CN114655965B - Method for preparing small-grain NaY - Google Patents
Method for preparing small-grain NaY Download PDFInfo
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- CN114655965B CN114655965B CN202011537312.8A CN202011537312A CN114655965B CN 114655965 B CN114655965 B CN 114655965B CN 202011537312 A CN202011537312 A CN 202011537312A CN 114655965 B CN114655965 B CN 114655965B
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- 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
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Abstract
The invention discloses a method for preparing a small-grain NaY molecular sieve, which comprises a step of preparing a guiding 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 guiding agent, the guiding agent raw materials are uniformly mixed and stirred at 11-30 ℃ and are kept stand for ageing for 1-40 hours without adding water; in the step of preparing the gel mixture, al is derived from the directing agent 2 O 3 Accounting for Al in the gel mixture 2 O 3 10 to 20 percent of the total amount. The method utilizes the existing NaY synthesis technology to obtain the small-grain NaY molecular sieve without reducing the silicon-aluminum ratio of the framework.
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 used as a main active component of petrochemical catalysts. In recent years, with the heavy and poor quality of raw oil, it is important to improve accessibility of active center of oil refining catalyst and raise its macromolecule cracking capability. The active sites exposed on the surface of the Y molecular sieve are greatly increased along with the reduction of crystal grains, the number of active sites on the outer surface of the Y molecular sieve is large, and the catalytic activity is improved along with the reduction of crystal grains; on the other hand, the pore canal of the small-grain Y molecular sieve communicated with the outside is shortened, thereby being beneficial to the diffusion of reactants and products, reducing the diffusion resistance and effectively reducing the reaction depth and 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 method for preparing small-grain Y-type molecular sieve. The silicon source used in the preparation of the guiding agent is silica sol, the prepared synthetic gel is aged for 10-40 hours at 10-40 ℃ and then heated for crystallization, and the grain size of the obtained small-grain NaY molecular sieve is 100-250 nm.
CN105084387A disclosesIn the method for preparing the small-grain NaY molecular sieve, the preparation method of the conventional guiding 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) 2 O:A1 2 O 3 :(6～25)SiO 2 Sequentially performing dynamic aging, standing aging and water supplementing to obtain the mixture.
CN101722023A discloses a preparation method of a small-grain NaY molecular sieve, which comprises the steps of firstly synthesizing a guiding agent at a low temperature of 0-10 ℃, adding purified water accounting for 20-40% of the weight of the guiding agent into the guiding agent before using the guiding agent, preparing synthetic gel at a low temperature of 0-10 ℃, and then carrying out two-stage variable-temperature dynamic crystallization on the synthetic gel at 50-90 ℃ and 80-120 ℃ respectively to obtain the small-grain NaY molecular sieve with a wavelength of 100-700 nm.
In the method for preparing the small-grain NaY molecular sieve, although a process method different from the conventional NaY production is adopted, 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 guiding agent, preparing the gel mixture and crystallizing the gel mixture, and is characterized in that in the step of preparing the guiding agent, the guiding agent raw materials are uniformly mixed and stirred at the temperature of 11-30 ℃ and are kept stand for ageing for 1-40 hours, and then water is not required to be added; in the step of preparing the gel mixture, al is derived from the directing agent 2 O 3 Accounting for Al in the gel mixture 2 O 3 10 to 20 percent of the total amount.
In the step of preparing the guiding agent, the guiding agent raw materials comprise a silicon source, an aluminum source and alkali liquor, and the molar ratio of the guiding agent raw materials is (15-18) Na 2 O:Al 2 O 3 :(15～17)SiO 2 :(280～380)H 2 O。
In the step of preparing the guiding agent, preferably, the guiding agent raw materials are mixed and stirred uniformly at the temperature of 12-27 ℃ and are kept stand for aging for 5-35 hours without adding water; more preferably, the guiding agent raw materials are mixed and stirred uniformly at 15-25 ℃ and are kept stand for aging for 8-30 hours without adding water.
In the step of preparing the guiding agent, the silicon source is water glass or silica sol, and the preferable silicon source is water glass from the aspects 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 carried out in accordance with Na while stirring 2 O：Al 2 O 3 ：SiO 2 ：H 2 O=1.5 to 8:1:5 to 18: molar ratio of 100 to 500, more preferably Na 2 O：Al 2 O 3 ：SiO 2 ：H 2 O=2 to 6:1: 7-10: and mixing the silicon source, the aluminum salt solution, the aluminate solution and the guiding agent uniformly in a molar ratio of 150-400.
