CN112723374A - NaY molecular sieve and synthesis method thereof - Google Patents

NaY molecular sieve and synthesis method thereof Download PDF

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CN112723374A
CN112723374A CN201911030846.9A CN201911030846A CN112723374A CN 112723374 A CN112723374 A CN 112723374A CN 201911030846 A CN201911030846 A CN 201911030846A CN 112723374 A CN112723374 A CN 112723374A
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molecular sieve
nay
stirring
sio
surface area
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CN112723374B (en
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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 m2(ii)/g; the external specific surface area is 140-250 m2(ii)/g; the mesoporous volume is 0.15-0.45 cm3(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, relates to a NaY molecular sieve and a synthesis method thereof, and particularly relates 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 to shorten the diffusion path of the material and the 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 the synthesis methods of small crystal grains and nano NaY molecular sieves, and the synthesis does 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-RSC Adv.2013, 3: 15075-]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. Moreover, the obtained products are NaY molecular sieves with low Si/Al ratio, even X-type molecular sieves, which undoubtedly increases the difficulty of forming ultrastable Y molecular sieves with high Si/Al ratio by subsequent dealumination and product loss. 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 m2Preferably 750 to 820 m/g2(iv)/g, more preferably 800 to 810 m2(ii)/g; the external specific surface area is 140-250 m2Preferably 160 to 220 m/g2(iv)/g, more preferably 180 to 210 m2(ii)/g; the mesoporous volume is 0.15-0.45 cm3Preferably 0.25 to 0.40 cm/g3A concentration of 0.30 to 0.35 cm3/g。
A method for synthesizing a NaY molecular sieve comprises the following steps:
(1) in a metered molar ratio (0).00~1.0) Na2O ：(0.30~0.5) Al2O3 ：5 SiO2 ：80~90 H2O, preferably (0.02 to 0.16) Na2O ：(0.3~0.4) Al2O3 ：5 SiO2 ：80~90 H2O; 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% of the total feeding mass, preferably 7-25%, and further preferably 14-18%; then, complementing an alkali source and water to ensure that the final molar ratio of all materials in the system is (1.5-2.0) Na2O:(0.30~0.5)Al2O3:5SiO2: (140~200) H2O, preferably (1.6 to 1.8) Na2O : (0.30~0.4) Al2O3: 5SiO2: (140~200) H2O；
(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 H2Stirring O fully, adding a proper amount of NaAlO2After fully stirring the aqueous solution, adding a proper amount of Al2(SO4)3An aqueous solution of (a); charged NaAlO2And Al2(SO4)3In a mass ratio of 0.5-1: 1.
in the method, the colloid in the step (1) is 20-80%oC (temperature T1) is sealed and stirred for 6-48 h (time T1); adding nano NaY seed crystal stock solution in the step (2), and then adding the nano NaY seed crystal stock solution to the solution at a temperature of 20-80 DEG CoAnd C (temperature T2), continuously stirring for 6-24 h (time T2), and adding the required NaOH solution and water.
The method comprises the step (2) of preparing the nano NaY seed crystal stock solutionCan be prepared by any of the prior art, preferably by the following method, according to Na2O : Al2O3 : SiO2 : H2O = (10-15): 1 (10-18): 200-400 mol ratio, preferably (12-13) Na2O : Al2O3 : (14~15) SiO2 : (220~240) H2The molar ratio of O is that the silicon source, the aluminum source and the water are in the range of 0-5oC, mixing in ice-water bath to obtain a colorless transparent mixture, stirring at room temperature, and performing stirring at 40-80 DEG CoAnd C, standing and crystallizing for 6-96 h to obtain semi-transparent, light white and sticky nano NaY molecular sieve seed crystal stock solution.
In the method, the crystallization temperature in the step (2) is 80-100 DEG CoC, crystallizing for 12-96 hours; the drying temperature is 100-150 deg.C oCThe drying time is 2-5 h, and the roasting temperature is 450-550oAnd C, roasting for 2-4 h.
