CN114655965A - Method for preparing small-grain NaY - Google Patents
Method for preparing small-grain NaY Download PDFInfo
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- CN114655965A CN114655965A CN202011537312.8A CN202011537312A CN114655965A CN 114655965 A CN114655965 A CN 114655965A CN 202011537312 A CN202011537312 A CN 202011537312A CN 114655965 A CN114655965 A CN 114655965A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a method for preparing a small-grain NaY molecular sieve, which comprises the steps of preparing a directing agent, preparing a gel mixture and crystallizing the gel mixture, and is characterized in that in the step of preparing the directing agent, the directing agent raw materials are uniformly mixed and stirred at the temperature of 11-30 ℃, and do not need to be added with water after standing and aging for 1-40 hours; in said step of preparing the gel mixture, Al comes from the directing agent2O3Al in the gel mixture2O310-20% of the total amount. The method utilizes the existing NaY synthesis process to obtain the small-grain NaY molecular sieve without reducing the framework silicon-aluminum ratio.
Description
Technical Field
The invention relates to a preparation method of a small-grain NaY molecular sieve, in particular to a preparation method of a small-grain NaY molecular sieve.
Background
The Y-type molecular sieve is widely applied as a main active component of a petrochemical catalyst. In recent years, with the upgrading and degradation of feedstock oil, it is important to improve the accessibility of the active centers of refinery catalysts and to improve the macromolecular cracking ability thereof. As the crystal grains are reduced, the exposed active sites on the surface of the Y molecular sieve are greatly increased, the number of active centers on the outer surface is large, and the catalytic activity is improved; on the other hand, the small crystal grain Y molecular sieve has shorter pore passage communicated with the outside, is beneficial to the diffusion of reactants and products, reduces the diffusion resistance and effectively reduces the reaction depth and the coking rate. Therefore, compared with the traditional Y-type molecular sieve, the small-grain Y-type molecular sieve has more excellent catalytic performance and becomes the key point of research and development of novel petrochemical catalytic materials.
CN109264743A discloses a preparation method of a small-grain Y-type molecular sieve. The silicon source used in the preparation of the guiding agent is silica sol, and the prepared synthetic gel needs to be aged for 10 to 40 hours at the temperature of between 10 and 40 ℃ and then heated for crystallization to obtain the small-grain NaY molecular sieve, wherein the grain size is between 100 and 250 nm.
In the method for preparing the small-grain NaY molecular sieve disclosed in CN105084387A, the preparation method of the conventional directing agent is changed, namely sodium metaaluminate is mixed with water glass, so that the molar concentration of aluminum element in the water glass is gradually increased from zero to form Na with the molar ratio of (6-25)2O:A12O3:(6～25)SiO2The mixture is obtained by dynamic aging, standing aging and water supplementing in sequence.
CN101722023A discloses a method for preparing a small-grain NaY molecular sieve, which comprises the steps of firstly synthesizing a directing agent at a low temperature of 0-10 ℃, supplementing purified water accounting for 20-40% of the weight of the directing agent before the directing agent is used, then preparing synthetic gel at a low temperature of 0-10 ℃, and then dynamically crystallizing the synthetic gel at two sections of temperature change at 50-90 ℃ and 80-120 ℃ respectively to obtain the small-grain NaY molecular sieve of 100-700 nm.
Although the method for preparing the small-grain NaY molecular sieve adopts a process method different from the conventional NaY production, the preparation process is complex, the silicon-aluminum ratio of the product is low, and the production cost is high.
Disclosure of Invention
The invention aims to provide a method for preparing a small-grain NaY molecular sieve on the basis of a conventional synthesis process without changing the conventional NaY synthesis proportion and increasing equipment.