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 and aluminum phosphate, and the aluminate is sodium metaaluminate. Preferably, the aluminum salt is aluminum sulfate.
In the step of preparing the gel mixture, al is derived from the directing agent 2 O 3 Accounting for Al in the gel mixture 2 O 3 10-20% of the total amount, al from the directing agent in order to balance the relationship between molecular sieve stability and control of grain size 2 O 3 Accounting for Al in the gel mixture 2 O 3 The total amount is preferably 12 to 15%.
The step of crystallizing the gel mixture according to the present invention is not particularly limited to crystallization conditions, and is conventional, for example, crystallization of the gel mixture at 70 to 120℃for 10 to 50 hours.
The method of the present invention further comprises the step of recovering the crystallized product, said product recovery comprising filtration, washing, drying, etc. The drying process can be carried out in an oven at 80-150 ℃ for 8-24 hours, and can also be carried out in a flash 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 the feeding proportioning of the conventional NaY molecular sieve, and can obtain the small-grain NaY molecular sieve by using the conventional NaY synthesis technology without reducing the framework silicon-aluminum ratio. The crystallinity of the NaY molecular sieve provided by the invention is above 85%, the framework silicon-aluminum ratio is above 5.0, the grain size is concentrated at 200 nm-700 nm, and more is concentrated at 300 nm-600 nm.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of a NaY molecular sieve prepared in example 1 of the present invention.
FIG. 2 is a Scanning Electron Micrograph (SEM) of the NaY molecular sieve prepared in comparative example 1.
FIG. 3 is a Scanning Electron Microscope (SEM) photograph of a NaY molecular sieve prepared in example 2 of the present invention.
FIG. 4 is a Scanning Electron Micrograph (SEM) of the NaY molecular sieve prepared in comparative example 2.
FIG. 5 is a Scanning Electron Microscope (SEM) photograph of a NaY molecular sieve prepared in example 3 of the present invention.
FIG. 6 is a Scanning Electron Micrograph (SEM) of a NaY molecular sieve prepared according to example 4 of the present invention.
FIG. 7 is a Scanning Electron Microscope (SEM) photograph of a NaY molecular sieve prepared in example 5 of the present invention.
FIG. 8 is a Scanning Electron Microscope (SEM) photograph of a NaY molecular sieve prepared in example 6 of the present invention.
FIG. 9 is a Scanning Electron Microscope (SEM) photograph of a NaY molecular sieve prepared in example 7 of the present invention.
Detailed Description
The following examples further illustrate the invention but are not intended to limit it.
The crystallinity of the NaY molecular sieve prepared by the embodiment of the invention is measured by adopting a RIPP 146-90 standard method.
The ratio of silicon to aluminum of the framework is determined by the following formula:
SiO 2 /Al 2 O 3 ＝2×(25.8575-a 0 )/(a 0 -24.191)；
wherein a is 0 Is a unit cell parameter of the molecular sieve, and is measured by using a RIPP 145-90 standard method.
The RIPP standard method mentioned here is described in particular in petrochemical analysis methods, yang Cuiding et al, 1990 edition.
Sample morphology (SEM) analysis was performed on an ISI-60A electron microscope from ISI corporation. Test conditions: acceleration voltage is 20kV, and sample inclination angle is 30 degrees.
