CN105084388B - Method for preparing and modifying Y-type molecular sieve - Google Patents
Method for preparing and modifying Y-type molecular sieve Download PDFInfo
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Abstract
The invention relates to a method for preparing and modifying a Y-type molecular sieve, wherein the method comprises the steps of ammonia exchange on a NaY molecular sieve, treatment under a hydrothermal condition, modification by adding a silica sol, a alcohol substrate and a citric acid solution, and the like. The NaY molecular sieve is obtained by successively adding a guiding agent, a silicon source, an aluminum source and water into a mixing pot to obtain a mixture A for hydrothermal crystallization, wherein, the guiding agent is obtained by the following processes: mixing sodium metaaluminate and water glass to make the mole concentration of the aluminum element in the water glass be increased from zero so as to form a mixture B having a mole ratio of (6-25)Na2O: Al2O3:(6-25)SiO2, sequentially carrying out dynamic aging and standing aging, and adding water. According to the molecular sieve product, the cell parameter is 2.461-2.467 nm, the molecular sieve has higher crystallization retention degree, and the average diameter of the crystalline grain is 50-800 nm.
Description
Technical field
The present invention relates to a kind of method of modifying for preparing of Y type molecular sieve, in particular the present invention relates to a kind of Y types molecule
Method of modifying is prepared under the non-template agent of 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
surfaceProPertles 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 yieldof 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.
Y type molecular sieve will be modified treatment 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 for changing aluminium, 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, selectivity it is de-
Except the non-framework aluminum in molecular sieve.But the non-framework aluminum of removing difficult for 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 breaks
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 the 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 process 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 the shortcomings of batch is small, and power consumption is higher in the industrial production in other this gas phase treatment method.
CN101941713A discloses a kind of preparation method of little crystal grain high-Si Y-type molecular sieve, and the method selects suitable modifying process,
I.e. ammonium exchange, ammonium hexafluorosilicate dealumination complement silicon, hydro-thermal process and aluminum saline solution treatment etc. obtain product；CN102311129A is public
A kind of preparation method of high-Si Y-type molecular sieve is opened, the method carries out fluosilicic acid treatment to molecular sieve pulp first, at fluosilicic acid
Ammonium salt is directly added into after reason, modified high-Si Y-type molecular sieve is obtained.Though above two method of modifying can improve the framework silicon of molecular sieve
Aluminum ratio, but the fluorine ion that is introduced into of additive is difficult to be eluted from slurries, the substantial amounts of fluorine ion of liquid residue after molecular sieve washing,
Environmental issue is caused in industrial production.
The content of the invention
The purpose of the present invention is directed to the deficiencies in the prior art, there is provided a kind of environment-friendly, inexpensive raising silica alumina ratio,
Method of modifying is prepared with the preferably small crystal grain Y-shaped molecular sieve of crystallization reservation degree.
Inventor has found in the synthetic test of substantial amounts of Y type molecular sieve, while optimizing directed agents raw material contact condition, moving
State is aging, static burn in, the composition of directed agents and in the reactive mixture addition, the raw material addition sequence of reactant mixture and
The parameter such as crystallization temperature and time, unexpectedly can obtain the NaY molecular sieve that high silica alumina ratio, average grain diameter are 50-800nm, and divide
Son sieve stability more preferably, further carries out the high silica alumina ratio molecular sieve that Si modification operation is obtained based on it, crystallizes reservation degree
More preferably.