Therefore, the method for preparing the small-grain NaY molecular sieve comprises the steps of preparing the directing agent, preparing the gel mixture and crystallizing the gel mixture, and is characterized in that in the step of preparing the directing agent, the directing agent raw materials are uniformly mixed and stirred at the temperature of 11-30 ℃ and are statically stirredAfter aging for 1-40 h, no water needs to be added; in said step of preparing the gel mixture, Al comes from the directing agent2O3Al in the gel mixture2O310-20% of the total amount.
In the step of preparing the guiding agent, raw materials of the guiding agent comprise a silicon source, an aluminum source and alkali liquor, wherein the molar ratio of Na is (15-18)2O:Al2O3:(15～17)SiO2:(280～380)H2O。
In the step of preparing the directing agent, preferably, the directing agent raw materials are mixed and stirred uniformly at the temperature of 12-27 ℃, and are kept stand and aged for 5-35 hours without adding water; more preferably, the raw materials of the directing agent are mixed and stirred uniformly at the temperature of 15-25 ℃, and are kept stand and aged for 8-30 hours without adding water.
In the step of preparing the directing agent, the silicon source is water glass or silica sol, and the preferred silicon source is water glass in view of simple operation and cost control; the aluminum source is sodium metaaluminate, and the alkali liquor is sodium hydroxide solution.
The procedure for preparing the gel mixture according to the invention is preferably as Na under stirring2O：Al2O3：SiO2：H2O is 1.5-8: 1: 5-18: 100 to 500 mol%, more preferably Na2O：Al2O3：SiO2：H2O is 2-6: 1: 7-10: 150-400, and uniformly mixing a silicon source, an aluminum salt solution, an aluminate solution and a guiding agent.
In the step of preparing the gel mixture, the silicon source is water glass, the aluminum salt is one or more selected from aluminum sulfate, aluminum chloride, aluminum nitrate or aluminum phosphate, and the aluminate is sodium metaaluminate. Preferably, the aluminum salt is aluminum sulfate.
In said step of preparing the gel mixture, Al comes from the directing agent2O3Al in the gel mixture2O310-20% of the total amount, in order to balance the relationship between molecular sieve stability and control of grain size, comes from the guiding agentAl2O3Al in the gel mixture2O3The total amount is preferably 12-15%.
The crystallization step of the gel mixture has no special requirements on crystallization conditions, and is a conventional crystallization condition, for example, the gel mixture is crystallized at 70-120 ℃ for 10-50 h.
The method of the invention also comprises a step of recovering the crystallized product, wherein the recovery of the product comprises filtration, washing, drying and the like. The drying process can be carried out for 8-24 h at 80-150 ℃ in an oven, and can also be carried out in a flash evaporation drying mode.
The method provided by the invention is a method for preparing the small-grain NaY molecular sieve by using conventional synthesis equipment under the condition of feeding proportioning of the conventional NaY molecular sieve, and the small-grain NaY molecular sieve can be obtained by using the conventional NaY synthesis process without reducing the framework silicon-aluminum ratio. The crystallinity of the NaY molecular sieve provided by the invention is more than 85 percent, the silicon-aluminum ratio of the framework is more than 5.0, the grain size is concentrated in 200 nm-700 nm, and more is concentrated in 300 nm-600 nm.
Drawings
FIG. 1 is a Scanning (SEM) electron micrograph of the NaY molecular sieve prepared in example 1 of the present invention.
FIG. 2 is a Scanning (SEM) electron micrograph of the NaY molecular sieve prepared in comparative example 1.
FIG. 3 is a Scanning (SEM) electron micrograph of a NaY molecular sieve prepared according to example 2 of the present invention.
FIG. 4 is a Scanning (SEM) electron micrograph of the NaY molecular sieve prepared in comparative example 2.
FIG. 5 is a Scanning (SEM) electron micrograph of a NaY molecular sieve prepared according to example 3 of the present invention.
FIG. 6 is a Scanning (SEM) electron micrograph of the NaY molecular sieve prepared in example 4 of the invention.
FIG. 7 is a Scanning (SEM) electron micrograph of a NaY molecular sieve prepared according to example 5 of the present invention.