The method of the invention promotes the material to form low-concentration AlO by controlling a plurality of synthesis parameters influencing the formation of the NaY molecular sieve nano-sheet structure under the conditions of low alkalinity, high Si/Al feed ratio, high aging temperature and proper nano NaY crystal seed amount2]-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 ] is2]-Ions can be preferentially combined with the side surface of the NaY nanocrystal to form rich AlO2]-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 adhesive2]-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 sides2]-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 SiO2/Al2O3When the feed ratio is higher, in the solution[AlO2]-Too high ion concentration with enough AlO2]-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 gel2]-The matching problem of the ion concentration and the quantity proportion of the nano crystal seeds enables the synthesis of the nano 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 N2The adsorption curve is different from that of the conventional microporous NaY molecular sieve in p/p0At the position of = 0.2-1.0, the sample is in a single-edge rising trend, and the sample is shown to have rich outer surfaces and accord with the adsorption characteristics of a nanosheet structure. The desorption curve is p/p0And the position of = 0.2-0.95 is not coincident 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 microscope photo shows that the crystal has the crystal morphology of lamella bridging growth with the thickness of 50-100 nm. These nanoplatelets provide up to 209 m2The external surface area of the nano sheet is/g, and the cross-linked growth and accumulation of the nano sheet provide up to 0.36 cm3The total pore volume is increased to 0.72 cm3Is much higher than that of a conventional microporous NaY molecular sieve (about 0.45 cm)3In terms of/g). The cross-grown nano-sheet NaY molecular sieve not only greatly shortens the micropore channels of the molecular sieve, but also provides rich and smooth 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 claims with the heading "known to those skilled in the art", "prior art", or the like, deriving materials, substances, methods, steps, etc., the subject matter that is derived from the heading encompasses those conventionally used in the art as proposed in the present application, but also includes those that are not currently in use, but would become known in the art to be suitable for a similar purpose.
The X-ray diffraction patterns in the examples were measured by a Bruker D4 type powder diffractometer, CuK α Radiation source, tube pressure 40 kV, tube flow 40 mA.
The low-temperature nitrogen adsorption-desorption curve of the molecular sieve is measured on a Micromeritics Tristar 3020 type analyzer at 77K, and the specific surface area of a sample is calculated by a BET method.
The pore size distribution curve of the molecular sieve of this example was determined on a Micromeritics Tristar 3020 analyzer at 77K, 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 scanning electron microscopy of this example was carried out on a Philip XL30 model, operating at a voltage of 20 kV.
Example 1:
1. and (3) synthesis of nano NaY molecular sieve seed crystal:
200 g of NaOH is dissolved in 500 g of water, after cooling, metal aluminum wires with the total amount of 37.80 g are slowly added for a plurality of times, after complete dissolution, the water loss is complemented, and the mixture is cooled to room temperature for standby (solution A); 520 g NaOH was dissolved in 980 g water, 2000 g SiO 30%2The silica sol is properly heated and stirred, and after the solution becomes transparent and no particles are determined, the solution is cooled to 0 to 5 ℃ by using ice water bathoC, adding the solution (A) prepared before one time, stirring to obtain a colorless transparent solution, stirring at room temperature for 24h, and 60oAnd C, standing and crystallizing for 24 hours. Obtain light white semitransparent sticky emulsion. Final composition of the liquid crystal: 12.9 Na2O : Al2O3 : 14.3 SiO2 : 229 H2O。
2. Synthesis of a nano-sheet NaY molecular sieve:
20.0 g H was added beforehand to 42.48 g of silica sol (30%)2O, fully stirring to ensure that the silica sol is well dispersed; 2.208 g of filter cake 150 are added oCBaking for 4 hr of NaAlO2 (content: 0.5 g NaOH/g and 0.5 g Al2O3/g) dissolved in 25.00 g H2O solution, after stirring well, 2.70 g of Al was added2(SO4)3.18H2O dissolved in 23.78 g H2O solution, the formed feed ratio is as follows: 0.04 Na2O ：0.35 Al2O3 ：5 SiO2 ：80~90 H2White colloid a of O. The colloid is at a temperature of T1=50oC, stirring for T1=24 h in a closed manner, adding 13.93% (22.5 g) of nano NaY seed crystal stock solution in percentage by mass of the total crystallization material, and stirring at T2=50oAfter stirring for t2=24 h under C, 2.841 g of NaOH are added and dissolved in 20.00 g H2O solution, final material feed ratio of 1.6 Na2O : 0.35 Al2O3: 5 SiO2 : 140 H2O，50 oStirring for 4h under C, and then 90 oCCrystallizing for 46 h, filtering, washing and drying to obtain a sample Nanosheet-NaY-1, wherein the structural parameters such as specific surface area, pore volume and the like are listed in Table 1.
