CN112723374B - NaY molecular sieve and synthesis method thereof - Google Patents

NaY molecular sieve and synthesis method thereof Download PDF

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CN112723374B
CN112723374B CN201911030846.9A CN201911030846A CN112723374B CN 112723374 B CN112723374 B CN 112723374B CN 201911030846 A CN201911030846 A CN 201911030846A CN 112723374 B CN112723374 B CN 112723374B
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molecular sieve
nay
stirring
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nay molecular
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方向晨
杜艳泽
牛国兴
秦波
黄曜
柳伟
赵东元
高杭
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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Abstract

The invention discloses a NaY molecular sieve and a synthesis method thereof. The NaY molecular sieve has a nanosheet shape; the specific surface area of the NaY molecular sieve is 700~850 m 2 (iv) g; the external specific surface area is 140 to 250 m 2 (ii)/g; the mesoporous volume is 0.15 to 0.45 cm 3 (ii) in terms of/g. The method does not need to adopt a template agent, and the prepared NaY molecular sieve has a rich mesoporous structure and a high external specific surface area.

Description

NaY molecular sieve and synthesis method thereof
Technical Field
The invention belongs to the technical field of material chemistry, catalytic chemistry and chemical engineering, and relates to a NaY molecular sieve and a synthesis method thereof, in particular to a high-specific surface area NaY molecular sieve rich in mesopores and a synthesis method thereof.
Background
With continuous exhaustion of conventional petroleum resources, deep processing of macromolecular heavy oil and residual oil is more and more widely regarded, but when the traditional catalytic cracking and hydrocracking catalyst taking the Y molecular sieve as an acidic component is used for treating heavy oil with large molecular weight and complex structure, the catalyst is constrained by the size of micropores of the molecular sieve, and the diffusion of materials in the pore channels of the molecular sieve is severely constrained, so that the activity of the catalyst is reduced, the deep cracking is increased, the selectivity is poor, the carbon deposition is intensified, the service life is shortened, and the wide application of the catalyst in the processing of the heavy oil is severely restricted. Therefore, the method breaks through the diffusion limitation of the Y molecular sieve on the macromolecular heavy oil, improves the capability of the Y molecular sieve for treating the macromolecular inferior oil, becomes a key link for the technical change of catalytic cracking and hydrocracking, and is also an important research hotspot in the field of molecular sieve synthesis at present.
At present, two important technical means can improve the diffusion limitation of the Y molecular sieve to macromolecules: firstly, introducing multi-stage pores into a Y molecular sieve crystal to form a multi-stage structure with large-medium-micropore pore size gradient distribution, and ensuring that heavy oil molecules are cracked in a catalyst stage by stage; the other is to reduce the grain size of the Y molecular sieve so as to shorten the diffusion path of the material and product molecules in the molecular sieve pore canal. Compared with the former, the latter technology is more mature, and a plurality of literatures and patents disclose synthesis methods of small crystal grains and nano NaY molecular sieves, and the synthesis methods do not need any organic template agent, so that the synthesis cost is lower, the energy consumption is lower, the pollution is less, and the method is more attractive in industrial application.
Although the nano NaY molecular sieve can effectively improve material diffusion, because the particles are too small, the separation becomes more difficult in the molecular sieve preparation and subsequent dealumination processes, special equipment or high pressure or separation time prolonging and the like are needed, and the product loss is large; and the surface energy of the nano molecular sieve is high, the framework structure is extremely unstable, the nano molecular sieve is easy to collapse in the process of forming the ultra-stable USY molecular sieve by subsequent dealumination, and some special dealumination technologies or processes are required to be supplemented, so that the dealumination process becomes complicated, the control of technical parameters becomes difficult, and the wide application of the nano molecular sieve is limited.
If the NaY molecular sieve with the nanosheet morphology can be synthesized, the above problems can be better solved. On one hand, the material has the nanometer characteristic and can effectively solve the problem of material diffusion; on the other hand, the method has the characteristics of easy separation of large particles and good stability.
Inayat A and the like successfully synthesize the 'tile-shaped' nano thin-layer stacking morphology X molecular sieve by using amphiphilic organosilane of 3-hexadecyl-3-diethylamino-propyltrimethoxysilanesulfonylammonium bromide (TPHAC) as a templateAngew. Chem. Int. Ed., 2012, 51(8): 1962-1965）； Khaleel M (Angew. Chem. Int. Ed.,2014，53(36)：9456-9461)、Jin (Ind. Eng. Chem. Res., 2014, 53(8): 3406-3411) 、Thittaya Y. (J Clean Prod.,2017, 142: 1244-1251) and Liu B. (lRSC Adv.2013, 3: 15075-15084), etc. with N, N-dimethyl-N- [3- (trimethicone) propyl group, respectively]Synthesizing FAU molecular sieve with leaf-shaped nano thin-layer structure by using ammonium stearyl chloride (TPOAC). However, these syntheses all require expensive amphiphilic organosilanes as templating agents, which not only increases the synthesis cost, but also pollutes the environment due to the release of large amounts of waste gases during the removal of the templating agents. And these resulting products are Si/AThe low l ratio of NaY molecular sieve, even X type molecular sieve, will undoubtedly increase the difficulty and product loss of the subsequent dealumination to form the ultra-stable Y molecular sieve with high Si/Al ratio. These factors greatly limit their widespread use in the actual industry.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a NaY molecular sieve and a synthesis method thereof. The method does not need to adopt a template agent, and the prepared NaY molecular sieve has a rich mesoporous structure and a high external specific surface area.
