waterglass mole
It is (6~25) Na that concentration is edged up to mol ratio is formed by zero2O:A12O3:(6~25) SiO2Mixture B, then sequentially pass through
It is dynamic ageing, still aging, then add what water was obtained.More specifically preparation process is comprised the following steps：(1) in 15~60 DEG C of temperature
Under degree and stirring condition, sodium metaaluminate is added in waterglass, form mol ratio for (6~25) Na2O:A12O3:(6~25)
SiO2Described mixture B；(2) mixture B is dynamically aged 5~48 hours at 15~60 DEG C, then at 15~60 DEG C
Still aging 5~48 hours；(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。
In the method for the present invention, described mixture A is made up of directed agents, water, silicon source and silicon source, and its mol ratio is (2
~6) Na2O:A12O3:(8~20) SiO2:(200~400) H2O.Wherein the addition of directed agents is rubbed with aluminium element in directed agents
Your number accounts for 3~30% meters of the molal quantity of total aluminium element in mixture A.Described mixture A is according to directed agents, silicon source, aluminium
The order of source and water sequentially adds what is obtained after mixing tank.
Described water can be deionized water or distilled water；Described silicon source can be waterglass, Ludox, silica gel and white
One or more in carbon black；Described silicon source can be sodium metaaluminate, aluminum sulfate, aluminium chloride, aluminum nitrate, aluminium hydroxide and plan
One or more in boehmite.
Described hydrothermal crystallizing is preferably mixture A and is carried out in closed reactor at 90-100 DEG C 15-48 hours.
The method of the present invention, it is using the directed agents preparation process different from prior art and suitable with reference to specific raw materials
The Y type molecular sieve that sequence Hydrothermal Synthesiss are obtained, with middle high silica alumina ratio and the characteristics of little crystal grain.The method is without additionally adding template
Or additive, it is raw materials used it is inexpensive, be easy to get, it is simple for process, advantageously reduce the manufacturing cost of Y types.
Specific embodiment
The present invention is further illustrated with reference to embodiment and comparative example, but the scope of the present invention is not limited only to this.
In each embodiment and comparative example, the XRD spectra of NaY molecular sieve sample is spread out with SIMADU XRD6000 type X-rays
Penetrate instrument and determine that (experiment condition is：CuKa is radiated, pipe pressure 40kv, tube current 40mA.).Sample silica alumina ratio is by SH/T0339-92
Standard method (《Standard of chemical industry collects》, China Standards Press, 2000 publish) calculate NaY molecular sieve lattice constant
A, then according to Breck-Flanigen formula Ss iO2/Al2O3=2 (25.858-a)/(a-24.191) draws；Sample crystallinity
According to SH/T0340-92 standard methods determine (《Standard of chemical industry collects》, China Standards Press publishes for 2000).
Sample topography is given by electromicroscopic photograph, is observed by JSM-5610LV type ESEMs instrument.
Embodiment 1
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 for ageing 48 hours in 3.3), is stirred at room temperature, then static ageing 5 hours at a temperature of 60 DEG C, finally in stirring
Under the conditions of add 15g deionized waters, the final mol ratio of directed agents for obtaining be 15Na2O:A12O3:15SiO2:320H2O。
Prepared 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, washing, dry NaY molecular sieve product.
It is 5.8 that XRD spectra surveys its silica alumina ratio, and relative crystallinity is 93.7%, and electromicroscopic photograph display average grain size is
300nm。
Comparative example 1
The explanation of this comparative example changes directed agents aging conditions during directed agents are synthesized, only with still aging and anti-
The situation for answering the feeding sequence of mixture to change.
Each raw material sources are with embodiment 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。
Prepared 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, washing, dry NaY molecular sieve product.
It is 4.8 that XRD spectra surveys its silica alumina ratio, and relative crystallinity is 88.7%, and electromicroscopic photograph display average grain size is
1000nm。
Embodiment 2
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 in 3.3), ageing 5 hours to be stirred 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 final mol ratio of directed agents for obtaining be 15Na2O:A12O3:15SiO2:320H2O。
Prepared 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, washing, dry NaY molecular sieve product.
It is 5.9 that XRD measures its silica alumina ratio, and relative crystallinity is 90.6%, and electromicroscopic photograph display average grain size is
800nm。
Comparative example 2
The explanation of this comparative example changes silicon source, the situation of the charging sequence of silicon source in prepared by directed agents.
Each raw material sources are with embodiment 2.
65.56g waterglass is added in 50.39g high alkali deflection aluminium acid sodium solution, ageing 5 hours is stirred at a temperature of 60 DEG C,
Then static ageing 5 hours at a temperature of 60 DEG C, finally add 15g deionized waters, the directed agents for obtaining under conditions of stirring
Final mol ratio is 15Na2O:A12O3:15SiO2:320H2O。
Prepared 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, washing, dry NaY molecular sieve product.