Example 2:
20.0 g H was added beforehand to 42.48 g of silica sol (30%)2O, fully stirring to ensure that the silica sol is well dispersed; 2.208 g of a catalyst was added thereto at 150 oCBaking the NaAlO for 4h2 (content: 0.5 g NaOH/g and 0.5 g Al2O3/g) dissolved in 25.00 g H2O solution, after stirring well, 2.70 g of Al was added2(SO4)3.18H2O dissolved in 23.78 g H2O solution, the formed feed ratio is as follows: 0.04 Na2O ：0.35 Al2O3 ：5 SiO2 ：80~90 H2White colloid a of O. The colloid is at T1=50oC, stirring for T1=24 h in a closed manner, adding nano NaY seed crystal stock solution with the mass fraction of 20.96% (38.6 g) of the total crystallization material, and stirring at T2=50oC, after stirring for t2=24 h, adding 1.080 g NaOH to dissolve in 20.00 g H2O solution, final material feed ratio of 1.6 Na2O : 0.35 Al2O3: 5 SiO2: 140 H2O，50 oStirring for 4h under C, and then 90 oCCrystallizing for 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 H was added beforehand to 42.48 g of silica sol (30%)2O, fully stirring to ensure that the silica sol is well dispersed; 2.208 g of a catalyst was added thereto at 150 oCBaking the NaAlO for 4h2 (content: 0.5 g NaOH/g and 0.5 g Al2O3/g) dissolved in 25.00 g H2O solution, after stirring well, 2.70 g of Al was added2(SO4)3.18H2O dissolved in 23.78 g H2O solution, the formed feed ratio is as follows: 0.04 Na2O ：0.35 Al2O3 ：5 SiO2 ：80~90 H2Of OWhite colloid a. The colloid is at T1=50oC, stirring for T1=24 h in a closed manner, adding a nano NaY seed crystal stock solution with the mass fraction of 24.49% (48.5 g) of the total crystallization material, and stirring at T2=50oAfter stirring for t2=24 h under C, adding 20.00 g H2O, the final material feed ratio is 1.6 Na2O : 0.35 Al2O3: 5 SiO2: 140 H2O，50 oStirring for 4h under C, and then 90 oCCrystallizing for 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 H was added beforehand to 42.48 g of silica sol (30%)2O, fully stirring to ensure that the silica sol is well dispersed; 2.666 g of a lubricant are added at 150 oCBaking the NaAlO for 4h2 (content: 0.5 g NaOH/g and 0.5 g Al2O3/g) dissolved in 25.00 g H2O solution, after stirring well, 3.973 g of Al was added2(SO4)3.18H2O dissolved in 23.78 g H2O solution, the formed feed ratio is as follows: 0.08 Na2O ：0.4 Al2O3 ：5 SiO2 ：80~90 H2White colloid a of O. The colloid is at T1=50oC, stirring for T1=24 h in a closed manner, adding 13.93% (22.5 g) of nano NaY seed crystal stock solution in percentage by mass of the total crystallization material, and stirring at T2=50oAfter stirring for t2=24 h under C, 2.922 g of NaOH are added and dissolved in 20.00 g H2O solution, final material feed ratio is 1.65 Na2O : 0.4 Al2O3: 5 SiO2 : 140 H2O，50 oStirring for 4h under C, and then 90 oCCrystallizing for 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 H was added beforehand to 42.48 g of silica sol (30%)2O, fully stirring to ensure that the silica sol is well dispersed; 2.208 g of a catalyst was added thereto at 150 oCBaking the NaAlO for 4h2 (content: 0.5 g NaOH/g and 0.5 g Al2O3/g) dissolved in 25.00 g H2Of OThe solution was thoroughly stirred, and then 2.70 g of Al was added2(SO4)3.18H2O dissolved in 23.78 g H2O solution, the formed feed ratio is as follows: 0.04 Na2O ：0.35 Al2O3 ：5 SiO2 ：80~90 H2White colloid a of O. The colloid is at T1=50oC, stirring for T1=24 h in a closed manner, adding 13.93% (22.5 g) of nano NaY seed crystal stock solution in percentage by mass of the total crystallization material, and stirring at T2= 20oAfter stirring for t2=24 h under C, 2.841 g of NaOH are added and dissolved in 20.00 g H2O solution, final material feed ratio of 1.6 Na2O : 0.35 Al2O3: 5 SiO2 : 140 H2O，20 oStirring for 4h under C, and then 90 oCCrystallizing for 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 H was added beforehand to 42.48 g of silica sol (30%)2O, fully stirring to ensure that the silica sol is well dispersed; 2.208 g of a catalyst was added thereto at 150 oCBaking the NaAlO for 4h2 (content: 0.5 g NaOH/g and 0.5 g Al2O3/g) dissolved in 25.00 g H2O solution, after stirring well, 2.70 g of Al was added2(SO4)3.18H2O dissolved in 23.78 g H2O solution, the formed feed ratio is as follows: 0.04 Na2O ：0.35 Al2O3 ：5 SiO2 ：80~90 H2White colloid a of O. The colloid is at T1=50oC, stirring for T1=24 h in a closed manner, adding 13.93% (22.5 g) of nano NaY seed crystal stock solution in percentage by mass of the total crystallization material, and stirring at T2=50oAfter stirring for t2=12 h under C, 2.841 g of NaOH are added and dissolved in 20.00 g H2O solution, final material feed ratio of 1.6 Na2O : 0.35 Al2O3: 5 SiO2 : 140 H2O，50 oStirring for 4h under C, and then 90 oCCrystallizing for 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 H was added beforehand to 42.48 g of silica sol (30%)2O, fully stirring to ensure that the silica sol is well dispersed; 2.208 g of a catalyst was added thereto at 150 oCBaking the NaAlO for 4h2 (content: 0.5 g NaOH/g and 0.5 g Al2O3/g) dissolved in 25.00 g H2O solution, after stirring well, 2.70 g of Al was added2(SO4)3.18H2O dissolved in 23.78 g H2O solution, the formed feed ratio is as follows: 0.04 Na2O ：0.35 Al2O3 ：5 SiO2 ：80~90 H2White colloid a of O. The colloid is at T1=50oC, sealing and stirring for T1=48 h, adding 13.93% (22.5 g) of nano NaY seed crystal stock solution in percentage by mass of the total crystallization material, and stirring at T2=50oAfter stirring for t2=12 h under C, 2.841 g of NaOH are added and dissolved in 20.00 g H2O solution, final material feed ratio of 1.6 Na2O : 0.35 Al2O3: 5 SiO2 : 140 H2O，50 oStirring for 4h under C, and then 90 oCCrystallizing for 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 H was added beforehand to 42.48 g of silica sol (30%)2O, fully stirring to ensure that the silica sol is well dispersed; 2.285 g of a lubricant are added at 150 oCBaking the NaAlO for 4h2 (content: 0.5 g NaOH/g and 0.5 g Al2O3/g) dissolved in 25.00 g H2O solution, after stirring well, 2.444 g of Al was added2(SO4)3.18H2O dissolved in 23.78 g H2O solution, the formed feed ratio is as follows: 0.04 Na2O ：0.35 Al2O3 ：5 SiO2 ：80~90 H2White colloid a of O. The colloid is at T1=50oC, sealing and stirring for T1=24 h, adding nano NaY seed crystal stock solution with 3.47% (4.737 g) of total crystallization material mass fraction, and stirring at T2=50oAfter stirring for t2=12 h under C, 4.656 g of NaOH are added and dissolved in 20.00 g H2O solution, final material feed ratio of 1.6Na2O : 0.35 Al2O3: 5 SiO2 : 140 H2O，50 oStirring for 24h under C, and then 90 oCCrystallizing for 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 H was added beforehand to 42.48 g of silica sol (30%)2O, fully stirring to ensure that the silica sol is well dispersed; 2.364 g of 150 g of oCBaking the NaAlO for 4h2 (content: 0.5 g NaOH/g and 0.5 g Al2O3/g) dissolved in 25.00 g H2O solution, after stirring well, 2.190 g of Al was added2(SO4)3.18H2O dissolved in 23.78 g H2O solution, the formed feed ratio is as follows: 0.12 Na2O ：0.35 Al2O3 ：5 SiO2 ：80~90 H2White colloid a of O. The colloid is at T1=50oC, stirring for T1=24 h in a closed manner, adding 13.93% (22.5 g) of nano NaY seed crystal stock solution in percentage by mass of the total crystallization material, and stirring at T2=50oAfter stirring for t2=12 h under C, 2.579 g of NaOH are added and dissolved in 20.00 g H2O solution, final material feed ratio of 1.6 Na2O : 0.35 Al2O3: 5 SiO2 : 140 H2O，50 oStirring for 24h under C, and then 90 oCCrystallizing for 46 h, filtering, washing and drying to obtain a control group sample Ref-NaY-2, wherein the structural parameters such as specific surface area, pore volume and the like are listed in Table 1.