FIG. 8 is a Scanning (SEM) electron micrograph of a NaY molecular sieve prepared according to example 6 of the present invention.
FIG. 9 is a Scanning (SEM) electron micrograph of a NaY molecular sieve prepared in example 7 of the invention.
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto.
The crystallinity of the NaY molecular sieve prepared by the embodiment of the invention is measured by a RIPP 146-90 standard method.
The framework silicon-aluminum ratio is determined by the following formula:
SiO2/Al2O3＝2×(25.8575-a0)/(a0-24.191)；
wherein, a0Is the unit cell parameter of the molecular sieve, and is determined by the RIPP 145-90 standard method.
The RIPP standard method mentioned here can be found in petrochemical analysis methods, ed by Yangcui et al, 1990 edition.
Sample morphology (SEM) analysis was performed on an American ISI corporation ISI-60A electron microscope. The test conditions are as follows: acceleration voltage 20kV and sample inclination angle 30 deg.
Example 1
1) Preparation of directing agent
282g of high-alkali sodium metaaluminate (from Changling catalysts, Inc., Al) are added at 25 deg.C2O3 41g/L，Na2O297 g/L, density 1353g/L) 378g of water glass (available from Changling catalysts, Inc., SiO) were added under vigorous stirring2250.9g/L, modulus 3.31 and density 1258g/L), keeping stirring for 50min, stopping stirring, standing the mixed solution in a closed container at 25 ℃ for aging for 8 hours to obtain the directing agent, wherein the directing agent after aging can be used directly without adding water. The mol ratio of the guiding agent is 16.4Na2O:Al2O3:15SiO2:325.5H2O。
2) Preparation and crystallization of synthetic gels
145g of room temperature aluminum sulfate (available from Chanling catalyst Co., Ltd., Al) was added to 242g of normal temperature water glass (available from Chanling catalyst Co., Ltd., SiO2250.9g/L, modulus 3.31, density 1258g/L) under vigorous stirring2O3 89.7g/L，H2SO4259g/L, density 1277g/L), 24g of normal temperature low alkali sodium metaaluminate (available from Chanling catalyst Co., Ltd., Na)2O 280.8g/L，Al2O3186.7g/L, 1416g/L) density, 140.5g of the 25 ℃ guiding agent obtained in the step 1) and 129g of water at normal temperature, and stirring for 60min after the materials are added to obtain a synthetic gel mixture with the molar composition of 2.1Na2O：Al2O3：7.20SiO2：199H2O, wherein Al is derived from the directing agent2O3Al in the gel mixture2O312% of the total amount. And (3) putting the obtained synthetic gel mixture into a stainless steel reaction kettle, crystallizing for 29 hours at the temperature of 100 ℃, filtering and washing a crystallized product, and drying overnight in an oven at the temperature of 120 ℃ to obtain the NaY molecular sieve.
The NaY molecular sieve has a crystallinity of 94% and a framework Si/Al ratio of 5.4, and an SEM micrograph shown in FIG. 1 shows that the average particle size is about 600 nm.
Comparative example 1
This comparative example illustrates the effect of conventional methods for preparing a directing agent and synthesizing NaY molecular sieve on the grain size of the synthesized product at the same feed ratio as in example 1.