Example 1
1) Preparation of a directing agent
282g of sodium high alkali metaaluminate (supplied by Kagaku catalyst Co., ltd., al 2 O 3 41g/L，Na 2 O297 g/L, density 1353 g/L) was added to 378g of water glass (supplied by Kagaku catalyst Co., ltd., siO) 2 250.9g/L, modulus 3.31 and density 1258 g/L), stirring for 50min, stopping stirring, standing the mixed solution in a closed container at 25deg.C, aging for 8 hr to obtain the final product, and directly using without adding water. The molar ratio of the guiding agent is 16.4Na 2 O:Al 2 O 3 :15SiO 2 :325.5H 2 O。
2) Preparation and crystallization of synthetic gel
To 242g of ordinary temperature water glass (supplied from Kaolin catalyst Co., ltd., siO2250.9g/L, modulus 3.31, density 1258 g/L) under vigorous stirring, 145g of ordinary temperature aluminum sulfate (supplied from Kaolin catalyst Co., ltd., al) was added in this order 2 O 3 89.7g/L，H 2 SO 4 259g/L, density 1277 g/L), 24g of sodium metaaluminate (NaA, available from Kagaku Co., ltd., normal temperature low alkali) 2 O 280.8g/L，Al 2 O 3 186.7g/L, density 1416 g/L), 140.5g of the guiding agent at 25 ℃ obtained in the step 1) and 129g of water at normal temperature, and stirring for 60min after the material is added to obtain a synthetic gel mixture with a molar composition of 2.1Na 2 O：Al 2 O 3 ：7.20SiO 2 ：199H 2 O from Al in directing agent 2 O 3 Accounting for Al in the gel mixture 2 O 3 12% of the total amount.And (3) putting the obtained synthetic gel mixture into a stainless steel reaction kettle, crystallizing for 29 hours at 100 ℃, filtering and washing a crystallized product, and drying overnight at 120 ℃ in an oven to obtain the NaY molecular sieve.
The crystallinity of the NaY molecular sieve is 94%, the ratio of skeleton silicon to aluminum is 5.4, and the SEM (electron microscope) photograph is shown in figure 1, and the average particle size is about 600nm.
Comparative example 1
This comparative example illustrates the effect of preparing a directing agent and synthesizing NaY molecular sieve according to conventional methods on the grain size of the synthesized product at the same feed ratio as example 1.
1) Preparation of a directing agent
Preparation of NaY molecular sieve crystallization directors according to the prior art (US 3639099 and US 3671191): 282g of sodium high alkali metaaluminate (supplied by Kagaku Co., ltd., al) 2 O 3 41g/L，Na 2 O297 g/L, density 1353 g/L) was added to 378g of water glass (supplied by Kagaku catalyst Co., ltd., siO) 2 250.9g/L, modulus 3.31, density 1258 g/L), stirring for 50min, stopping stirring, standing and aging in a closed container at 30deg.C for 20 hr, adding 85g water, and stirring. The molar ratio of the guiding agent is 16.4Na 2 O:Al 2 O 3 :15SiO 2 :382H 2 O。
2) Preparation and crystallization of synthetic gel
To 240g of ordinary temperature water glass (supplied from Kaolin catalyst Co., ltd., siO2250.9g/L, modulus 3.31, density 1258 g/L) under vigorous stirring, 99g of ordinary temperature aluminum sulfate (supplied from Kaolin catalyst Co., ltd., al) was added in this order 2 O 3 89.7g/L，H 2 SO 4 259g/L, density 1277 g/L), 38g of sodium metaaluminate (NaA, available from Kagaku Co., ltd., low alkali at normal temperature 2 O 280.8g/L，Al 2 O 3 186.7g/L, density 1416 g/L), 55g of the guiding agent obtained in step 1) and 125g of water at normal temperature, stirring for 60min after the addition of the materials, to obtain a synthetic gel mixture having the same molar composition as in example 1 and a molar composition of 2.1Na 2 O：Al 2 O 3 ：7.20SiO 2 ：199H 2 O from Al in directing agent 2 O 3 Accounting for Al in the gel mixture 2 O 3 5% of the total amount. And (3) putting the obtained synthetic gel mixture into a stainless steel reaction kettle, crystallizing for 29 hours at 100 ℃, filtering and washing a crystallized product, and drying overnight at 120 ℃ in an oven to obtain the NaY molecular sieve.
The crystallinity of the NaY molecular sieve is 93%, the ratio of skeleton silicon to aluminum is 5.4, and SEM (electron microscope) photograph is shown in figure 2, and the average particle size is about 800nm.