Example 10 (control 3):
20.0 g H was added beforehand to 42.48 g of silica sol (30%)2O, fully stirring to ensure that the silica sol is well dispersed; 2.208 g of a catalyst was added thereto at 150 oCBaking the NaAlO for 4h2 (content: 0.5 g NaOH/g and 0.5 g Al2O3/g) dissolved in 25.00 g H2O solution, after stirring well, 2.70 g of Al was added2(SO4)3.18H2O dissolved in 23.78 g H2O solution, the formed feed ratio is as follows: 0.04 Na2O ：0.35 Al2O3 ：5 SiO2 ：80~90 H2White colloid a of O. The colloid is at T1= 30oC, stirring for T1=24 h in a closed manner, adding 13.93% (22.5 g) of nano NaY seed crystal stock solution in percentage by mass of the total crystallization material, and stirring at T2= 30oAfter stirring for t2=24 h under C, 2.841 g of NaOH is added and dissolved in 20.00 g H2O solution, final material feed ratio of 1.6 Na2O : 0.35 Al2O3: 5 SiO2 : 140 H2O，30 oAfter stirring for 4h at C, at 90 oCCrystallizing for 46 h, filtering, washing and drying to obtain a control group sample Ref-NaY-3, wherein the structural parameters such as specific surface area, pore volume and the like are listed in Table 1.
Example 11 (control 4):
20.0 g H was added beforehand to 42.48 g of silica sol (30%)2O, fully stirring to ensure that the silica sol is well dispersed; 2.208 g of a catalyst was added thereto at 150 oCBaking the NaAlO for 4h2 (content: 0.5 g NaOH/g and 0.5 g Al2O3/g) dissolved in 25.00 g H2O solution, after stirring well, 2.70 g of Al was added2(SO4)3.18H2O dissolved in 23.78 g H2O solution, the formed feed ratio is as follows: 0.04 Na2O ：0.35 Al2O3 ：5 SiO2 ：80~90 H2White colloid a of O. The colloid is at T1=20oC, stirring for T1=24 h in a closed manner, adding 13.93% (22.5 g) of nano NaY seed crystal stock solution in percentage by mass of the total crystallization material, and stirring at T2=50oAfter stirring for t2=24 h under C, 2.841 g of NaOH are added and dissolved in 20.00 g H2O solution, final material feed ratio of 1.6 Na2O : 0.35 Al2O3: 5 SiO2 : 140 H2O，50 oStirring for 4h under C, and then 90 oCCrystallizing for 46 h, filtering, washing and drying to obtain a control group sample Ref-NaY-4, wherein the structural parameters such as specific surface area, pore volume and the like are listed in Table 1.