1) Preparation of directing agent
Preparation of NaY molecular sieve crystallization directing agent according to the prior art (US3639099 and US 3671191): at ambient temperature, 282g of high-alkali sodium metaaluminate (supplied by Changling catalyst Co., Ltd., Al)2O3 41g/L，Na2O297 g/L, density 1353g/L) 378g of water glass (from Changling catalysts, Inc., SiO) were added with vigorous stirring2250.9g/L, modulus 3.31, density 1258g/L), stirring for 50min, stopping stirring, aging the mixed solution in a sealed container at 30 deg.C for 20 hr, adding 85g water into the aged guiding agent, and stirring. The mol ratio of the guiding agent is 16.4Na2O:Al2O3:15SiO2:382H2O。
2) Preparation and crystallization of synthetic gels
99g of room temperature aluminum sulfate (Changling catalysis, Inc., available from Changling catalysis, Inc., with a modulus of 3.31, a density of 1258g/L) was added to 240g of normal temperature water glass (available from Changling catalysis, Inc., SiO2250.9 g/L) under vigorous stirringSupplied by agent Co., Ltd., Al2O3 89.7g/L，H2SO4259g/L, 1277g/L density), 38g of normal temperature low alkali sodium metaaluminate (provided by Changling catalyst Co., Ltd., Na)2O 280.8g/L，Al2O3186.7g/L, 1416g/L) of density, 55g of directing agent obtained in step 1) and 125g of water at room temperature, and stirring for 60min after the addition to obtain a synthetic gel mixture having the same molar composition as in example 1, the molar composition being 2.1Na2O：Al2O3：7.20SiO2：199H2O, wherein Al is derived from the directing agent2O3Al in the gel mixture2O35% of the total amount. And (3) putting the obtained synthetic gel mixture into a stainless steel reaction kettle, crystallizing for 29 hours at the temperature of 100 ℃, filtering and washing a crystallized product, and drying in an oven at the temperature of 120 ℃ overnight to obtain the NaY molecular sieve.
The NaY molecular sieve has a crystallinity of 93% and a framework Si/Al ratio of 5.4, and an SEM micrograph shown in FIG. 2 shows that the average particle size is about 800 nm.
Example 2
1) Preparation of low temperature directing agent
282g of high-alkali sodium metaaluminate (from Changling catalysts, Inc., Al) are added at 27 deg.C2O3 41g/L，Na2O297 g/L, density 1353g/L) 378g of water glass (available from Changling catalysts, Inc., SiO) were added under vigorous stirring2250.9g/L, modulus 3.31 and density 1258g/L), keeping stirring for 50min, stopping stirring, standing the mixed solution in a closed container at 27 ℃ for aging for 6 hours to obtain the directing agent, wherein the directing agent after aging can be used directly without adding water. The mol ratio of the guiding agent is 16.4Na2O:Al2O3:15SiO2:325.5H2O。
2) Preparation and crystallization of synthetic gels
To 300g of normal temperature water glass (available from Chanling catalyst Co., Ltd., SiO2250.9g/L, modulus 3.31, density 1258g/L) was added 155g of normal temperature aluminum sulfate (available from Chanling catalyst Co., Ltd., Al) in this order under vigorous stirring2O3 89.7g/L，H2SO4259g/L, density1277g/L), 19g of normal temperature low alkali sodium metaaluminate (available from Changling catalysts, Inc., Na)2O 280.8g/L，Al2O3186.7g/L, 1416g/L) of density, 182.5g of the directing agent obtained in step 1) at 27 ℃ and 100g of water at normal temperature, and keeping stirring for 60min after the materials are added to obtain a synthetic gel mixture with the molar composition of 2.73Na2O：Al2O3：8.7SiO2：209H2O, wherein Al is derived from the directing agent2O3Al in the gel mixture2O315% of the total amount. And (3) putting the obtained synthetic gel into a stainless steel reaction kettle, crystallizing for 29 hours at the temperature of 100 ℃, filtering and washing a crystallized product, and drying in an oven at the temperature of 120 ℃ overnight to obtain the NaY molecular sieve.
The NaY molecular sieve has a crystallinity of 93% and a framework Si/Al ratio of 5.6, and an SEM micrograph shows that the average particle size is about 500nm, as shown in FIG. 3.
Comparative example 2
This comparative example illustrates the effect of conventional methods for preparing directing agent and synthesizing NaY molecular sieve on the grain size of the synthesized product at the same feed ratio as in example 2.
