CN110422854B - Preparation method of pure silicon beta molecular sieve nanocrystal - Google Patents
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Abstract
The invention discloses a preparation method of pure silicon beta molecular sieve nanocrystal, which comprises the following steps: drying 4.21-15 g of solution with the mass fraction of tetraethylammonium hydroxide of 35% at the temperature of 40-90 ℃ for 30-720 min, and uniformly mixing with 0.8-5 g of white carbon black to obtain a mixture; under the steam-assisted condition, carrying out crystallization treatment on the mixture to obtain a crystallized product; and sequentially cooling, washing, drying and calcining the crystallized product to obtain the pure silicon beta molecular sieve nanocrystal with high crystallinity. The template agent and water used in the synthesis process provided by the method are small in dosage, so that the method also has the advantages of low cost, small environmental pollution, contribution to industrial production and the like.
Description
Technical Field
The invention belongs to the technical field of molecular sieve nanocrystals, and particularly relates to a preparation method of a pure silicon beta molecular sieve nanocrystal.
Background
The traditional zeolite has the advantages of uniform micropores, rich surface acid points, large specific surface area, good hydrothermal stability and the like, and is widely applied to the aspects of adsorption, heterogeneous catalysis, molecular separation and the like. However, since the pore diameter of zeolite is generally less than 0.7nm, when a catalyst for macromolecular reaction is involved, its diffusion limitation in the crystal is a very serious problem. The nanometer molecular sieve can be prepared, and the diffusion path length is shortened, so that the problem is solved. At present, the nano molecular sieve is widely applied to the traditional fields of adsorbents, heterogeneous catalysis, molecular separation and the like, and the application of the nano molecular sieve is also expanded to the emerging fields of microbial fuel cells, chemical sensing, cosmetics and foods, optical devices, biomedicine, drug delivery and the like.
The nanometer molecular sieve is generally prepared by a conventional hydrothermal crystallization synthesis method, and compared with the conventional micron zeolite, the preparation synthesis process is complex, F ions or crystal seeds need to be introduced, the water consumption is large, the product is difficult to filter and collect, the production cost is high, the wastewater treatment is difficult, and the large-scale production is difficult to form.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of pure silicon beta molecular sieve nanocrystal.
In order to realize the technical purpose, the invention is realized according to the following technical scheme:
a preparation method of pure silicon beta molecular sieve nanocrystal comprises the following steps:
drying 4.21-15 g of solution with the mass fraction of tetraethylammonium hydroxide of 35% at the temperature of 40-90 ℃ for 30-720 min, and uniformly mixing with 0.8-5 g of white carbon black to obtain a mixture;
under the steam-assisted condition, carrying out crystallization treatment on the mixture to obtain a crystallized product;
and sequentially cooling, washing, drying and calcining the crystallized product to obtain the pure silicon beta molecular sieve nanocrystal with high crystallinity.
Further, after the tetraethyl ammonium hydroxide solution and the white carbon black are mixed, stirring is carried out for 1-2 hours at a stirring speed of 450-550 r/min.
Further, the crystallization temperature of the crystallization treatment is 100-180 ℃, and the crystallization time is 3-24 hours.
Further, the crystallization treatment is carried out in a hydrothermal reaction kettle, and 1-10 ml of deionized water is put into a kettle liner of the hydrothermal reaction kettle.
Further, the mixture is placed into an open glass vessel, and then the glass vessel is placed into a kettle liner of the hydrothermal reaction kettle, and water in the kettle liner of the hydrothermal reaction kettle is prevented from entering the glass vessel.
Further, the washing treatment comprises: and carrying out centrifugal washing treatment on the liquid gel product, wherein the washing times are 1-3 times, and the centrifugal rotating speed is 8000-12000 r/min.
Furthermore, the calcining temperature of the calcining treatment is 500-600 ℃, and the calcining time is 6-24 hours.
Further, the grain size of the pure silicon beta molecular sieve nano-crystal is 30-90 nm.
The preparation method of the pure silicon beta molecular sieve nanocrystal provided by the invention has the advantages that the synthesis steps are simple, seed crystals are not required to be used, F ions are not required to be introduced, the pure silicon beta molecular sieve nanocrystal can be completely crystallized in a short time, the prepared pure silicon beta molecular sieve nanocrystal has good dispersibility and uniform particle size distribution, and meanwhile, the template agent and the water used in the synthesis process are small, so that the method also has the advantages of low cost, small environmental pollution, contribution to industrial production and the like.