A NaY molecular sieve having a nanosheet morphology; the specific surface area of the NaY molecular sieve is 700-850 m 2 The ratio of the acid to the base is preferably 750 to 820 m/g 2 (iv)/g, more preferably 800 to 810 m 2 (ii)/g; the external specific surface area is 140 to 250 m 2 Per g, preferably 160 to 220 m 2 (iv)/g, more preferably 180 to 210 m 2 (ii)/g; the mesoporous volume is 0.15 to 0.45 cm 3 Per g, preferably 0.25 to 0.40 cm 3 Per g, more preferably 0.30 to 0.35 cm 3 /g。
A method for synthesizing a NaY molecular sieve comprises the following steps:
(1) In a metered molar ratio (0.00 to 1.0) Na 2 O ：(0.30~0.5) Al 2 O 3 ：5 SiO 2 ：80~90 H 2 O, preferably (0.02 to 0.16) Na 2 O ：(0.3~0.4) Al 2 O 3 ：5 SiO 2 ：80~90 H 2 O; uniformly mixing a proper amount of silicon source, aluminum source, alkali source and water to form colloid;
(2) Adding nano NaY seed crystal stock solution into the material obtained in the step (1), wherein the adding amount is 2-30%, preferably 7-25%, and more preferably 14-18% of the total feeding mass; then, the alkali source and the water are complemented to ensure that the final molar ratio of the materials in the system is (1.5 to 2.0) Na 2 O:(0.30~0.5)Al 2 O 3 :5SiO 2 : (140~200) H 2 O, preferably (1.6 to 1.8) Na 2 O : (0.30~0.4) Al 2 O 3 : 5SiO 2 : (140~200) H 2 O；
(3) And (3) crystallizing, filtering, drying and roasting the material in the step (2) to obtain the NaY molecular sieve.
According to the method, in the step (1), the silicon source is one or more of water glass, silica sol, silica gel and white carbon black, wherein the silica sol is preferred; the aluminum source is one or more of aluminum nitrate, aluminum sulfate, sodium metaaluminate and metal aluminum, wherein the preferred aluminum source is sodium metaaluminate and aluminum sulfate; the alkali source is one or more of sodium hydroxide, potassium hydroxide or ammonia water.
The method comprises the step (1) of mixing all silicon sources and part of H 2 Stirring O fully, adding a proper amount of NaAlO 2 After fully stirring the aqueous solution, adding a proper amount of Al 2 (SO 4 ) 3 An aqueous solution of (a); charged NaAlO 2 And Al 2 (SO 4 ) 3 In a mass ratio of 0.5-1:1.
the method comprises the step (1) that the colloid is 20 to 80 o C (temperature T1), stirring for 6 to 48 hours in a sealed manner (time T1); adding nano NaY seed crystal stock solution into the step (2), and then, controlling the temperature to be 20 to 80 DEG o C (temperature T2), continuously stirring for 6 to 24h (time T2), and adding the required NaOH solution and water.
The method of the present invention, the preparation of the nano NaY seed crystal stock solution in step (2) can adopt any one of the prior art, and preferably adopts the following method to prepare the nano NaY seed crystal stock solution according to Na 2 O : Al 2 O 3 : SiO 2 : H 2 O = (10 to 15) in a molar ratio of 1 (10 to 18) to 200 to 400, preferably 12 to 13) Na 2 O : Al 2 O 3 : (14~15) SiO 2 : (220~240) H 2 The molar ratio of O is that the silicon source, the aluminum source and the water are mixed in 0~5 o C, mixing in an ice water bath to obtain a colorless transparent mixture, stirring at room temperature, and keeping the temperature within 40-80 DEG o And C, standing and crystallizing for 6 to 96 hours to obtain semi-transparent, pale and viscous nano NaY molecular sieve seed crystal stock solution.
In the method, the crystallization temperature in the step (2) is 80 to 100 o C, crystallizing for 12 to 96 hours; the drying temperature is 100 to 150 DEG oC The drying time is 2 to 5 hours, and the baking temperature is 450 to 550 o And C, roasting for 2 to 4 hours.