1) Preparation of conventional directing agents
Preparation of NaY molecular sieve crystallization directing agent according to the prior art (US3639099 and US 3671191): at ambient temperature, 282g of high-alkali sodium metaaluminate (supplied by Changling catalyst Co., Ltd., Al)2O3 41g/L，Na2O297 g/L, density 1353g/L) 378g of water glass (available from Changling catalysts, Inc., SiO) were added under vigorous stirring2250.9g/L, modulus 3.31, density 1258g/L), stirring for 50min, stopping stirring, aging the mixed solution in a sealed container at 30 deg.C for 20 hr, adding 85g water into the aged guiding agent, and stirring. The mol ratio of the guiding agent is 16.4Na2O:Al2O3:15SiO2:382H2O。
2) Preparation and crystallization of synthetic gels
Under vigorous stirring, 251g of normal temperature water glass (available from Changling catalyst Co., Ltd., SiO)2250.9g/L, modulus 3.31 and density 1258g/L, 79g of normal temperature aluminum sulfate (long aluminum sulfate)Al from Ling catalyst Co2O389.7g/L, H2SO 4259 g/L, density 1277g/L), 35g of normal temperature low alkali sodium metaaluminate (Na, available from Changling catalyst Co., Ltd.)2O 280.8g/L，Al2O3186.7g/L, 1416g/L density), 46.7g of directing agent obtained in step 1) and 92g of water at normal temperature, and stirring for 60min after the addition to obtain a synthetic gel mixture with the same molar composition as in example 2, the molar composition being 2.73Na2O：Al2O3：8.7SiO2：209H2O, wherein Al is derived from the directing agent2O3Al in the gel mixture2O35% of the total amount. And (3) putting the obtained synthetic gel into a stainless steel reaction kettle, crystallizing for 29 hours at the temperature of 100 ℃, filtering and washing a crystallized product, and drying in an oven at the temperature of 120 ℃ overnight to obtain the NaY molecular sieve.
The NaY molecular sieve has a crystallinity of 93% and a framework Si/Al ratio of 5.6, and an SEM photograph shown in FIG. 4 shows that the average particle size is about 900 nm.
Example 3
1) Preparation of low temperature directing agent
282g of high-alkali sodium metaaluminate (from Changling catalysts, Al) are added at 23 deg.C2O3 41g/L，Na2O297 g/L, density 1353g/L) 378g of water glass (available from Changling catalysts, Inc., SiO) were added under vigorous stirring2250.9g/L, modulus 3.31 and density 1258g/L), keeping stirring for 50min, stopping stirring, standing the mixed solution in a closed container at 23 ℃ for aging for 12 hours to obtain the directing agent, wherein the directing agent after aging can be used directly without adding water. The mol ratio of the guiding agent is 16.4Na2O:Al2O3:15SiO2:325.5H2O。
2) Preparation and crystallization of synthetic gels
Under vigorous stirring, 200g of a water glass (SiO, from Changling catalyst Co., Ltd.) at normal temperature was charged2250.9g/L, modulus 3.31, density 1258g/L), 119g of room temperature aluminum sulfate (available from Changling catalyst Co., Ltd., Al)2O3 89.7g/L，H2SO4259g/L, 1277g/L) density,22g of normal temperature low alkali sodium metaaluminate (Na 2O 280.8g/L, Al2O3186.7g/L, density 1416g/L, from Changling catalyst Co., Ltd.), 107.5g of the directing agent obtained in step 1) at 23 ℃ and 93g of normal temperature water, adding the materials, maintaining stirring for 60min to obtain a synthetic gel, wherein the molar composition is 2.0Na2O：Al2O3：7.0SiO2：189H2O, wherein Al is derived from the directing agent2O3Al in the gel mixture2O311% of the total amount. And (3) putting the obtained synthetic gel into a stainless steel reaction kettle, crystallizing for 29 hours at the temperature of 100 ℃, filtering and washing a crystallized product, and drying in an oven at the temperature of 120 ℃ overnight to obtain the NaY molecular sieve.