Example 2
1) Preparation of low temperature guiding agent
282g of sodium high alkali metaaluminate (supplied by Kagaku catalyst Co., ltd., al 2 O 3 41g/L，Na 2 O297 g/L, density 1353 g/L) was added to 378g of water glass (supplied by Kagaku catalyst Co., ltd., siO) 2 250.9g/L, modulus 3.31 and density 1258 g/L), stirring for 50min, stopping stirring, standing the mixed solution in a closed container at 27 ℃ for aging for 6 hours to obtain the guiding agent, and directly using the aged guiding agent without adding water. The molar ratio of the guiding agent is 16.4Na 2 O:Al 2 O 3 :15SiO 2 :325.5H 2 O。
2) Preparation and crystallization of synthetic gel
155g of room-temperature aluminum sulfate (supplied by Kaolin catalyst Co., ltd., al) was added in this order to 300g of room-temperature water glass (supplied by Kaolin catalyst Co., ltd., siO2250.9g/L, modulus 3.31, density 1258 g/L) 2 O 3 89.7g/L，H 2 SO 4 259g/L, density 1277 g/L), 19g of sodium metaaluminate (NaA, available from Kagaku Co., ltd., low alkali at normal temperature 2 O 280.8g/L，Al 2 O 3 186.7g/L, density 1416 g/L), 182.5g of the guiding agent obtained in the step 1) at 27 ℃ and 100g of water at normal temperature, and stirring for 60min after the material is added to obtain a synthetic gel mixture with a molar composition of 2.73Na 2 O：Al 2 O 3 ：8.7SiO 2 ：209H 2 O from Al in directing agent 2 O 3 Accounting for Al in the gel mixture 2 O 3 1 of the total amount5%. And (3) putting the obtained synthetic gel into a stainless steel reaction kettle, crystallizing for 29 hours at 100 ℃, filtering and washing a crystallized product, and drying overnight at 120 ℃ in an oven to obtain the NaY molecular sieve.
The crystallinity of the NaY molecular sieve is 93%, the ratio of skeleton silicon to aluminum is 5.6, and the SEM (electron microscope) photograph shows that the average particle size is about 500nm.
Comparative example 2
This comparative example illustrates the effect of preparing a directing agent and synthesizing NaY molecular sieve according to conventional methods on the grain size of the synthesized product at the same feed ratio as example 2.
1) Preparation of conventional directing agents
Preparation of NaY molecular sieve crystallization directors according to the prior art (US 3639099 and US 3671191): 282g of sodium high alkali metaaluminate (supplied by Kagaku Co., ltd., al) 2 O 3 41g/L，Na 2 O297 g/L, density 1353 g/L) was added to 378g of water glass (supplied by Kagaku catalyst Co., ltd., siO) 2 250.9g/L, modulus 3.31, density 1258 g/L), stirring for 50min, stopping stirring, standing and aging in a closed container at 30deg.C for 20 hr, adding 85g water, and stirring. The molar ratio of the guiding agent is 16.4Na 2 O:Al 2 O 3 :15SiO 2 :382H 2 O。
2) Preparation and crystallization of synthetic gel
251g of water glass at room temperature (supplied by Kagaku Co., ltd., siO) 2 250.9g/L, modulus 3.31, density 1258 g/L) of aluminum sulfate at room temperature (supplied by Kagaku Co., ltd., al) 2 O 3 89.7g/L, H2SO4 259g/L, density 1277 g/L), 35g of sodium metaaluminate (NaN, available from Kagaku Co., ltd., low alkali at room temperature) 2 O 280.8g/L，Al 2 O 3 186.7g/L, density 1416 g/L), 46.7g of the guiding agent obtained in step 1) and 92g of water at normal temperature, stirring for 60min after the addition of the materials, to obtain a synthetic gel mixture having the same molar composition as in example 2 and a molar composition of 2.73Na 2 O：Al 2 O 3 ：8.7SiO 2 ：209H 2 O, which isFrom Al in the directing agent 2 O 3 Accounting for Al in the gel mixture 2 O 3 5% of the total amount. And (3) putting the obtained synthetic gel into a stainless steel reaction kettle, crystallizing for 29 hours at 100 ℃, filtering and washing a crystallized product, and drying overnight at 120 ℃ in an oven to obtain the NaY molecular sieve.
The crystallinity of the NaY molecular sieve is 93%, the ratio of skeleton silicon to aluminum is 5.6, and SEM (electron microscope) photograph is shown in figure 4, and the average particle size is about 900nm.