The method of the invention is realized by controlling a plurality ofThe synthesis parameters influencing the formation of the NaY molecular sieve nano-sheet structure promote the material to form low-concentration AlO under the conditions of low alkalinity, high Si/Al charge ratio, high aging temperature and proper nano NaY crystal seed amount 2 ] - Ions, the surface energy of the side surface is higher than that of the front surface of the nano NaY molecular sieve crystal grains, and the [ AlO ] is 2 ] - Ions can be preferentially combined with the side surface of the NaY nanocrystal to form rich AlO 2 ] - And (3) anchoring points, inducing a silicon source to be stacked along the side surface of the nano-crystal, forming a flaky nano-particle aggregate through directional bridging, and crystallizing after supplementing required alkali to form the complete nano-sheet NaY molecular sieve with a smooth surface. Wherein the technical key is to control the AlO in the initial silicon-aluminum adhesive 2 ] - The appropriate ratio of ion concentration to amount of nanocrystal seed. If the amount of the nanocrystals is small, [ AlO ] 2 ] - Excess [ AlO ] while preferentially binding to the nanocrystal sides 2 ] - Ions can be gathered on the front surface of the nano crystal to form anchor points which are as rich as the side surfaces, and at the moment, the accumulation and bridging of the silicon source on the front surface and the side surfaces of the nano crystal seed have no obvious difference and the molecular sieve with the sheet structure can not be formed. Likewise, high basicity, low SiO 2 /Al 2 O 3 When the feed ratio is high, [ AlO ] in the solution 2 ] - The ion concentration is too high, and enough AlO exists 2 ] - Ions can be combined with the side surface and the front surface of the nano crystal, and the NaY molecular sieve of the nano sheet cannot be formed. The key point of the invention is to discover key factors influencing the formation of NaY nanosheet structure and solve the problem of [ AlO ] in the initial silica-alumina gel 2 ] - The matching problem of the ion concentration and the quantity proportion of the nano crystal seeds enables the synthesis of the nano sheet NaY molecular sieve to be effectively controllable and reproducible.
According to the method, no organic template agent is needed, and the nanosheet NaY molecular sieve which is high in crystallinity, uniform in appearance, 50-100 nm in thickness and rich in mesoporous structure and high in specific surface area can be synthesized by using conventional raw materials, processes and equipment. The method is simple, low in cost and beneficial to industrial production and application popularization. The nano-sheet Y molecular sieve prepared by the method can be used as a catalyst or a carrier for isomerization pour point depression, hydrocracking, catalytic cracking and the like.
The NaY molecular sieve synthesized by the invention has low temperature N 2 The adsorption curve is different from that of the conventional microporous NaY molecular sieve in p/p 0 And (4) the samples at the positions of =0.2 to 1.0 show a single-edge raising trend, which indicates that the samples have rich outer surfaces and accord with the adsorption characteristics of the nanosheet structure. The desorption curve is p/p 0 The position of =0.2 to 0.95 does not coincide with the adsorption curve, and a wide hysteresis loop exists, which indicates that meso pores and macro pores with various pore diameters exist in the sample. The electron micrograph shows that the crystal morphology of the crystal grows by the bridging of 50 to 100nm thick lamella. These nanoplatelets provide up to 209 m 2 The cross-linked growth and accumulation of the nano-sheets provide up to 0.36 cm 3 The total pore volume is increased to 0.72 cm 3 Is much higher than that of the conventional microporous NaY molecular sieve (about 0.45 cm) 3 In terms of/g). The cross-grown nano-sheet NaY molecular sieve not only greatly shortens micropore channels of the molecular sieve, but also provides rich and unobstructed mesopore channels, is convenient for rapid diffusion of materials, and is particularly suitable for being used as a catalyst or a carrier material for macromolecular hydrocracking and catalytic cracking.
The method adopts the nano NaY molecular sieve synthetic stock solution as the seed crystal to replace the traditional transparent guiding agent and induce the formation of the nano lamellar NaY molecular sieve. Compared with the traditional transparent guiding agent, the nano NaY molecular sieve crystal seed has stronger capabilities of inducing material crystallization and directional growth.
Description of the drawings:
FIG. 1 is an X-ray diffraction pattern of the Nanosheet-NaY-1 molecular sieve synthesized by the method of example 1 of the present invention.
FIG. 2 is a low temperature nitrogen adsorption-desorption curve for the synthesis of Nanosheet-NaY-1 molecular sieves according to example 1 of the process of the present invention.
FIG. 3 is a plot of the pore size distribution of the Nanosheet-NaY-1 molecular sieve synthesized according to inventive method example 1.
FIG. 4 is a scanning electron micrograph of the Nanosheet-NaY-1 molecular sieve synthesized by the method of example 1 of the present invention.
The specific implementation mode is as follows:
the following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
When the specification concludes with the claims defining the matters, materials, methods, steps, etc. that are regarded as being known to one of ordinary skill in the art, such that the objects, materials, methods, steps, etc., that are derived from the heading "known to one of ordinary skill in the art", "prior art", or the like, are intended to include those matters conventionally used in the art at the time of filing, but including those matters not yet commonly used in the art, but rather, to be construed as being suitable for the purpose for which the present disclosure is directed.
The X-ray diffraction pattern in this example was measured by Bruker D4 powder diffractometer, cuK α The source, tube pressure 40 kV, tube flow 40 mA.
The low-temperature nitrogen adsorption-desorption curve of the molecular sieve is measured in a Micromeritics Tristar 3020 type analyzer at 77K, and the BET method is used for calculating the specific surface area of a sample.
The pore size distribution curve of the molecular sieve of this example was measured at 77K on a Micromeritics Tristar 3020 analyzer, the pore size distribution was calculated by the BJH method, the pore volume was calculated from the adsorption at a relative pressure of 0.995, and the micropores were analyzed by the t-plot method.