Therefore, the Y type molecular sieve that the present invention is provided prepares method of modifying, it is characterised in that comprise the following steps：(1) make
Standby NaY molecular sieve；(2) NaY molecular sieve is exchanged the NH for obtaining the weight content of sodium oxide molybdena for 2.5-5% through ammonium4NaY molecules
Sieve；(3) NH is processed under hydrothermal conditions4NaY molecular sieve；(4) by NH4After NaY molecular sieve mashing, add pH molten for the silicon of 2-4
The organic alcohols material of glue and C2-C4 and with citric acid solution adjust pH be 3-6, temperature be 80-120 DEG C at be sufficiently mixed, then
Through washing and being dried to obtain modified product；Wherein, the process for NaY molecular sieve being prepared in described step (1) is in NaY points of synthesis
Under conditions of son sieve, the mixture A obtained after mixing tank will be sequentially added according to the order of directed agents, silicon source, silicon source and water and is entered
Water-filling thermal crystallisation simultaneously reclaims the product for obtaining, and described directed agents are to mix sodium metaaluminate with waterglass, make aluminium in waterglass
It is (6~25) Na that the molar concentration of element is edged up to mol ratio is formed by zero2O:A12O3:(6~25) SiO2Mixture B,
Dynamic ageing, still aging is sequentially passed through again, then adds what water was obtained.
The process of the preparation NaY molecular sieve in the present invention described in step (1) is to use direct synthesis technique：First prepare guiding
Agent, then prepare reactant mixture, most afterwards through crystallization, filtering, washing, dry and obtain middle high silicon aluminium ratio small crystal NaY molecular sieve.
Any template or additive are added without in described reactant mixture, need not also chemistry be carried out to the molecular sieve that synthesis is obtained
Or physical method carries out dealuminzation, or dealumination complement silicon to be secondary synthesis improve silica alumina ratio.It is raw materials used it is inexpensive, be easy to get, technique
It is simple and easy to apply, advantageously reduce manufacturing cost.
In the present invention, the preparation of the directed agents described in step (1) synthesizes the system of NaY molecular sieve directed agents different from conventional method
Standby process (mixing silicon source and silicon source with any order, aging under quiescent conditions after being well mixed), also different from
It is described in CN1785807A, CN1785808A that aging prepared directed agents are stirred at 15~60 DEG C.Directed agents in the present invention
Preparation be to mix sodium metaaluminate with waterglass, the molar concentration of aluminium element in waterglass is edged up to being formed by zero and mole match somebody with somebody
Than being (6~25) Na2O:A12O3:(6~25) SiO2Mixture B, then sequentially pass through dynamic ageing, still aging, then add
What water was obtained.More specifically preparation process is comprised the following steps：(1) at 15~60 DEG C of temperature and stirring condition, by meta-aluminic acid
Sodium is added in waterglass, forms 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 still aging 5~48 hours at 15~60 DEG C；(3) it is old
After change 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 obtaining directed agents through said process, NaY molecular sieve described in step (1) of the present invention prepares further step
For：Water, silicon source, silicon source, directed agents are added to obtain mixture A at room temperature, the mol ratio of mixture A is (2~6) Na2O:
A12O3:(8~20) SiO2:(200~400) H2O, the addition of directed agents accounts for total aluminium according to the molal quantity of aluminium element in directed agents
3~30% calculating of element molal quantity.Described mixture A is sequentially added according to the order of directed agents, silicon source, silicon source and water
Obtained after mixing tank.Wherein, described water is deionized water or distilled water, silicon source can be waterglass, Ludox, silica gel and
One or more in white carbon of mixture, described silicon source is sodium metaaluminate, aluminum sulfate, aluminium chloride, aluminum nitrate, hydroxide
One or more in aluminium and boehmite of mixture.The hydrothermal crystallizing of described mixture A is close at 90-100 DEG C
Close is carried out 15-48 hours in reactor.
Using the directed agents preparation process different from prior art and with reference to specific raw materials order water in step (1)
The NaY molecular sieve that thermal synthesis is obtained, with middle high silica alumina ratio and the characteristics of little crystal grain, skeleton SiO2/Al2O3Mol ratio 5.0~
Between 6.0, and average crystal grain in 50~800nm, and can be adjusted between 50~200nm, 200~500nm, 500~800nm
It is whole.The step without additionally plus template or additive, it is raw materials used it is inexpensive, be easy to get, it is simple for process, advantageously reduce system
Cause this.