Example 3
1) Preparation of low temperature guiding agent
282g of sodium high alkali metaaluminate (supplied by Kagaku catalyst Co., ltd., al 2 O 3 41g/L，Na 2 O297 g/L, density 1353 g/L) was added to 378g of water glass (supplied by Kagaku catalyst Co., ltd., siO) 2 250.9g/L, modulus 3.31 and density 1258 g/L), stirring for 50min, stopping stirring, standing the mixed solution in a closed container at 23 ℃ for aging for 12 hours to obtain the guiding agent, and the guiding agent after aging can be directly used without adding water. The molar ratio of the guiding agent is 16.4Na 2 O:Al 2 O 3 :15SiO 2 :325.5H 2 O。
2) Preparation and crystallization of synthetic gel
200g of a normal temperature water glass (supplied by Kagaku Co., ltd., siO) 2 250.9g/L, modulus 3.31, density 1258 g/L), 119g of normal temperature aluminum sulfate (supplied by Kagaku catalyst Co., ltd., al 2 O 3 89.7g/L，H 2 SO 4 259g/L, density 1277 g/L), 22g normal temperature low alkali sodium metaaluminate (Na 2O 280.8g/L, al2O3 186.7g/L, density 1416 g/L) 107.5g guiding agent of 23 ℃ and 93g normal temperature water obtained in step 1), stirring for 60min after the addition of the materials to obtain synthetic gel with molar composition of 2.0Na 2 O：Al 2 O 3 ：7.0SiO2：189H 2 O from Al in directing agent 2 O 3 Accounting for Al in the gel mixture 2 O 3 11% of the total amount. Putting the obtained synthetic gel into a stainless steel reaction kettle at 100 DEG CCrystallizing for 29h, filtering and washing the crystallized product, and drying overnight at 120 ℃ in an oven to obtain the NaY molecular sieve.
The crystallinity of the NaY molecular sieve is 95%, the ratio of skeleton silicon to aluminum is 5.3, and SEM (electron microscope) photograph is shown in figure 5, and the average particle size is about 650nm.
Example 4
1) Preparation of low temperature guiding agent
282g of sodium high alkali metaaluminate (supplied by Kagaku catalyst Co., ltd., al 2 O 3 41g/L，Na 2 O297 g/L, density 1353 g/L) was added to 378g of water glass (supplied by Kagaku catalyst Co., ltd., siO) 2 250.9g/L, modulus 3.31 and density 1258 g/L), stirring for 50min, stopping stirring, standing and aging in a closed container at 20deg.C for 25 hr to obtain the final product, and directly using without adding water. The molar ratio of the guiding agent is 16.4Na 2 O:Al 2 O 3 :15SiO 2 :325.5H 2 O。
2) Preparation and crystallization of synthetic gel
Under vigorous stirring, 230g of ordinary temperature water glass (supplied by Kagaku Co., ltd., siO) 2 250.9g/L, modulus 3.31, density 1258 g/L) of aluminum sulfate at room temperature (supplied by Kagaku Co., ltd., al) 2 O 3 89.7g/L，H 2 SO 4 259g/L, density 1277 g/L), 22g of sodium metaaluminate (NaA, available from Kagaku Co., ltd., normal temperature low alkali) 2 280.8g/L of O, 186.7g/L of Al2O3, 1416g/L of density), 127g of the guiding agent obtained in the step 1) at 20 ℃ and 80g of water at normal temperature, and stirring for 60min after the material is added to obtain synthetic gel (the molar composition is 2.21Na 2 O：Al2O3：7.5SiO 2 ：188H 2 O) wherein Al is derived from a directing agent 2 O 3 Accounting for Al in the gel mixture 2 O 3 12% of the total amount. And (3) putting the obtained synthetic gel into a stainless steel reaction kettle, crystallizing for 32 hours at 98 ℃, filtering and washing a crystallized product, and drying overnight at 120 ℃ in an oven to obtain the NaY molecular sieve.
The crystallinity of the NaY molecular sieve was 93%, the ratio of framework silica to alumina was 5.4, and SEM photograph was shown in FIG. 6, showing an average particle size of about 500nm.