The NaY molecular sieve has a crystallinity of 95% and a framework Si/Al ratio of 5.3, and an SEM photograph shown in FIG. 5 shows that the average particle size is about 650 nm.
Example 4
1) Preparation of low temperature directing agent
282g of high-alkali sodium metaaluminate (from Changling catalysts, Inc., Al) are added at 20 ℃2O3 41g/L，Na2O297 g/L, density 1353g/L) 378g of water glass (available from Changling catalysts, Inc., SiO) were added under vigorous stirring2250.9g/L, modulus 3.31 and density 1258g/L), keeping stirring for 50min, stopping stirring, standing the mixed solution in a closed container at 20 ℃ for aging for 25 hours to obtain the directing agent, wherein the directing agent after aging can be used directly without adding water. The mol ratio of the guiding agent is 16.4Na2O:Al2O3:15SiO2:325.5H2O。
2) Preparation and crystallization of synthetic gels
Under vigorous stirring, 230g of a water glass (SiO, available from Chanling catalyst Co., Ltd.) at normal temperature was charged2250.9g/L, modulus 3.31, density 1258g/L), 130g of room temperature aluminum sulfate (provided by Changling catalyst Co., Ltd., Al)2O3 89.7g/L，H2SO4259g/L, 1277g/L density), 22g of normal temperature low alkali sodium metaaluminate (available from Changling catalyst Co., Ltd., Na)2O280.8 g/L, Al2O3186.7g/L, density 1416g/L), 127g of directing agent obtained in step 1) at 20 ℃ and 80g of water at normal temperature, addingStirring for 60min after finishing the reaction to obtain synthetic gel (molar composition of 2.21 Na)2O：Al2O3：7.5SiO2：188H2O), wherein Al is derived from the directing agent2O3Al in the gel mixture2O312% of the total amount. And (3) putting the obtained synthetic gel into a stainless steel reaction kettle, crystallizing for 32 hours at the temperature of 98 ℃, filtering and washing a crystallized product, and drying in an oven at the temperature of 120 ℃ overnight to obtain the NaY molecular sieve.
The NaY molecular sieve has a crystallinity of 93% and a framework Si/Al ratio of 5.4, and an SEM photograph shown in FIG. 6 shows that the average particle size is about 500 nm.
Example 5
1) Preparation of low temperature directing agent
282g of high-alkali sodium metaaluminate (from Changling catalysts, Al) are added at 15 deg.C2O3 41g/L，Na2O297 g/L, density 1353g/L) 378g of water glass (from Changling catalysts, Inc., SiO) were added with vigorous stirring2250.9g/L, modulus 3.31 and density 1258g/L), keeping stirring for 50min, stopping stirring, standing the mixed solution in a closed container at 15 ℃ for aging for 30 hours to obtain the directing agent, wherein the directing agent after aging can be used directly without adding water. The mol ratio of the guiding agent is 16.4Na2O:Al2O3:15SiO2:325.5H2O。
2) Preparation and crystallization of synthetic gels
While vigorously stirring, 284g of a normal-temperature water glass (available from Chanling catalyst Co., Ltd., SiO)2250.9g/L, modulus 3.31, density 1258g/L), 169g of room temperature aluminum sulfate (provided by Changling catalyst Co., Ltd., Al)2O3 89.7g/L，H2SO4259g/L, 1277g/L density), 18g of normal temperature low alkali sodium metaaluminate (available from Changling catalyst Co., Ltd., Na)2O 280.8g/L，Al2O3186.7g/L, 1416g/L density), 194g of the directing agent obtained in step 1) at 15 ℃ and 90g of water at normal temperature, and stirring for 60min after the materials are added to obtain the synthetic gel (the molar composition is 2.43 Na)2O：Al2O3：8.0SiO2：196H2O, whichIn the presence of Al from the directing agent2O3Al in the gel mixture2O315% of the total amount. And (3) putting the obtained synthetic gel into a stainless steel reaction kettle, crystallizing for 32 hours at the temperature of 98 ℃, filtering and washing a crystallized product, and drying in an oven at the temperature of 120 ℃ overnight to obtain the NaY molecular sieve.