In the method for the present invention, also NaY molecular sieve is by step (2) through the weight content that ammonium exchange obtains sodium oxide molybdena
The NH of 2.5-5%4NaY molecular sieve.The process that described ammonium is exchanged carries out one or many, and the process that described ammonium is exchanged includes
It is the ammonium salt solution of 0.1~1.0mol/L to use ammonium concentration, is 8~15 in 50~100 DEG C of temperature, solvent and solute weight ratio：1
Under the conditions of, constant temperature is processed 0.5~1.5 hour.Described ammonium salt is the one kind in ammonium nitrate, ammonium sulfate, ammonium chloride and ammonium acetate
Or it is various.
In the method for the present invention, further also NH is processed under step (3) hydrothermal condition4NaY molecular sieve.Described hydro-thermal
Under the conditions of process process be at 100% vapor, 0.1~0.2MPa of gauge pressure, 500~650 DEG C of temperature process 1~3 hour.
In the method for the present invention, further also step (4) is by NH4After NaY molecular sieve mashing, it is the silicon of 2-4 to add pH
The small molecule organic alcohols material of colloidal sol and C2-C4 and with citric acid solution adjust pH be 3-6, temperature be 80-120 DEG C at fully
Mixing, then through washing and being dried to obtain modified product.Described mashing, solvent and solute weight ratio is 3-10：1；Described pH is 2-4's
Ludox is addition at 80-120 DEG C of slurry of mashing, is added with SiO according to every 100 gram molecule sieve2The Ludox of 0.1-10 grams of meter
Ratio add.The organic alcohols material of described C2-C4 can reduce the high surface energy of Ludox as dispersant, increased
Repulsion between micelle, it is ensured that the fine dispersion of micelle, the preferred glycerine of organic alcohols material, the ethylene glycol of described C2-C4
With one or more in isopropanol.The organic alcohols material of described C2-C4 according to every 100g molecular sieves 1-30g alcohols thing
The ratio of matter is added.Regulation pH is to use citric acid solution for 3-6, and the concentration of described citric acid solution can be 0.1-
0.3mol/L；Described is sufficiently mixed, and can be stirred 0.5-5 hours under constant temperature constant speed.The present invention adds acidic silicasol,
The silicon in Ludox is supplemented in molecular sieve surface and skeleton because of some crystal defects that hydrothermal aging is produced, improve molecule
The crystallization reservation degree of sieve, and the silica alumina ratio of Y type molecular sieve can be increased considerably.
The inventive method preparation process is simple, and low production cost, the pollution in production process to environment is small.
The Y type molecular sieve that method of modifying is obtained is prepared through what the present invention was provided, is small crystal grain Y-shaped molecular sieve, average crystal grain
Can be adjusted between 50-800nm, body phase SiO2/Al2O3Mol ratio 5-10, crystallization reservation degree is more than 85%, and relative crystallinity is
85%-95%, product structure cell only has minimal shrink, and cell parameter is 2.461-2.467nm, and sodium oxide molybdena weight content≤
0.1wt%.
Specific embodiment
Below by embodiment, the present invention is further illustrated, but scope not thereby limiting the invention.
In each embodiment and comparative example, sample topography is given by electromicroscopic photograph, by JSM-5610LV type ESEM instrument
Observation.
NaY molecular sieve silica alumina ratio be by SH/T0339-92 standard methods (《Standard of chemical industry collects》, Chinese Industrial Standards (CIS) goes out
Version society, 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.Relative crystallinity according to SH/T0340-92 standard methods determine (《Chemical industry
Standard compendium》, China Standards Press publishes for 2000).Modified sieve sample body phase SiO2/Al2O3Mol ratio is used
XRF methods are determined, and crystallize reservation degree：The peak height of 5 characteristic peaks and be foundation in the XRD spectrum of Y type molecular sieve, with by modified
The peak height sum of 5 characteristic peaks of the Y type molecular sieve sample after treatment divided by 5 peak heights of characteristic peak of raw material Y type molecular sieve it
The percentage of sum, 5 characteristic peaks are respectively that 2 θ are characteristic peak corresponding to 15.8,20.7,24.0,27.4 and 31.8 peak positions.XRD
Spectrogram SIMADU XRD6000 types X-ray diffractometer determines that (experiment condition is：CuKa is radiated, pipe pressure 40kv, tube current
40mA。)。
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。
Compound concentration is 10 liters of 0.5mol/L aqueous ammonium nitrate solutions.1000 grams of small crystal grain NaY molecular sieve is weighed, 10 liters are dissolved in
In the aqueous ammonium nitrate solution for preparing, speed of agitator is 300rpm, constant temperature stirring 1 hour at 90 DEG C, then filtering molecular sieve.