The SEM image of this example was completed on a Philip XL30 model at a working voltage of 20 kV.
Example 1:
1. and (3) synthesis of nano NaY molecular sieve seed crystal:
200 Dissolving NaOH in 500 g water, cooling, slowly adding metal aluminum wires with the total amount of 37.80 g for multiple times, supplementing the lost water after complete dissolution, and cooling to room temperature for later use (solution A); 520 g NaOH was dissolved in 980 g water, 2000 g was added containing 30% SiO 2 Heating and stirring the silica sol properly, cooling the solution to 0~5 by using an ice-water bath after the solution becomes transparent and no particles are determined o C, adding the solution (A) prepared before one time, and stirring to ensure that the solution is colorless and transparentStirring at room temperature for 24h, 60 o C static crystallization 24 h. Obtain light white semitransparent sticky emulsion. Final composition of the liquid crystal: 12.9 Na (Na) 2 O : Al 2 O 3 : 14.3 SiO 2 : 229 H 2 O。
2. Synthesis of a nano-sheet NaY molecular sieve:
20.0 g of H were added beforehand to 42.48 g silica sol (30%) 2 O, fully stirring to ensure that the silica sol is well dispersed; 2.208 g is added via 150 oC Baking of 4h NaAlO 2 (content: 0.5 g NaOH/g and 0.5 g Al 2 O 3 /g) dissolved in 25.00 g H 2 O solution, after stirring well, 2.70 g of Al was added 2 (SO 4 ) 3 .18H 2 O dissolved in 23.78 g H 2 O solution, the formed feed ratio is as follows: 0.04 Na (Na) 2 O ：0.35 Al 2 O 3 ：5 SiO 2 ：80~90 H 2 White colloid a of O. The colloid is at a temperature T1=50 o C, stirring in a closed manner for T1=24 h, adding nano NaY seed crystal stock solution with the total crystallization material mass fraction of 13.93% (22.5 g), and stirring at T2=50 o C, after stirring for a time t2= 24H, 2.841 g of NaOH was added and dissolved in 20.00 g of H 2 O solution, the final material feeding ratio is 1.6 Na 2 O : 0.35 Al 2 O 3 : 5 SiO 2 : 140 H 2 O，50 o Stirring for 4h under C, and then 90oC Crystallizing 46 h, filtering, washing and drying to obtain a sample Nanosheet-NaY-1, wherein the structural parameters such as specific surface area and pore volume are listed in Table 1.
Example 2:
20.0 g of H were added beforehand to 42.48 g silica sol (30%) 2 O, fully stirring to ensure that the silica sol is well dispersed; 2.208 g was added at 150 oC Baking NaAlO after baking 4h 2 (content: 0.5 g NaOH/g and 0.5 g Al 2 O 3 /g) dissolved in 25.00 g H 2 O solution, after stirring well, 2.70 g of Al was added 2 (SO 4 ) 3 .18H 2 O dissolved in 23.78 g H 2 O solution, wherein the forming feed ratio is as follows: 0.04 Na (Na) 2 O ：0.35 Al 2 O 3 ：5 SiO 2 ：80~90 H 2 White colloid a of O. The colloid is used at T1=50 o C, stirring in a closed manner for T1=24 h, adding nano NaY seed crystal stock solution with 20.96% of total crystallization material (38.6 g) in mass fraction, and stirring at T2=50 o Stirring for t2= 24H under C, and adding 1.080 g NaOH to dissolve in 20.00 g H 2 O solution, the final material feeding ratio is 1.6 Na 2 O : 0.35 Al 2 O 3 : 5 SiO 2 : 140 H 2 O，50 o Stirring for 4h under C, and then 90 oC Crystallizing 46 h, filtering, washing and drying to obtain a sample Nanosheet-NaY-2, wherein the structural parameters such as specific surface area, pore volume and the like are listed in Table 1.
Example 3:
20.0 g of H were added beforehand to 42.48 g silica sol (30%) 2 O, fully stirring to ensure that the silica sol is well dispersed; 2.208 g was added at 150 oC Baking NaAlO after baking 4h 2 (content: 0.5 g NaOH/g and 0.5 g Al 2 O 3 /g) dissolved in 25.00 g H 2 O solution, after stirring well, 2.70 g of Al was added 2 (SO 4 ) 3 .18H 2 O in 23.78 g H 2 O solution, the formed feed ratio is as follows: 0.04 Na (Na) 2 O ：0.35 Al 2 O 3 ：5 SiO 2 ：80~90 H 2 White colloid a of O. The colloid is used at T1=50 o C, stirring the mixture hermetically for T1=24 h, adding nano NaY seed crystal stock solution with the total crystallization material mass fraction of 24.49% (48.5 g), and stirring the mixture hermetically at T2=50 o After stirring time t2= 24H under C, 20.00 g of H is added 2 O, the final material feed ratio is 1.6 Na 2 O : 0.35 Al 2 O 3 : 5 SiO 2 : 140 H 2 O，50 o Stirring for 4h under C, and then 90 oC Crystallizing 46 h, filtering, washing and drying to obtain a sample Nanosheet-NaY-3, wherein the structural parameters such as specific surface area, pore volume and the like are listed in Table 1.