The NaY molecular sieve has a crystallinity of 94% and a framework Si/Al ratio of 5.4, and an SEM micrograph shown in FIG. 7 shows that the average particle size is about 400 nm.
Example 6
1) Preparation of low-temperature guiding agent
282g of high-alkali sodium metaaluminate (from Changling catalysts, Inc., Al) are added at 13 deg.C2O3 41g/L，Na2O297 g/L, density 1353g/L) 378g of water glass (available from Changling catalysts, Inc., SiO) were added under vigorous stirring2250.9g/L, modulus 3.31, density 1258g/L), stirring for 50min, stopping stirring, aging the mixture in a sealed container at 13 deg.C for 34 hr to obtain the guiding agent, and the guiding agent after aging can be used directly without adding water. The mol ratio of the guiding agent is 16.4Na2O:Al2O3:15SiO2:325.5H2O。
2) Preparation and crystallization of synthetic gels
To 236g of normal temperature water glass (available from Chanling catalyst Co., Ltd., SiO2250.9g/L, modulus 3.31, density 1258g/L) was added 140g of normal temperature aluminum sulfate (available from Chanling catalyst Co., Ltd., Al) in this order under vigorous stirring2O3 89.7g/L，H2SO4259g/L, 1277g/L density), 10g of normal temperature low alkali sodium metaaluminate (provided by Changling catalyst Co., Ltd., Na)2O 280.8g/L，Al2O3186.7g/L, 1416g/L density), 176.5g of the directing agent obtained in step 1) at 10 ℃ and 70g of water at normal temperature, and stirring for 60min after the materials are added to obtain the synthetic gel (the molar composition is 2.64 Na)2O：Al2O3：8.5SiO2：204H2O), wherein Al is derived from the directing agent2O3Al in the gel mixture2O317% of the total amount. Filling the obtained synthetic gel into a stainless steel reaction kettleCrystallizing at 98 deg.C for 32 hr, filtering, washing, and drying in oven at 120 deg.C overnight to obtain NaY molecular sieve.
The crystallinity of the NaY molecular sieve was 92%, the framework silica-alumina ratio was 5.6, and the SEM micrograph shown in fig. 8 shows that the average particle size was about 300 nm.
Example 7
1) Preparation of low temperature directing agent
282g of high-alkali sodium metaaluminate (from Changling catalysts, Al) are added at 11 ℃2O3 41g/L，Na2O297 g/L, density 1353g/L) 378g of water glass (available from Changling catalysts, Inc., SiO) were added under vigorous stirring2250.9g/L, modulus 3.31 and density 1258g/L), keeping stirring for 50min, stopping stirring, standing the mixed solution in a closed container at 11 ℃ for aging for 38 hours to obtain the directing agent, wherein the directing agent after aging can be used directly without adding water. The mol ratio of the guiding agent is 16.4Na2O:Al2O3:15SiO2:325.5H2O。
2) Preparation and crystallization of synthetic gels
240g of room temperature aluminum sulfate (available from Chanling catalyst Co., Ltd., Al) was added to 387g of normal temperature water glass (available from Chanling catalyst Co., Ltd., SiO2250.9g/L, modulus 3.31, density 1258g/L) under vigorous stirring2O3 89.7g/L，H2SO4259g/L, 1277g/L density), 5g of normal temperature low alkali sodium metaaluminate (Na 2O 280.8g/L, Al2O3186.7g/L, 1416g/L density from ChangLing catalyst Co.), 338g of 5 deg.C directing agent obtained in step 1) and 95g of normal temperature water, stirring for 60min after adding the materials to obtain a synthetic gel mixture with a molar composition of 2.86Na2O：Al2O3：9.0SiO2：210H2O, wherein Al is derived from the directing agent2O3Al in the gel mixture2O320% of the total amount. And (3) putting the obtained synthetic gel into a stainless steel reaction kettle, crystallizing for 32 hours at the temperature of 98 ℃, filtering and washing a crystallized product, and drying overnight in an oven at the temperature of 120 ℃ to obtain the NaY molecular sieve.