Aforesaid operations are repeated, until Na in molecular sieve2The content of O reaches 2.5wt%.Obtain dried sample 500 DEG C, 100%
Hydro-thermal process 1.5h under conditions of vapor gauge pressure 0.1MPa.Measure 1 liter of water purification and 200 grams of above-mentioned samples be dissolved in water purification,
Be rapidly heated stirring, and temperature is 80 DEG C, and speed of agitator is 300rpm.Quickly to addition acidic silicasol, third in molecular sieve slurry
Triol, adds with SiO altogether2The acidic silicasol solution of 18 grams of meter, 36g glycerine is adjusted with the citric acid solution of 0.1mol/L
The pH of solution is 3.0, and then constant temperature constant speed is stirred 2 hours, and filtering is dried, and obtains production code member NY-1, and property is listed in table 1.
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。
Compound concentration is 10 liters of 0.5mol/L aqueous ammonium nitrate solutions.1000 grams of small crystal grain NaY molecular sieve is weighed, 10 liters are dissolved in
In the aqueous ammonium nitrate solution for preparing, speed of agitator is 300rpm, constant temperature stirring 1 hour at 90 DEG C, then filtering molecular sieve.
Aforesaid operations are repeated, until Na in molecular sieve2The content of O reaches 2.5wt%.Obtain dried sample 500 DEG C, 100%
Hydro-thermal process 1.5h under conditions of vapor gauge pressure 0.1MPa.Measure 1 liter of water purification and 200 grams of above-mentioned samples be dissolved in water purification,
Be rapidly heated stirring, and temperature is 80 DEG C, and speed of agitator is 300rpm.Quickly to addition acidic silicasol, third in molecular sieve slurry
Triol, adds with SiO altogether2The acidic silicasol solution of 20 grams of meter, 40g glycerine is adjusted with the citric acid solution of 0.1mol/L
The pH of solution is 3.0, and then constant temperature constant speed is stirred 2 hours, and filtering is dried, and obtains production code member NY-D-1, and property is listed in table 1.
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.
According to directed agents (abovementioned steps preparation), 1682.6 under conditions of room temperature and high-speed stirredgWaterglass (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。
Ammonium is exchanged.Compound concentration is 10 liters of 0.2mol/L ammonium sulfate solutions.1000 grams of small crystal grain NaY molecular sieve is weighed,
It is dissolved in 10 liters of aqueous ammonium nitrate solutions for preparing, speed of agitator is 300rpm, constant temperature stirring 1 hour at 90 DEG C, then mistake
Filter molecular sieve.Aforesaid operations are repeated, until Na in molecular sieve2O content reaches 3wt%.Dried sample is obtained 580
DEG C, hydro-thermal process 2.0h under conditions of 100% vapor gauge pressure 0.2MPa.Measure 1 liter of water purification and by obtained by 300 grams of abovementioned steps
Sample be dissolved in water purification, be rapidly heated stirring, temperature be 90 DEG C, speed of agitator is 300rpm.Rapidly in molecular sieve slurry
Acidic silicasol and ethylene glycol are added, is added with SiO altogether2The acidic silicasol solution of 20 grams of meter, 50g ethylene glycol uses 0.2mol/
The pH of the citric acid solution regulation solution of L is 4.0, and then constant temperature constant speed is stirred 2 hours, and filtering is dried, and obtains production code member
NY-2, property is listed in table 1
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。
Compound concentration is 10 liters of 0.2mol/L ammonium sulfate solutions.1000 grams of small crystal grain NaY molecular sieve is weighed, 10 liters are dissolved in
In the aqueous ammonium nitrate solution for preparing, speed of agitator is 300rpm, constant temperature stirring 1 hour at 90 DEG C, then filtering molecular sieve.