Example 4:
20.0 g of H were added beforehand to 42.48 g silica sol (30%) 2 O, fully stirring to ensure that the silica sol is well dispersed; add 2.666 g at 150 oC NaAlO after baking 4h 2 (content: 0.5 g NaOH/g and 0.5 g Al 2 O 3 /g) soluble in 25.00g H 2 O solution, after stirring well, 3.973 g of Al was added 2 (SO 4 ) 3 .18H 2 O dissolved in 23.78 g H 2 O solution, the formed feed ratio is as follows: 0.08 Na (Na) 2 O ：0.4 Al 2 O 3 ：5 SiO 2 ：80~90 H 2 White colloid a of O. The colloid is used at T1=50 o C, stirring the mixture hermetically for T1=24 h, adding nano NaY seed crystal stock solution with the total crystallization material mass fraction of 13.93% (22.5 g), and stirring the mixture hermetically at T2=50 o C, after stirring for a time t2= 24H, 2.922 g of NaOH was added and dissolved in 20.00 g of H 2 O solution, the final material feeding ratio is 1.65 Na 2 O : 0.4 Al 2 O 3 : 5 SiO 2 : 140 H 2 O，50 o Stirring for 4h under C, and then 90 oC Crystallizing 46 h, filtering, washing and drying to obtain a sample Nanosheet-NaY-4, wherein the structural parameters such as specific surface area, pore volume and the like are listed in Table 1.
Example 5:
20.0 g of H were added beforehand to 42.48 g silica sol (30%) 2 O, fully stirring to ensure that the silica sol is well dispersed; 2.208 g was added at 150 oC Baking NaAlO after baking 4h 2 (content: 0.5 g NaOH/g and 0.5 g Al 2 O 3 /g) dissolved in 25.00 g H 2 O solution, after stirring well, 2.70 g of Al was added 2 (SO 4 ) 3 .18H 2 O dissolved in 23.78 g H 2 O solution, the formed feed ratio is as follows: 0.04 Na (Na) 2 O ：0.35 Al 2 O 3 ：5 SiO 2 ：80~90 H 2 White colloid a of O. The colloid is used at T1=50 o C, stirring the mixture hermetically for T1=24 h, adding nano NaY seed crystal stock solution with the total crystallization material mass fraction of 13.93% (22.5 g), and stirring the mixture hermetically at T2= 20 o C, after stirring for a time t2= 24H, 2.841 g of NaOH was added and dissolved in 20.00 g of H 2 O solution, the final material feeding ratio is 1.6 Na 2 O : 0.35 Al 2 O 3 : 5 SiO 2 : 140 H 2 O，20 o Stirring for 4h under C, and then 90 oC Crystallizing 46 h, filtering, washing and drying to obtain a sample Nanosheet-NaY-5, wherein the structural parameters such as specific surface area, pore volume and the like are listed in Table 1.
Example 6:
20.0 g of H were added beforehand to 42.48 g silica sol (30%) 2 O, fully stirring to ensure that the silica sol is well dispersed; 2.208 g was added at 150 oC Baking NaAlO after baking 4h 2 (content: 0.5 g NaOH/g and 0.5 g Al 2 O 3 /g) dissolved in 25.00 g H 2 O solution, after stirring well, 2.70 g of Al was added 2 (SO 4 ) 3 .18H 2 O dissolved in 23.78 g H 2 O solution, the formed feed ratio is as follows: 0.04 Na (Na) 2 O ：0.35 Al 2 O 3 ：5 SiO 2 ：80~90 H 2 White colloid a of O. The colloid is used at T1=50 o C, stirring in a closed manner for T1=24 h, adding nano NaY seed crystal stock solution with the total crystallization material mass fraction of 13.93% (22.5 g), and stirring at T2=50 o C stirring time t2= 12H, adding 2.841 g NaOH to dissolve in 20.00 g H 2 O solution, the final material feeding ratio is 1.6 Na 2 O : 0.35 Al 2 O 3 : 5 SiO 2 : 140 H 2 O，50 o Stirring for 4h under C, and then 90 oC Crystallizing 46 h, filtering, washing and drying to obtain a sample Nanosheet-NaY-6, wherein the structural parameters such as specific surface area, pore volume and the like are listed in Table 1.
Example 7:
20.0 g of H were added beforehand to 42.48 g silica sol (30%) 2 O, fully stirring to ensure that the silica sol is well dispersed; 2.208 g was added at 150 oC Baking NaAlO after baking 4h 2 (content: 0.5 g NaOH/g and 0.5 g Al 2 O 3 /g) dissolved in 25.00 g H 2 O solution, after stirring well, 2.70 g of Al was added 2 (SO 4 ) 3 .18H 2 O dissolved in 23.78 g H 2 O solution, the formed feed ratio is as follows: 0.04 Na (Na) 2 O ：0.35 Al 2 O 3 ：5 SiO 2 ：80~90 H 2 White colloid a of O. The colloid has a molecular weight of T1=50 o C, stirring in a closed manner for T1=48 h, adding nano NaY seed crystal stock solution with the total crystallization material mass fraction of 13.93% (22.5 g), and stirring at T2=50 o C stirring time t2= 12H, adding 2.841 g NaOH to dissolve in 20.00 g H 2 Solution of O, final materialThe feed ratio is 1.6 Na 2 O : 0.35 Al 2 O 3 : 5 SiO 2 : 140 H 2 O，50 o Stirring for 4h under C, and then 90 oC Crystallizing 46 h, filtering, washing and drying to obtain a sample Nanosheet-NaY-7, wherein the structural parameters such as specific surface area, pore volume and the like are listed in Table 1.