Drawings
FIG. 1 is an XRD pattern of pure silicon beta molecular sieve nanocrystals prepared in exemplary embodiment 1 of the present invention;
FIG. 2 is an SEM photograph of pure silicon beta molecular sieve nanocrystals prepared in exemplary embodiment 1 of the present invention;
FIG. 3 is an XRD pattern of pure silicon beta molecular sieve nanocrystals prepared in exemplary embodiment 2 of the present invention;
FIG. 4 is an SEM photograph of pure silicon beta molecular sieve nanocrystals prepared in exemplary embodiment 2 of the present invention;
FIG. 5 is an XRD pattern of pure silicon beta molecular sieve nanocrystals prepared in exemplary embodiment 3 of the present invention;
FIG. 6 is an SEM photograph of pure silicon beta molecular sieve nanocrystals prepared in exemplary embodiment 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be described in more detail below with reference to the accompanying drawings in the preferred embodiments of the present invention. In the drawings, the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The described embodiments are only some, but not all embodiments of the invention. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
A preparation method of pure silicon beta molecular sieve nanocrystal comprises the following steps:
(1) drying 4.21-15 g of a solution with the mass fraction of tetraethylammonium hydroxide of 35% at the temperature of 40-90 ℃ for 30-720 min, then stirring with 0.8-5 g of white carbon black at the stirring speed of 450-550 r/min for 1-2 h, and uniformly mixing to obtain a mixture;
(2) transferring the mixture into an open glass vessel, then placing the glass vessel into a hydrothermal reaction kettle liner filled with 1-10 ml of deionized water in a kettle liner, and preventing water in the hydrothermal reaction kettle liner from entering the glass vessel; under the steam-assisted condition, adjusting the temperature of the hydrothermal reaction kettle to 100-180 ℃, and crystallizing for 3-24 hours to obtain a crystallized product;
(3) and naturally cooling the crystallized product to room temperature, washing the crystallized product for 1-3 times in a centrifuge with the centrifugal rotation speed of 8000-12000 r/min, drying, and calcining for 6-24 hours at the temperature of 500-600 ℃ in an air atmosphere to obtain the high-crystallinity pure silicon beta molecular sieve nanocrystal with the particle size of 30-90 nm.
The preparation method of the pure silicon beta molecular sieve nanocrystal provided by the invention has the advantages that the synthesis steps are simple, seed crystals are not required to be used, F ions are not required to be introduced, the complete crystallization can be prepared in a short time (the crystallization time is short, the crystallization can be carried out within the shortest 3 h), the prepared pure silicon beta molecular sieve nanocrystal has good dispersibility and uniform particle size distribution, and the particle size of the pure silicon beta molecular sieve nanocrystal is controlled by controlling parameters during crystallization treatment; meanwhile, different from the traditional xerogel conversion method, the reactant is kept with a small amount of water to enable the nanocrystal to be rapidly formed, on one hand, the loss of the template agent (tetraethylammonium hydroxide solution) caused by complete evaporation is prevented, on the other hand, the small amount of water is beneficial to improving the supersaturation degree and is beneficial to large-scale nucleation and crystal growth, therefore, the template agent and the water used in the synthetic process of the method are small in dosage, the cost of the method is further reduced, the pollution to the environment is also reduced, and the method is beneficial to industrial production.
Example 1
A preparation method of pure silicon beta molecular sieve nanocrystal comprises the following steps:
(1) drying 4.21g of solution with the mass fraction of tetraethylammonium hydroxide of 35% at the temperature of 70 ℃ for 30min, then stirring with 0.8g of white carbon black at the stirring speed of 500r/min for 1.5h, and uniformly mixing to obtain a mixture;
(2) transferring the mixture into an open glass vessel, then placing the glass vessel into a hydrothermal reaction kettle liner filled with 1ml of deionized water in the kettle liner, and preventing water in the hydrothermal reaction kettle liner from entering the glass vessel; under the steam-assisted condition, the temperature of the hydrothermal reaction kettle is adjusted to 160 ℃, and the crystallization time is 3 hours, so that a crystallization product is obtained;
(3) naturally cooling the crystallized product to room temperature, washing the crystallized product in a centrifuge with the centrifugal speed of 10000r/min for 3 times, drying, and finally calcining at 580 ℃ for 12 hours in air atmosphere to obtain the high-crystallinity pure silicon beta molecular sieve nanocrystal with the particle size of about 50 nanometers.
As can be seen from figure 1, a characteristic peak of beta appears to prove successful crystallization of beta, and as can be seen from figure 2, the morphology of beta is complete, the particle size distribution is uniform, and is basically about 50 nm.