Example 5
1) Preparation of low temperature guiding agent
282g of sodium high alkali metaaluminate (supplied by Kagaku catalyst Co., ltd., al 2 O 3 41g/L，Na 2 O297 g/L, density 1353 g/L) was added to 378g of water glass (supplied by Kagaku catalyst Co., ltd., siO) 2 250.9g/L, modulus 3.31 and density 1258 g/L), stirring for 50min, stopping stirring, standing and aging in a closed container at 15deg.C for 30 hr to obtain the final product, and directly using without adding water. The molar ratio of the guiding agent is 16.4Na 2 O:Al 2 O 3 :15SiO 2 :325.5H 2 O。
2) Preparation and crystallization of synthetic gel
284g of water glass at room temperature (supplied by Kagaku Co., ltd., siO) 2 250.9g/L, modulus 3.31, density 1258 g/L), and 169g of aluminum sulfate at room temperature (supplied by Kagaku catalyst Co., ltd., al 2 O 3 89.7g/L，H 2 SO 4 259g/L, density 1277 g/L), 18g of sodium metaaluminate (NaA, available from Kagaku Co., ltd., normal temperature low alkali) 2 O 280.8g/L，Al 2 O 3 186.7g/L, density 1416 g/L), 194g of guiding agent at 15 ℃ obtained in the step 1) and 90g of water at normal temperature, stirring for 60min after the material is added, and obtaining synthetic gel (molar composition is 2.43 Na) 2 O：Al 2 O 3 ：8.0SiO 2 ：196H 2 O from Al in directing agent 2 O 3 Accounting for Al in the gel mixture 2 O 3 15% of the total amount. And (3) putting the obtained synthetic gel into a stainless steel reaction kettle, crystallizing for 32 hours at 98 ℃, filtering and washing a crystallized product, and drying overnight at 120 ℃ in an oven to obtain the NaY molecular sieve.
The crystallinity of the NaY molecular sieve was 94%, the ratio of skeletal silica to alumina was 5.4, and SEM photograph was shown in FIG. 7, showing an average particle size of about 400nm.
Example 6
1) Preparation of low temperature guiding agent
282g of sodium high alkali metaaluminate (supplied by Kagaku catalyst Co., ltd., al 2 O 3 41g/L，Na 2 O297 g/L, density 1353 g/L) was added to 378g of water glass (supplied by Kagaku catalyst Co., ltd., siO) 2 250.9g/L, modulus 3.31 and density 1258 g/L), stirring for 50min, stopping stirring, standing and aging in a closed container at 13deg.C for 34 hr to obtain the final product, and directly using without adding water. The molar ratio of the guiding agent is 16.4Na 2 O:Al 2 O 3 :15SiO 2 :325.5H 2 O。
2) Preparation and crystallization of synthetic gel
Under vigorous stirring, 140g of room temperature aluminum sulfate (supplied by Kaolin catalyst Co., ltd., al) was added sequentially to 236g of room temperature water glass (supplied by Kaolin catalyst Co., ltd., siO2250.9g/L, modulus 3.31, density 1258 g/L) 2 O 3 89.7g/L，H 2 SO 4 259g/L, density 1277 g/L), 10g of sodium metaaluminate (NaA, available from Kagaku Co., ltd., low alkali at normal temperature 2 O 280.8g/L，Al 2 O 3 186.7g/L, density 1416 g/L), 176.5g of guiding agent at 10 ℃ obtained in step 1) and 70g of water at normal temperature, stirring for 60min after the addition of the materials, and obtaining synthetic gel (molar composition is 2.64 Na) 2 O：Al2O3：8.5SiO 2 ：204H 2 O) wherein Al is derived from a directing agent 2 O 3 Accounting for Al in the gel mixture 2 O 3 17% of the total amount. And (3) putting the obtained synthetic gel into a stainless steel reaction kettle, crystallizing for 32 hours at 98 ℃, filtering and washing a crystallized product, and drying overnight at 120 ℃ in an oven to obtain the NaY molecular sieve.
The crystallinity of the NaY molecular sieve was 92%, the ratio of framework silica to alumina was 5.6, and SEM photograph was shown in FIG. 8, showing an average particle size of about 300nm.