The crystallinity of the NaY molecular sieve was 94% with a framework silica-alumina ratio of 5.8, and the SEM micrograph shown in fig. 9 shows an average particle size of about 200 nm.
From the results of the above examples and comparative examples, it can be seen that the present invention prepares a small-grained NaY molecular sieve by changing the preparation method and the amount of the conventional directing agent, compared to the conventional method for preparing NaY molecular sieve: the NaY molecular sieve has the same crystallinity and silicon-aluminum ratio, but the crystal grain (200 nm-700 nm) of the NaY molecular sieve prepared by the method is obviously smaller than the crystal grain (700 nm-1000 nm) of the NaY molecular sieve prepared by the conventional method.
The method for preparing the small-grain NaY molecular sieve provided by the invention does not need to change the conventional NaY synthesis proportion and process equipment, and has the advantages of simple equipment, low cost, no reduction of the silicon-aluminum ratio of the product and the like.
Claims (11)
1. A method for preparing a small-grain NaY molecular sieve comprises a step of preparing a directing agent, a step of preparing a gel mixture and a step of crystallizing the gel mixture, and is characterized in that in the step of preparing the directing agent, raw materials of the directing agent are mixed and stirred uniformly at the temperature of 11-30 ℃, and do not need to be added with water after standing and aging for 1-40 hours; in said step of preparing the gel mixture, Al comes from the directing agent2O3Al in the gel mixture2O310-20% of the total amount.
2. The method according to claim 1, wherein in the step of preparing the directing agent, the raw materials of the directing agent comprise a silicon source, an aluminum source and alkali liquor, and the molar ratio is (15-18) Na2O:Al2O3:(15～17)SiO2:(280～380)H2O。
3. The method according to claim 1, wherein the step of preparing the directing agent is to mix and stir the directing agent raw materials uniformly at 12-27 ℃, and to stand and age for 5-35 hours without adding water.
4. The method according to claim 1, wherein the step of preparing the directing agent is to mix and stir the directing agent raw materials uniformly at 15-25 ℃, and to stand and age for 8-30 hours without adding water.
5. The process of claim 2 wherein the silicon source is water glass, the aluminum source is sodium metaaluminate and the caustic is sodium hydroxide solution.
6. The method of claim 1, wherein said step of preparing the gel mixture is performed under agitation in accordance with Na2O：Al2O3：SiO2：H2O is 1.5-8: 1: 5-18: and uniformly mixing a silicon source, an aluminum salt solution, an aluminate solution and a guiding agent according to a molar ratio of 100-500.
7. The method of claim 1, wherein said step of preparing the gel mixture is performed under agitation in accordance with Na2O：Al2O3：SiO2：H2O is 2-6: 1: 7-10: and uniformly mixing a silicon source, an aluminum salt solution, an aluminate solution and a guiding agent according to a molar ratio of 150-400.
8. The method of claim 6 or 7, wherein the silicon source is water glass, the aluminum salt is one or more selected from aluminum sulfate, aluminum chloride, aluminum nitrate and aluminum phosphate, and the aluminate is sodium metaaluminate.
9. The method of claim 8 wherein said aluminum salt is aluminum sulfate.
10. The method of claim 1, wherein, in said step of preparing a gel mixture, Al is derived from the directing agent2O3Al in the gel mixture2O312-15% of the total amount.
11. The method according to claim 1, wherein the step of crystallizing the gel mixture comprises crystallizing the gel mixture at 70 to 120 ℃ for 10 to 50 hours.
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