Example 12 (control 5):
20.0 g H was added beforehand to 42.48 g of silica sol (30%)2O, fully stirring to ensure that the silica sol is well dispersed; 2.208 g of a catalyst was added thereto at 150 oCN after baking for 4haAlO2 (content: 0.5 g NaOH/g and 0.5 g Al2O3/g) dissolved in 25.00 g H2O solution, after stirring well, 2.70 g of Al was added2(SO4)3.18H2O dissolved in 23.78 g H2O solution, the formed feed ratio is as follows: 0.04 Na2O ：0.35 Al2O3 ：5 SiO2 ：80~90 H2White colloid a of O. The colloid is at T1=50oC, sealing and stirring for T1=6 h, adding 13.93% (22.5 g) of nano NaY seed crystal stock solution in the total crystallization material mass fraction, and stirring at T2=50oAfter stirring for t2=12 h under C, 2.841 g of NaOH are added and dissolved in 20.00 g H2O solution, final material feed ratio of 1.6 Na2O : 0.35 Al2O3: 5 SiO2 : 140 H2O，50 oStirring for 4h under C, and then 90 oCCrystallizing for 46 h, 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% seed amount has only 84.5 m in the complete case of crystallization2Specific surface area of mesopores/g and 0.12 cm3Per 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 m2G and 0.19 cm3(ii)/g; 30 at T1, T2oThe specific surface area of the mesopores of a sample Ref-NaY-3 synthesized under C is only 93.5 m2Per g, the mesoporous volume is only 0.12 cm3(ii)/g; at T1=20oStirring for 24h under C and T1=50oCRef-NaY-4 and Ref-NaY-5 samples synthesized by stirring for 6 hours have small mesoporous specific surface area and mesoporous volume. In contrast, the white initial gum had a Na/Si ratio of 0.016, T1, T2 of 50oStirring under C24After h, when the seed crystal amount is increased to 20-35%, the mesoporous specific surface area of the Nanosheet-NaY-1, Nanosheet-NaY-2 and Nanosheet-NaY-3 samples is rapidly increased to>180 m2The mesoporous volume is increased to 0.30 cm3The samples per gram, in particular Nanosheet-NaY-1, have the highest mesopore specific surface area and mesopore volume; at a temperature of 50 ℃ at T1oC, even if T2 is reduced to 20 oCOr put T2=50 oCThe stirring time is shortened to 12 h, and under the condition that other synthesis conditions are similar to that of Nanosheet-NaY-1, the obtained Nanosheet-NaY-5 and Nanosheet-NaY-6 samples can still maintain high mesoporous specific surface area and mesoporous volume. These results show that the Na of the white initial gum2O/SiO2The ratio, the stirring temperature (T2), the stirring time (T1) and the amount of the nano-crystal are key parameters influencing the formation of the nano-sheet NaY molecular sieve, and the flaky bridging growth and the complete crystallization with the thickness of 50-100 nm, the width of 500nm and the width/thickness ratio of 5-10 can be obtained under the optimal condition, and the thickness of the flaky bridging growth and the complete crystallization can reach 209 m20.36 cm per gram of external surface area3The volume of each mesoporous is 0.72 cm3A nanosheet NaY molecular sieve (example Sheet-NaY-1) per gram.

Claims (11)

1. A NaY molecular sieve characterized by: the NaY molecular sieve has a nanosheet shape; the specific surface area of the NaY molecular sieve is 700-850 m2(ii)/g; the external specific surface area is 140-250 m2(ii)/g; the mesoporous volume is 0.15-0.45 cm3/g。
2. The molecular sieve of claim 1, characterized in that: the specific surface area of the NaY molecular sieve is 750-820 m2(ii)/g; the external specific surface area is 160-220 m2(ii)/g; the mesoporous volume is 0.25-0.40 cm3/g。
3. The molecular sieve of claim 1 or 2, characterized in that: the specific surface area of the NaY molecular sieve is 800-810 m2(ii)/g; the external specific surface area is 180-210 m2(ii)/g; the mesoporous volume is 0.30-0.35 cm3/g。
4. A method for synthesizing NaY molecular sieve is characterized in that: the method comprises the following steps:
(1) in a metered molar ratio (0.00-1.0) Na2O ：(0.30~0.5) Al2O3 ：5 SiO2 ：80~90 H2O, preferably (0.02 to 0.16) Na2O ：(0.3~0.4) Al2O3 ：5 SiO2 ：80~90 H2O; 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% of the total feeding mass, preferably 7-25%, and further preferably 14-18%; then, complementing an alkali source and water to ensure that the final molar ratio of all materials in the system is (1.5-2.0) Na2O:(0.30~0.5)Al2O3:5SiO2: (140~200) H2O, preferably (1.6 to 1.8) Na2O : (0.30~0.4) Al2O3: 5SiO2: (140~200) H2O；
(3) And (3) crystallizing, filtering, drying and roasting the material in the step (2) to obtain the NaY molecular sieve.