Example 7
1) Preparation of low temperature guiding agent
282g of sodium high alkali metaaluminate (supplied by Kagaku catalyst Co., ltd., al 2 O 3 41g/L，Na 2 O297 g/L, density 1353 g/L) was added to 378g of water glass (supplied by Kagaku catalyst Co., ltd., siO) 2 250.9g/L, modulus 3.31 and density 1258 g/L), stirring for 50min, stopping stirring, standing and aging in a closed container at 11 deg.C for 38 hr to obtain the final product, and directly using without adding water. The molar ratio of the guiding agent is 16.4Na 2 O:Al 2 O 3 :15SiO 2 :325.5H 2 O。
2) Preparation and crystallization of synthetic gel
Under vigorous stirring, 240g of room temperature aluminum sulfate (supplied by Kaolin catalyst Co., ltd., siO2250.9g/L, modulus 3.31, density 1258 g/L) was added sequentially to 387g of room temperature water glass (supplied by Kaolin catalyst Co., ltd., al) 2 O 3 89.7g/L，H 2 SO 4 259g/L, density 1277 g/L), 5g normal temperature low alkali sodium metaaluminate (Na 2O 280.8g/L, al2O3 186.7g/L, density 1416 g/L) obtained in step 1), 338g 5 ℃ guiding agent obtained in step 1) and 95g normal temperature water, stirring for 60min after the addition of the materials to obtain a synthetic gel mixture with a molar composition of 2.86Na 2 O：Al 2 O 3 ：9.0SiO 2 ：210H 2 O from Al in directing agent 2 O 3 Accounting for Al in the gel mixture 2 O 3 20% of the total amount. And (3) putting the obtained synthetic gel into a stainless steel reaction kettle, crystallizing for 32 hours at 98 ℃, filtering and washing a crystallized product, and drying overnight at 120 ℃ in an oven to obtain the NaY molecular sieve.
The crystallinity of the NaY molecular sieve was 94%, the ratio of skeletal silica to alumina was 5.8, and SEM photograph was shown in FIG. 9, showing an average particle size of about 200nm.
As can be seen from the results of the above examples and comparative examples, the present invention prepares a small-sized NaY molecular sieve by changing the preparation method and the amount of the conventional directing agent, as compared with the preparation of the NaY molecular sieve by the conventional method: the crystal grain (200 nm-700 nm) of the NaY molecular sieve prepared by the method is obviously smaller than that of the NaY molecular sieve prepared by the conventional method (700 nm-1000 nm).
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 (7)
1. A method for preparing a small-grain NaY molecular sieve comprising the steps of preparing a directing agent, preparing a gel mixture, and crystallizing the gel mixture, characterized by:
in the step of preparing the guiding agent, guiding agent raw materials are mixed and stirred uniformly at the temperature of 11-30 ℃ and are kept stand for ageing for 1-40 hours without adding water, the guiding agent raw materials comprise sodium silicate, sodium metaaluminate and sodium hydroxide solution, and the molar ratio of the guiding agent raw materials is (15-18) Na 2 O:Al 2 O 3 :(15～17)SiO 2 :(280～380)H 2 O；
The step of preparing the gel mixture is to stir the gel mixture according to Na 2 O：Al 2 O 3 ：SiO 2 ：H 2 O=1.5 to 8:1:5 to 18: mixing silicon source, aluminium salt solution, aluminate solution and guiding agent in the molar ratio of 100-500, and in this step, al from the guiding agent 2 O 3 Accounting for Al in the gel mixture 2 O 3 10-20% of the total amount, wherein the silicon source is water glass, the aluminum salt is one or more of aluminum sulfate, aluminum chloride, aluminum nitrate or aluminum phosphate, and the aluminate is sodium metaaluminate.
2. The method according to claim 1, wherein in the step of preparing the directing agent, the directing agent raw materials are mixed and stirred uniformly at 12-27 ℃ and are kept stand for aging for 5-35 hours without adding water.
3. The method according to claim 1, wherein in the step of preparing the guiding agent, the guiding agent raw materials are mixed and stirred uniformly at 15-25 ℃ and are kept stand for aging for 8-30 hours without adding water.
4. Pressing the buttonThe method according to claim 1, wherein the step of preparing the gel mixture is performed under stirring according to Na 2 O：Al 2 O 3 ：SiO 2 ：H 2 O=2 to 6:1: 7-10: mixing silicon source, aluminium salt solution, aluminate solution and guiding agent in the molar ratio of 150-400.
5. The method of claim 1 wherein said aluminum salt is aluminum sulfate.
6. The method according to claim 1, wherein, in said step of preparing the gel mixture, al is derived from a directing agent 2 O 3 Accounting for Al in the gel mixture 2 O 3 12-15% of the total amount.
7. The method according to claim 1, wherein the step of crystallizing the gel mixture is crystallizing the gel mixture at 70 to 120 ℃ for 10 to 50 hours.
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