Example 8 (control 1):
20.0 g of H were added beforehand to 42.48 g silica sol (30%) 2 O, fully stirring to ensure that the silica sol is well dispersed; add 2.285 g at 150 oC Baking NaAlO after baking 4h 2 (content: 0.5 g NaOH/g and 0.5 g Al 2 O 3 /g) dissolved in 25.00 g H 2 O solution, after stirring well, 2.444 g of Al was added 2 (SO 4 ) 3 .18H 2 O dissolved in 23.78 g H 2 O solution, the formed feed ratio is as follows: 0.04 Na (Na) 2 O ：0.35 Al 2 O 3 ：5 SiO 2 ：80~90 H 2 White colloid a of O. The colloid is used at T1=50 o C, stirring in a closed manner for T1=24 h, adding nano NaY seed crystal stock solution with 3.47% of total crystallization material (4.737 g) by mass, and stirring at T2=50 o C stirring time t2= 12H, adding 4.656 g NaOH to dissolve in 20.00 g H 2 O solution, the final material feeding ratio is 1.6 Na 2 O : 0.35 Al 2 O 3 : 5 SiO 2 : 140 H 2 O，50 o Stirring for 24h under C, and then 90 oC Crystallizing 46 h, filtering, washing and drying to obtain a control group sample Ref-NaY-1, wherein the structural parameters such as specific surface area, pore volume and the like are listed in Table 1.
Example 9 (control 2):
20.0 g of H were added beforehand to 42.48 g silica sol (30%) 2 O, fully stirring to ensure that the silica sol is well dispersed; 2.364 g was added at 150 oC Baking NaAlO after baking 4h 2 (content: 0.5 g NaOH/g and 0.5 g Al 2 O 3 /g) dissolved in 25.00 g H 2 O solution, after stirring well, 2.190 g Al is added 2 (SO 4 ) 3 .18H 2 O dissolved in 23.78 g H 2 O solution, the formed feed ratio is as follows: 0.12 Na (Na) 2 O ：0.35 Al 2 O 3 ：5 SiO 2 ：80~90 H 2 White colloid a of O. The colloid has a molecular weight of T1=50 o C, stirring in a closed manner for T1=24 h, adding nano NaY seed crystal stock solution with the total crystallization material mass fraction of 13.93% (22.5 g), and stirring at T2=50 o C stirring time t2= 12H, adding 2.579 g NaOH to dissolve in 20.00 g H 2 O solution, the final material feeding ratio is 1.6 Na 2 O : 0.35 Al 2 O 3 : 5 SiO 2 : 140 H 2 O，50 o Stirring for 24h under C, and then 90 oC Crystallizing 46 h, filtering, washing, drying to obtain a control sample Ref-NaY-2, wherein the structural parameters such as specific surface area and pore volume are listed in Table 1.
Example 10 (control 3):
20.0 g of H were added beforehand to 42.48 g silica sol (30%) 2 O, fully stirring to ensure that the silica sol is well dispersed; 2.208 g was added at 150 oC Baking NaAlO after baking 4h 2 (content: 0.5 g NaOH/g and 0.5 g Al 2 O 3 /g) dissolved in 25.00 g H 2 O solution, after stirring well, 2.70 g of Al was added 2 (SO 4 ) 3 .18H 2 O dissolved in 23.78 g H 2 O solution, the formed feed ratio is as follows: 0.04 Na (Na) 2 O ：0.35 Al 2 O 3 ：5 SiO 2 ：80~90 H 2 White colloid a of O. The colloid has a molecular weight of T1= 30 o C, stirring in a closed manner for T1=24 h, adding nano NaY seed crystal stock solution with the total crystallization material mass fraction of 13.93% (22.5 g), and stirring at T2= 30 o After stirring time t2= 24H under C, 2.841 g of NaOH is added and dissolved in 20.00 g of H 2 O solution, the final material feeding ratio is 1.6 Na 2 O : 0.35 Al 2 O 3 : 5 SiO 2 : 140 H 2 O，30 o After stirring for 4h at C, at 90 oC Crystallizing 46 h, filtering, washing, drying to obtain a control sample Ref-NaY-3, wherein the structural parameters such as specific surface area and pore volume are listed in Table 1.