Aforesaid operations are repeated, until Na in molecular sieve2O content reaches 3wt%.Dried sample is obtained in 580 DEG C, 100% water
Hydro-thermal process 2.0h under conditions of steam gauge pressure 0.2MPa.Measure 1 liter of water purification and be dissolved in the sample obtained by 300 grams of abovementioned steps
In water purification, be rapidly heated stirring, and temperature is 90 DEG C, and speed of agitator is 300rpm.Rapidly to the acid silicon of addition in molecular sieve slurry
Colloidal sol and ethylene glycol, add with SiO altogether2The acidic silicasol solution of 20 grams of meter, 50g ethylene glycol, with the citric acid of 0.2mol/L
The pH of solution regulation solution is 4.0, and then constant temperature constant speed is stirred 2 hours, and filtering is dried, and obtains production code member NY-D-2, property
It is listed in table 1
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。
Compound concentration is 10 liters of 0.5mol/L aqueous ammonium chloride solutions.1000 grams of small crystal grain NaY molecular sieve is weighed, 10 liters are dissolved in
In the aqueous ammonium nitrate solution for preparing, speed of agitator is 300rpm, constant temperature stirring 1 hour at 90 DEG C, then filtering molecular sieve.
Aforesaid operations are repeated, until Na in molecular sieve2O content reaches 3.5wt%.Obtain dried sample 550 DEG C, 100%
Hydro-thermal process 2.5h under conditions of vapor gauge pressure 0.2MPa.Measure 1 liter of water purification and be dissolved in the sample obtained by above-mentioned experiment only
In water, be rapidly heated stirring, and temperature is 90 DEG C, and speed of agitator is 300rpm.It is rapid molten to the acid silicon of addition in molecular sieve slurry
Glue and isopropanol, add with SiO altogether2The acidic silicasol solution of 20 grams of meter, 40g isopropanols, the citric acid with 0.3mol/L is molten
The pH of liquid regulation solution is 5.0, and then constant temperature constant speed is stirred 2 hours, and filtering is dried, and obtains production code member NY-3, and property is listed in
Table 1
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。
Compound concentration is 10 liters of 0.5mol/L aqueous ammonium chloride solutions.1000 grams of small crystal grain NaY molecular sieve is weighed, 10 liters are dissolved in
In the aqueous ammonium nitrate solution for preparing, speed of agitator is 300rpm, constant temperature stirring 1 hour at 90 DEG C, then filtering molecular sieve.
Aforesaid operations are repeated, until Na in molecular sieve2O content reaches 3.5wt%.Obtain dried sample 550 DEG C, 100%
Hydro-thermal process 2.5h under conditions of vapor gauge pressure 0.2MPa.Measure 1 liter of water purification and be dissolved in the sample obtained by above-mentioned experiment only
In water, be rapidly heated stirring, and temperature is 90 DEG C, and speed of agitator is 300rpm.It is rapid molten to the acid silicon of addition in molecular sieve slurry
Glue and isopropanol, add with SiO altogether2The acidic silicasol solution of 20 grams of meter, 40g isopropanols, the citric acid with 0.3mol/L is molten
The pH of liquid regulation solution is 5.0, and then constant temperature constant speed is stirred 2 hours, and filtering is dried, and obtains production code member NY-D-3, property row
In table 1
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。
Compound concentration is 10 liters of 0.7mol/L aqueous ammonium chloride solutions.1000 grams of small crystal grain NaY molecular sieve is weighed, 10 liters are dissolved in
In the aqueous ammonium nitrate solution for preparing, speed of agitator is 300rpm, constant temperature stirring 1 hour at 90 DEG C, then filtering molecular sieve.