It is 5.0 that XRD measures its silica alumina ratio, and relative crystallinity is 87%, and electromicroscopic photograph display average grain size is
1000nm。
Embodiment 3
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 in 3.3), ageing 20 hours to be stirred 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 final mol ratio of directed agents for obtaining is 20Na2O:A12O3:20SiO2:380H2O。
Prepared 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, washing, dry NaY molecular sieve product.
It is 5.2 that XRD measures 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 during directed agents are synthesized, only with the feelings of dynamic ageing
Condition.
Raw material sources are with embodiment 3.
164.54g high alkali deflection aluminium acid sodium solution is added in 291.37g waterglass, ageing 20 is stirred at a temperature of 30 DEG C small
When, 60g deionized waters are finally added under conditions of stirring, the final mol ratio of directed agents for obtaining is 20Na2O:A12O3:
20SiO2:380H2O。
Prepared 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, washing, dry NaY molecular sieve product.
It is 5.0 that XRD measures its silica alumina ratio, and relative crystallinity is 55.1%, and electromicroscopic photograph display average grain size is
1000nm。
Embodiment 4
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 in 3.3), ageing 15 hours to be stirred 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 final mol ratio of directed agents for obtaining is 16Na2O:A12O3:16SiO2:290H2O。
Prepared 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, washing, dry NaY molecular sieve product.
It is 5.8 that XRD measures 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 illustrated during reactant mixture is prepared, the situation that the addition sequence of raw material changes.
Each raw material sources are with embodiment 4.
251.76g high alkali deflection aluminium acid sodium solution is added in 349.64g waterglass, ageing 15 is stirred at a temperature of 40 DEG C small
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。
Prepared 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,
The order of 1129.04g waterglass, directed agents (abovementioned steps preparation) and 489.2g water is 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, washing, dry NaY molecular sieve product.
It is 5.0 that XRD measures its silica alumina ratio, and relative crystallinity is 87%, and electromicroscopic photograph display average grain size is
1000nm。
Embodiment 5
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 in 3.3), ageing 10 hours to be stirred 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 final mol ratio of directed agents for obtaining is 16Na2O:A12O3:16SiO2:290H2O。
Prepared 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 1.2829) and the order of 528.7g water sequentially adds 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, washing, dry NaY molecular sieve product.
It is 5.6 that XRD measures its silica alumina ratio, and relative crystallinity is 92.5%, and electromicroscopic photograph display average grain size is
100nm。
Comparative example 5
The preparation of this comparative example explanation directed agents is according to process of the invention, but the raw material of reactant mixture is added simultaneously
Situation.
Each raw material sources are with embodiment 5
335.69g high alkali deflection aluminium acid sodium solution is added in 466.18g waterglass, ageing 10 is stirred at a temperature of 50 DEG C small
When, then static ageing 36 hours at a temperature of 20 DEG C, finally add 104g deionized waters under conditions of stirring, and what is obtained leads
It is 16Na to the final mol ratio of agent2O:A12O3:16SiO2:290H2O。
Prepared 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 filter, washing, dry NaY molecular sieve product.
It is 5.0 that XRD measures its silica alumina ratio, and relative crystallinity is 88%, and electromicroscopic photograph display average grain size is
1000nm。
Embodiment 6
By 527.89g 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 220g/L, and proportion is 1.387) to be added to 437.05g 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 in 3.3), ageing 24 hours to be stirred at a temperature of 20 DEG C, then static ageing 48 hours at a temperature of 30 DEG C, finally in stirring
Under conditions of add 121g deionized waters.The final mol ratio of directed agents for obtaining is 10Na2O:A12O3:12SiO2:220H2O。
Prepared 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 30% calculating of total aluminium element molal quantity.
It is (same according to directed agents (abovementioned steps preparation), 1529.67g waterglass under conditions of room temperature and high-speed stirred
On), 89.53g 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), 337.79g aluminum sulfate (sinopec limited company catalyst
Chang Ling branch company provides, Al2O3Content is 88.9g/L, and proportion is reaction mixing during order 1.2829) sequentially adds mixing tank
Total molar ratio of thing is 6Na2O:A12O3:15SiO2:250H2O.After stirring, it is loaded into stainless steel cauldron,
In 90 DEG C of static crystallizations 48 hours, then filter, washing, dry NaY molecular sieve product.
It is 5.0 that XRD measures its silica alumina ratio, and relative crystallinity is 93.0%, and electromicroscopic photograph display average grain size is
800nm。
Claims (5)
1. a kind of synthetic method of small crystal grain NaY molecular sieve, is included under conditions of synthesis NaY molecular sieve, be directed to agent, water,
The mixture A of silicon source and silicon source composition carries out hydrothermal crystallizing and reclaims the product for obtaining, it is characterised in that wherein described guiding
Agent is at 15~60 DEG C of temperature and stirring condition, sodium metaaluminate to be added in waterglass, makes rubbing for aluminium element in waterglass
It is (6~25) Na that your concentration is edged up to mol ratio is formed by zero2O:A12O3:(6~25) SiO2Mixture B, by mixture B
Dynamically it is aged at stirring condition, 15~60 DEG C 5~48 hours, then still aging 5~48 hours at 15~60 DEG C, has been aged
Bi Hou, adds into water under conditions of stirring, makes final mol ratio be (6~25) Na2O:A12O3:(6~25) SiO2:(200
~400) H2What O was obtained；Wherein described mixture A is to sequentially add batch mixing according to the order of directed agents, silicon source, silicon source and water
Obtained after tank.