Example 11 (control 4):
20.0 g of H were added beforehand to 42.48 g silica sol (30%) 2 O, fully stirring to ensure that the silica sol is well dispersed; 2.208 g was added at 150 oC Baking NaAlO after baking 4h 2 (content: 0.5 g NaOH/g and 0.5 g Al 2 O 3 /g) dissolved in 25.00 g H 2 O solution, after stirring well, 2.70 g of Al was added 2 (SO 4 ) 3 .18H 2 O dissolved in 23.78 g H 2 O solution, the formed feed ratio is as follows: 0.04 Na (Na) 2 O ：0.35 Al 2 O 3 ：5 SiO 2 ：80~90 H 2 White colloid a of O. The colloid is used at T1=20 o C, stirring in a closed manner for T1=24 h, adding nano NaY seed crystal stock solution with the total crystallization material mass fraction of 13.93% (22.5 g), and stirring at T2=50 o C stirring time t2= 24H, then 2.841 g NaOH was added and dissolved in 20.00 g H 2 O solution, the final material feeding ratio is 1.6 Na 2 O : 0.35 Al 2 O 3 : 5 SiO 2 : 140 H 2 O，50 o Stirring for 4h under C, and then 90 oC Crystallizing 46 h, filtering, washing, drying to obtain a control sample Ref-NaY-4, wherein the structural parameters such as specific surface area and pore volume are listed in Table 1.
Example 12 (control 5):
20.0 g of H were added beforehand to 42.48 g silica sol (30%) 2 O, fully stirring to ensure that the silica sol is well dispersed; 2.208 g was added at 150 oC NaAlO after baking 4h 2 (content: 0.5 g NaOH/g and 0.5 g Al 2 O 3 /g) dissolved in 25.00 g H 2 O solution, after stirring well, 2.70 g of Al was added 2 (SO 4 ) 3 .18H 2 O in 23.78 g H 2 O solution, wherein the forming feed ratio is as follows: 0.04 Na (Na) 2 O ：0.35 Al 2 O 3 ：5 SiO 2 ：80~90 H 2 White colloid a of O. The colloid is used at T1=50 o C, stirring the mixture hermetically for T1=6 h, adding nano NaY seed crystal stock solution with the total crystallization material mass fraction of 13.93% (22.5 g), and stirring the mixture hermetically at T2=50 o C stirring time t2= 12H, adding 2.841 g NaOH to dissolve in 20.00 g H 2 O solution, the final material feeding ratio is 1.6 Na 2 O : 0.35 Al 2 O 3 : 5 SiO 2 : 140 H 2 O，50 o Stirring for 4h under C, and then 90 oC Crystallization of 46 h,then filtering, washing and drying to obtain a control group sample Ref-NaY-5, wherein the structural parameters such as specific surface area, pore volume and the like are listed in Table 1.
TABLE 1
Figure 968929DEST_PATH_IMAGE002
1. Proportion in the initial white colloid a; 2, proportion in the final crystallized material; 3, the mass percentage of the seed crystal in the crystallization material;
the sample Ref-NaY-1 synthesized with only 5% of seed crystal amount has only 84.5 m under the condition of complete crystallization 2 Specific mesoporous surface area/g of 0.12 cm 3 Per g mesoporous volume; when Na/Si in the white initial glue is increased to 0.048, the mesopore specific surface area and the mesopore volume of the Ref-NaY-2 sample are only 131.8 m 2 /g and 0.19 cm 3 (ii)/g; at T1 and T2 of 30 o The mesoporous specific surface area of a sample Ref-NaY-3 synthesized under C is only 93.5 m 2 The mesoporous volume is only 0.12 cm 3 (ii)/g; at T1=20 o Stirring under C24 h and T1=50 oC Ref-NaY-4 and Ref-NaY-5 samples synthesized by 6 h are stirred only, and the mesopore specific surface area and the mesopore volume are also very small. In contrast, the white initial paste had Na/Si of 0.016, and T1 and T2 of 50 o Stirring the mixture under C for 24h, and then rapidly increasing the mesoporous specific surface area of the Nanosheet-NaY-1, nanosheet-NaY-2 and Nanosheet-NaY-3 samples when the seed crystal amount is increased to 20 to 35 percent>180 m 2 The volume of the mesopores also rises to 0.30 cm 3 The samples per gram, especially Nanosheet-NaY-1, have the highest mesopore specific surface area and mesopore volume; at a T1 temperature of 50 o C, even if T2 is reduced to 20 oC Or let T2=50 oC The stirring time is shortened to 12 h, and the obtained samples Nanosheet-NaY-5 and Nanosheet-NaY-6 can still keep high mesopore specific surface area and mesopore volume under the condition that other synthesis conditions are similar to those of Nanosheet-NaY-1. These results show that the Na of the white initial gum 2 O/SiO 2 The ratio, the stirring temperature (T2), the stirring time (T1) and the amount of the nanocrystalline are key parameters influencing the formation of the nano-sheet NaY molecular sieve, and the nano-sheet NaY molecular sieve can obtain the nano-sheet NaY molecular sieve with the thickness of 50-100nm, the width of-500 nm and the width under the optimal conditionsFlaky bridging growth with a thickness ratio of 5 to 10, complete crystallization, and a thickness ratio of 209 m 2 0.36 cm external surface area/g 3 The volume of each mesoporous is 0.72 cm 3 A nanosheet NaY molecular sieve (example Sheet-NaY-1) per gram.