Aforesaid operations are repeated, until Na in molecular sieve2O content reaches 4.5wt%.Obtain dried sample 600 DEG C, 100%
Hydro-thermal process 1h under conditions of vapor gauge pressure 0.2MPa.Measure 1 liter of water purification and be dissolved in 200 grams of sample obtained by above-mentioned experiment
In water purification, be rapidly heated stirring, and temperature is 95 DEG C, and speed of agitator is 300rpm.Rapidly to the acid silicon of addition in molecular sieve slurry
Colloidal sol and glycerine, add with SiO altogether2The acidic silicasol solution of 10 grams of meter, 20 grams of glycerine, with the citric acid of 0.3mol/L
The pH of solution regulation solution is 5.0, and then constant temperature constant speed is stirred 2 hours, and filtering is dried, and obtains production code member NY-4, property row
In table 1
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。
Compound concentration is 10 liters of 0.7mol/L aqueous ammonium chloride solutions.1000 grams of small crystal grain NaY molecular sieve is weighed, 10 liters are dissolved in
In the aqueous ammonium nitrate solution for preparing, speed of agitator is 300rpm, constant temperature stirring 1 hour at 90 DEG C, then filtering molecular sieve.
Aforesaid operations are repeated, until Na in molecular sieve2O content reaches 4.5wt%.Obtain dried sample 600 DEG C, 100%
Hydro-thermal process 1h under conditions of vapor gauge pressure 0.2MPa.Measure 1 liter of water purification and be dissolved in 200 grams of sample obtained by above-mentioned experiment
In water purification, be rapidly heated stirring, and temperature is 95 DEG C, and speed of agitator is 300rpm.Rapidly to the acid silicon of addition in molecular sieve slurry
Colloidal sol and glycerine, add with SiO altogether2The acidic silicasol solution of 10 grams of meter, 20 grams of glycerine, with the citric acid of 0.3mol/L
The pH of solution regulation solution is 5.0, and then constant temperature constant speed is stirred 2 hours, and filtering is dried, and obtains production code member NY-D-4, property
It is listed in table 1
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。
Compound concentration is 10 liters of 0.5mol/L aqueous ammonium chloride solutions.1000 grams of small crystal grain NaY molecular sieve is weighed, 10 liters are dissolved in
In the aqueous ammonium nitrate solution for preparing, speed of agitator is 300rpm, constant temperature stirring 1 hour at 90 DEG C, then filtering molecular sieve.
Aforesaid operations are repeated, until Na in molecular sieve2O content reaches 4wt%.Dried sample is obtained in 600 DEG C, 100% water
Hydro-thermal process 1h under conditions of steam gauge pressure 0.2MPa.Measure 1 liter of water purification and be dissolved in 200 grams of sample obtained by above-mentioned experiment only
In water, be rapidly heated stirring, and temperature is 100 DEG C, and speed of agitator is 300rpm.It is rapid molten to the acid silicon of addition in molecular sieve slurry
Glue and ethylene glycol, add with SiO altogether2The acidic silicasol solution of 10 grams of meter, 25 grams of ethylene glycol, the citric acid with 0.2mol/L is molten
The pH of liquid regulation solution is 4.0, and then constant temperature constant speed is stirred 2 hours, and filtering is dried, and obtains production code member NY-5, and property is listed in
Table 1.
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。
Compound concentration is 10 liters of 0.5mol/L aqueous ammonium chloride solutions.1000 grams of small crystal grain NaY molecular sieve is weighed, 10 liters are dissolved in
In the aqueous ammonium nitrate solution for preparing, speed of agitator is 300rpm, constant temperature stirring 1 hour at 90 DEG C, then filtering molecular sieve.
Aforesaid operations are repeated, until Na in molecular sieve2O content reaches 4wt%.Dried sample is obtained in 600 DEG C, 100% water
Hydro-thermal process 1h under conditions of steam gauge pressure 0.2MPa.Measure 1 liter of water purification and be dissolved in 200 grams of sample obtained by above-mentioned experiment only
In water, be rapidly heated stirring, and temperature is 90 DEG C, and speed of agitator is 300rpm.It is rapid molten to the acid silicon of addition in molecular sieve slurry
Glue and ethylene glycol, add with SiO altogether2The acidic silicasol solution of 10 grams of meter, 25 grams of ethylene glycol, the citric acid with 0.2mol/L is molten
The pH of liquid regulation solution is 4.0, and then constant temperature constant speed is stirred 2 hours, and filtering is dried, and obtains production code member NY-D-5, property row
In table 1
From data in table 1, this method prepares the modified Y type molecular sieve for obtaining, with crystal grain is small, silica alumina ratio is high, knot
The characteristics of crystalline substance reservation degree is high.