Example 2
A preparation method of pure silicon beta molecular sieve nanocrystal comprises the following steps:
(1) drying 8g of a solution with the mass fraction of tetraethylammonium hydroxide of 35% at the temperature of 40 ℃ for 240min, then stirring the solution with 3.4g of white carbon black at the stirring speed of 450r/min for 1h, and uniformly mixing to obtain a mixture;
(2) transferring the mixture into an open glass vessel, then placing the glass vessel into a hydrothermal reaction kettle liner filled with 10ml of deionized water in the kettle liner, and preventing water in the hydrothermal reaction kettle liner from entering the glass vessel; under the steam-assisted condition, adjusting the temperature of the hydrothermal reaction kettle to 155 ℃, and crystallizing for 9 hours to obtain a crystallized product;
(3) naturally cooling the crystallized product to room temperature, washing the crystallized product for 1 time in a centrifuge with the centrifugal speed of 8000r/min, drying, and calcining for 6 hours at the temperature of 500 ℃ in the air atmosphere to obtain the high-crystallinity pure silicon beta molecular sieve nanocrystal with the particle size of about 50 nanometers.
As can be seen from figure 3, a characteristic peak of beta appears to prove successful crystallization of beta, and as can be seen from figure 4, the morphology of beta is complete, the particle size distribution is uniform, and is basically about 50 nm.
Example 3
A preparation method of pure silicon beta molecular sieve nanocrystal comprises the following steps:
(1) drying 15g of a solution with the mass fraction of tetraethylammonium hydroxide of 35% at the temperature of 90 ℃ for 720min, then stirring the solution with 5g of white carbon black at the stirring speed of 550r/min for 2h, and uniformly mixing to obtain a mixture;
(2) transferring the mixture into an open glass vessel, then placing the glass vessel into a hydrothermal reaction kettle liner filled with 5ml of deionized water in the kettle liner, and preventing water in the hydrothermal reaction kettle liner from entering the glass vessel; under the steam-assisted condition, the temperature of the hydrothermal reaction kettle is adjusted to 165 ℃, and the crystallization time is 24 hours, so as to obtain a crystallization product;
(3) and naturally cooling the crystallized product to room temperature, washing the crystallized product for 2 times in a centrifuge with the centrifugal rotation speed of 12000r/min, drying, and calcining for 6-24 hours at 600 ℃ in an air atmosphere to obtain the high-crystallinity pure silicon beta molecular sieve nanocrystal with the particle size of about 30 nanometers.
As can be seen from FIG. 5, a characteristic peak of beta appears to prove successful crystallization of beta, and as can be seen from FIG. 6, the morphology of beta is complete, the particle size distribution is uniform, and is basically about 30 nm.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. A preparation method of pure silicon beta molecular sieve nanocrystal is characterized by comprising the following steps:
drying 4.21-15 g of solution with the mass fraction of tetraethylammonium hydroxide of 35% at the temperature of 40-90 ℃ for 30-720 min, and uniformly mixing with 0.8-5 g of white carbon black to obtain a mixture;
under the steam-assisted condition, carrying out crystallization treatment on the mixture to obtain a crystallized product;
and sequentially cooling, washing, drying and calcining the crystallized product to obtain the pure silicon beta molecular sieve nanocrystal with high crystallinity.
2. The method for preparing pure silicon beta molecular sieve nanocrystal as claimed in claim 1, wherein the tetraethyl ammonium hydroxide solution is mixed with the white carbon black and then stirred at a stirring speed of 450-550 r/min for 1-2 h.
3. The method for preparing pure silicon beta molecular sieve nanocrystal as claimed in claim 1, wherein the crystallization temperature of the crystallization treatment is 100-180 ℃ and the crystallization time is 3-24 h.
4. The method for preparing pure silicon beta molecular sieve nanocrystal as claimed in claim 1, wherein the crystallization is performed in a hydrothermal reaction kettle, and 1-10 ml of deionized water is put into a kettle liner of the hydrothermal reaction kettle.
5. The method as claimed in claim 4, wherein the mixture is placed in an open glass vessel, and then the glass vessel is placed in the hydrothermal reaction kettle liner, and water in the hydrothermal reaction kettle liner is prevented from entering the glass vessel.
6. The method for preparing pure silicon beta molecular sieve nanocrystal as claimed in claim 1, wherein the washing treatment comprises: and carrying out centrifugal washing treatment on the liquid gel product, wherein the washing times are 1-3 times, and the centrifugal rotating speed is 8000-12000 r/min.
7. The method for preparing pure silicon beta molecular sieve nanocrystal as claimed in claim 1, wherein the calcination temperature of the calcination treatment is 500-600 ℃ and the calcination time is 6-24 hours.
8. The method for preparing pure silicon beta molecular sieve nanocrystal according to claim 1, wherein the particle size of the pure silicon beta molecular sieve nanocrystal is 30-90 nm.
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