Claims (11)

1. A NaY molecular sieve characterized by: the specific surface area of the NaY molecular sieve is 750 to 820 m 2 (ii)/g; the external specific surface area is 160 to 220 m 2 (ii)/g; the mesoporous volume is 0.25 to 0.40 cm 3 /g；
The NaY molecular sieve is obtained according to a synthesis method comprising the following steps:
(1) The molar ratio is (0.02 to 0.16) Na 2 O:(0.3~0.4) Al 2 O 3 :5SiO 2 :80~90 H 2 O; uniformly mixing a proper amount of silicon source, aluminum source, sodium hydroxide and water to form colloid;
(2) Adding nano NaY seed crystal stock solution into the material obtained in the step (1), wherein the addition amount is 7-25% of the total feeding mass; then sodium hydroxide and water are added to make the final molar ratio of the materials in the system be (1.5 to 2.0) Na 2 O:(0.30~0.5)Al 2 O 3 :5SiO 2 :(140~200) H 2 O；
(3) Crystallizing, filtering, drying and roasting the material in the step (2) to obtain a NaY molecular sieve;
the colloid in the step (1) is stirred in a closed manner for 6 to 48 hours at the temperature of 20 to 80 ℃; and (3) adding the nano NaY seed crystal stock solution in the step (2), continuously stirring for 6 to 24 hours at the temperature of 20 to 80 ℃, and adding the required NaOH solution and water.
2. The molecular sieve of claim 1, characterized in that: the specific surface area of the NaY molecular sieve is 800 to 810 m 2 (ii)/g; the external specific surface area is 180 to 210 m 2 (ii)/g; the mesoporous volume is 0.30 to 0.35 cm 3 /g。
3. A method for synthesizing NaY molecular sieve according to claim 1 or 2, characterized in that: the method comprises the following steps:
(1) In metered molar ratios (0.02 to0.16) Na 2 O:(0.3~0.4) Al 2 O 3 :5 SiO 2 :80~90 H 2 O; uniformly mixing a proper amount of silicon source, aluminum source, sodium hydroxide and water to form colloid;
(2) Adding nano NaY seed crystal stock solution into the material obtained in the step (1), wherein the addition amount is 7-25% of the total feeding mass; then sodium hydroxide and water are added to make the final molar ratio of the materials in the system be (1.5 to 2.0) Na 2 O:(0.30~0.5)Al 2 O 3 :5SiO 2 :(140~200)H 2 O；
(3) Crystallizing, filtering, drying and roasting the material in the step (2) to obtain a NaY molecular sieve;
the colloid in the step (1) is stirred in a closed manner for 6 to 48 hours at the temperature of 20 to 80 ℃; and (3) adding the nano NaY seed crystal stock solution in the step (2), continuously stirring for 6 to 24 hours at the temperature of 20 to 80 ℃, and adding the required NaOH solution and water.
4. The method of claim 3, wherein: in the step (2), adding nano NaY seed crystal stock solution into the material obtained in the step (1), wherein the adding amount is 14-18% of the total feeding mass.
5. The method of claim 3, wherein: in the step (2), the final molar ratio of the materials in the system is (1.6 to 1.8) Na 2 O:(0.30~0.4)Al 2 O 3 :5SiO 2 :(140~200)H 2 O。
6. The method of claim 3, wherein: in the step (1), the silicon source is one or more of water glass, silica sol, silica gel and white carbon black; the aluminum source is one or more of aluminum nitrate, aluminum sulfate, sodium metaaluminate and metal aluminum.
7. The method of claim 3, wherein: in the step (1), all silicon sources and part of H 2 Stirring O fully, adding a proper amount of NaAlO 2 After fully stirring the aqueous solution, adding a proper amount of Al 2 (SO 4 ) 3 An aqueous solution of (a); is thrown inNaAlO 2 And Al 2 (SO 4 ) 3 The mass ratio of (A) is 0.5-1:1.
8. The method of claim 3, wherein: the nano NaY crystal seed stock solution in the step (2) is prepared by adopting the following method according to Na 2 O:Al 2 O 3 :SiO 2 :H 2 O = (10 to 15) = (10 to 18): 1 (200 to 400), mixing a silicon source, an aluminum source and water in an ice water bath at 0~5 ℃ to obtain a colorless transparent state, stirring at room temperature, and standing and crystallizing at 40 to 80 ℃ for 6 to 96 hours to obtain a semitransparent, pale and viscous nano NaY molecular sieve seed crystal stock solution.
9. The method of claim 8, wherein: according to Na 2 O:Al 2 O 3 :SiO 2 :H 2 O = (12~13) Na 2 O:Al 2 O 3 :(14~15) SiO 2 :(220~240) H 2 Molar ratio of O.
10. The method of claim 3, wherein: in the step (3), the crystallization temperature is 80-100 ℃, and the crystallization time is 12-96 h.
11. The method of claim 3, wherein: in the step (3), the drying temperature is 100 to 150 ℃, the drying time is 2 to 5 hours, the baking temperature is 450 to 550 ℃, and the baking time is 2 to 4 hours.
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