5. The method of claim 4, 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; the alkali source is one or more of sodium hydroxide, potassium hydroxide or ammonia water.
6. The method of claim 4, wherein: in the step (1), all silicon sources and part of H2Stirring O fully, adding a proper amount of NaAlO2After fully stirring the aqueous solution, adding a proper amount of Al2(SO4)3An aqueous solution of (a); charged NaAlO2And Al2(SO4)3In a mass ratio of 0.5-1: 1.
7. the method of claim 4, wherein the method is performed in a batch processCharacterized in that: in the step (1), the colloid is 20-80%oC, stirring for 6-48 hours in a closed manner; adding nano NaY seed crystal stock solution in the step (2), and then adding the nano NaY seed crystal stock solution to the solution at a temperature of 20-80 DEG CoAnd C, continuously stirring for 6-24 hours, and supplementing the required NaOH solution and water.
8. The method of claim 4, wherein: the nano NaY crystal seed stock solution in the step (2) is prepared by adopting the following method according to Na2O : Al2O3 : SiO2 : H2O = (10-15): 1 (10-18): 200-400 mol ratio, preferably (12-13) Na2O : Al2O3 : (14~15) SiO2 : (220~240) H2The molar ratio of O is that the silicon source, the aluminum source and the water are in the range of 0-5oC, mixing in ice-water bath to obtain a colorless transparent mixture, stirring at room temperature, and performing stirring at 40-80 DEG CoAnd C, standing and crystallizing for 6-96 h to obtain semi-transparent, light white and sticky nano NaY molecular sieve seed crystal stock solution.
9. The method of claim 8, wherein: according to Na2O : Al2O3 : SiO2 : H2O = (12~13) Na2O : Al2O3 : (14~15) SiO2 : (220~240) H2Molar ratio of O.
10. The method of claim 4, wherein: in the step (2), the crystallization temperature is 80-100 DEG CoAnd C, crystallizing for 12-96 hours.
11. The method of claim 4, wherein: in the step (2), the drying temperature is 100-150 DEG C oCThe drying time is 2-5 h, and the roasting temperature is 450-550oAnd C, roasting for 2-4 h.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113893817A (en) * 2021-09-26 2022-01-07 武汉工程大学 NaY type molecular sieve, preparation method thereof and application thereof in carbonyl sulfide adsorption

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102333728A (en) * 2009-01-19 2012-01-25 里福技术股份有限公司 In low Si/Al zeolite, introduce mesoporous
CN105523567A (en) * 2016-01-19 2016-04-27 菏泽学院 Method for preparing size-controllable NaY molecular sieve
CN105621445A (en) * 2014-11-03 2016-06-01 中国石油化工股份有限公司 NaY type molecular sieves and preparation method therefor
CN109967117A (en) * 2017-12-28 2019-07-05 中国石油化工股份有限公司 A kind of preparation method of Modified Zeolite Y

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102333728A (en) * 2009-01-19 2012-01-25 里福技术股份有限公司 In low Si/Al zeolite, introduce mesoporous
CN105621445A (en) * 2014-11-03 2016-06-01 中国石油化工股份有限公司 NaY type molecular sieves and preparation method therefor
CN105523567A (en) * 2016-01-19 2016-04-27 菏泽学院 Method for preparing size-controllable NaY molecular sieve
CN109967117A (en) * 2017-12-28 2019-07-05 中国石油化工股份有限公司 A kind of preparation method of Modified Zeolite Y

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113893817A (en) * 2021-09-26 2022-01-07 武汉工程大学 NaY type molecular sieve, preparation method thereof and application thereof in carbonyl sulfide adsorption
CN113893817B (en) * 2021-09-26 2024-03-26 武汉工程大学 NaY type molecular sieve, preparation method thereof and application thereof in adsorption of carbonyl sulfide

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