Claims (10)
1. a kind of Y type molecular sieve prepares method of modifying, it is characterised in that comprise the following steps：(1) NaY molecular sieve is prepared；(2)
NaY molecular sieve is exchanged the NH for obtaining the weight content of sodium oxide molybdena for 2.5-5% through ammonium4NaY molecular sieve；(3) in hydrothermal condition
Lower treatment NH4NaY molecular sieve；(4) by NH4NaY molecular sieve mashing after, add pH for 2-4 Ludox and C2-C4 it is organic
Alcohols material and to adjust pH with citric acid solution be 3-6, is sufficiently mixed, then through washing and being dried to obtain at being 80-120 DEG C in temperature
Modified product；Wherein, the process for NaY molecular sieve being prepared in described step (1) is under conditions of NaY molecular sieve is synthesized, to incite somebody to action
The mixture A obtained after mixing tank is sequentially added according to the order of directed agents, silicon source, silicon source and water to carry out hydrothermal crystallizing and reclaims
The product for obtaining, described directed agents are at 15~60 DEG C of temperature and stirring condition, sodium metaaluminate to be added in waterglass,
The molar concentration of aluminium element in waterglass is set to be edged up to forming mol ratio for (6~25) Na by zero2O:A12O3:(6~25)
SiO2Mixture B, mixture B is carried out 5~48 hours at stirring condition, 15~60 DEG C, then in static conditions, 15~60
Carried out at DEG C 5~48 hours, add water again afterwards, make final mol ratio be (6~25) Na2O:A12O3:(6~25) SiO2:
(200~400) H2What O was obtained.
2. according to the method for 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 method for claim 1 wherein the molal quantity of aluminium element accounts for rubbing for total aluminium element in mixture A in directed agents
The 3~30% of that number.
4. according to the method for claim 1 wherein described hydrothermal crystallizing is to be carried out at 90~100 DEG C 15~48 hours.
5. it is that to use ammonium concentration be 0.1- according to the method for claim 1 wherein, the ammonium of described step (2) is exchanged
The ammonium salt solution of 1mol/L, is 50-100 DEG C in temperature, and solvent and solute weight ratio is 8-15：Carried out under conditions of 1.
6. according to the method for claim 5, wherein, described ammonium salt is in ammonium nitrate, ammonium sulfate, ammonium chloride and ammonium acetate
Plant or various.
7. according to the method for claim 1 wherein the hydrothermal condition of described step (3) is 100% vapor, gauge pressure 0.1-
500-650 DEG C of 0.2MPa, temperature, process time 1-3 hours.
8. according to the method for claim 1 wherein the mashing described in step (4) is to carry out at normal temperatures, and solvent and solute weight ratio is 3-
10：1；Described pH is to be beaten at 80-120 DEG C of slurry to add for the Ludox of 2-4, and every 100 gram molecule sieve is added with SiO2Meter
0.1-10 grams of Ludox.
9. according to the method for claim 1 wherein the additional proportion of the organic alcohols material of C2-C4 is every 100g in step (4)
The organic alcohols material of molecular sieve 1-30g.
10. according to the method for claim 1 or 9, wherein, the organic alcohols material of described C2-C4 is selected from the third three in step (4)
One or more in alcohol, ethylene glycol and isopropanol.
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| CN101759198A (en) * | 2008-12-24 | 2010-06-30 | 中国石油化工股份有限公司 | Small crystal particle Y-shaped molecular sieve 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 |
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| CN101759198A (en) * | 2008-12-24 | 2010-06-30 | 中国石油化工股份有限公司 | Small crystal particle Y-shaped molecular sieve and preparation method thereof |
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