2. according to the synthetic method of claim 1, wherein the mol ratio of described mixture A is (2~6) Na2O:A12O3:(8
~20) SiO2:(200~400) H2O。
3. according to the synthetic method of claim 1, wherein, the molal quantity of aluminium element accounts for total aluminium element in mixture A in directed agents
Molal quantity 3~30%.
4. according to the synthetic method of claim 1, wherein, described hydrothermal crystallizing is that 15~48 are carried out at 90~100 DEG C is small
When.
5. the molecular sieve that the synthetic method of one of claim 1-4 is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410199054.5A CN105084387B (en) | 2014-05-12 | 2014-05-12 | Synthetic method of small-crystal grain NaY molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410199054.5A CN105084387B (en) | 2014-05-12 | 2014-05-12 | Synthetic method of small-crystal grain NaY molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105084387A CN105084387A (en) | 2015-11-25 |
| CN105084387B true CN105084387B (en) | 2017-05-24 |
Family
ID=54565843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410199054.5A Active CN105084387B (en) | 2014-05-12 | 2014-05-12 | Synthetic method of small-crystal grain NaY molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105084387B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106698462A (en) * | 2017-01-19 | 2017-05-24 | 吉林大学 | Method for enhancing silica-alumina ratio of NaY molecular sieve framework |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101468802A (en) * | 2007-12-28 | 2009-07-01 | 中国石油化工股份有限公司 | Method for synthesizing fine grain NaY molecular sieve |
| CN101722023A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | NaY-type molecular sieves and preparation method thereof |
| CN102951655A (en) * | 2012-11-27 | 2013-03-06 | 华东师范大学 | Modified method of Y-type molecular sieve |
-
2014
- 2014-05-12 CN CN201410199054.5A patent/CN105084387B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101468802A (en) * | 2007-12-28 | 2009-07-01 | 中国石油化工股份有限公司 | Method for synthesizing fine grain NaY molecular sieve |
| CN101722023A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | NaY-type molecular sieves and preparation method thereof |
| CN102951655A (en) * | 2012-11-27 | 2013-03-06 | 华东师范大学 | Modified method of Y-type molecular sieve |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105084387A (en) | 2015-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5689890B2 (en) | Method for producing ZSM-5 zeolite using nanocrystalline ZSM-5 core | |
| CN102451740B (en) | Preparation method of nano Y-shaped molecular sieve/amorphous silica-alumina composite material | |
| CN107555446A (en) | A kind of preparation method of multi-stage porous Y type molecular sieve | |
| CN100404418C (en) | Preparation method of high-silica-alumina-ratio small-grain NaY molecular sieve | |
| CN102211779B (en) | Preparation method of beta zeolite | |
| CN103204515A (en) | Preparation method for high-dispersion zeolite molecular sieves | |
| CN105080589B (en) | A kind of catalyst containing Y type molecular sieve and preparation method | |
| CN105668586B (en) | A kind of preparation method of nanometer of molecular sieve of ZSM 5 and the molecular sieves of its P Modification ZSM 5 | |
| CN106044793A (en) | Method for synthesis of nanometer ZSM-5 molecular sieve from mother liquor flocculate | |
| CN103626203A (en) | Preparation method of nanometer ZSM-5 molecular sieve | |
| CN101205073B (en) | Method for preparing aluminium-containing MCM-41 molecular sieve | |
| CN105712371B (en) | A kind of USY Y compound molecular sieves and preparation method thereof | |
| CN1785807A (en) | High-silica-alumina-ratio small-crystal-grain NaY molecular sieve | |
| CN105621449B (en) | A kind of NaY types molecular sieve and preparation method thereof | |
| CN105084388B (en) | Method for preparing and modifying Y-type molecular sieve | |
| CN101717092A (en) | Method for preparing nanometer high specific surface Beta zeolite | |
| CN105080590B (en) | A kind of preparation method of the catalyst containing small crystal grain Y-shaped molecular sieve | |
| US20180029894A1 (en) | Preparation method for beta zeolite | |
| CN105084387B (en) | Synthetic method of small-crystal grain NaY molecular sieve | |
| CN105314651B (en) | A kind of preparation method of small crystal grain NaY molecular sieve | |
| CN105621441A (en) | Phosphorus containing ZSM-5/Y composite-structure molecular sieve preparation method | |
| CN105621448B (en) | A kind of preparation method of fine grain NaY type molecular sieve | |
| CN105084386B (en) | A kind of surface Silicon-rich small crystal grain Y-shaped molecular sieve and preparation method thereof | |
| CN101468803B (en) | Method for synthesizing fine grain NaY molecular sieve | |
| CN106145133A (en) | A kind of H beta molecular sieve and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |