CN113149029B - Preparation method of B @ HS hollow sphere molecular sieve - Google Patents
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Abstract
The invention relates to a preparation method of a B @ HS hollow sphere molecular sieve, which comprises TEOS, TPAOH, acetone and H 3 BO 3 Mixing with deionized water to obtain solution, and crystallizingCrystallizing in a crystallization kettle; carrying out suction filtration, washing and drying on the crystallized slurry, and then extracting by using an organic solvent to remove the template agent to obtain a spherical B-Silicalite molecular sieve; TPAOH and deionized water are mixed to prepare a solution, the prepared solution is dropwise added into a spherical B-Silicalite molecular sieve under the condition of reduced pressure suction filtration, the spherical B-Silicalite molecular sieve is subjected to suction filtration and wetting, transferred into a crystallization kettle for crystallization, filtered, washed, dried and extracted by an organic solvent to remove a template agent, and the B @ HS hollow sphere molecular sieve is obtained. The advantages are that: the synthesis steps are simple, the operation process is easy to control, and the shell of the hollow sphere molecular sieve can keep a ZSM-5 microporous structure.
Description
Technical Field
The invention relates to the technical field of molecular sieve preparation, in particular to a preparation method of a microporous hollow sphere molecular sieve containing framework boron.
Background
Since 2002, the synthesis of hollow spheres has attracted more and more attention in the field of material science. The hollow ball has a large cavity inside, and the micropores or mesopores on the surface of the ball shell can provide channels for the substances to enter and exit the cavity inside. Because the hollow sphere has the unique structure, the hollow sphere shows very special performances in catalysis, electromagnetism, adsorption, optics and the like. Hollow spheres have traditionally been synthesized by Using an organic templating agent method [ Lynch D E, Nawaz Y, Bostrom T, et al.preparation of Sub-micrometer silicon Shells Using Poly (1-methylpyrrol-2-ylsquaraine). ], and finally creating cavities by dissolving the cores of the templating agent by calcination or chemical means. People also synthesize hollow spheres with different sizes and topological structures by different methods, for example, hard inorganic spheres such as silicon spheres and the like or organic spheres such as polymer spheres and the like are used as templates to synthesize hollow spheres; the hollow sphere is synthesized by using a double template consisting of emulsion drops, surfactant micelles, polymerized macromolecules, aerosol bubbles and other soft templates and a surfactant. Venkatathri et al [ Venkatathri N, A novel route to synthesis of Aluminum silicate hollow ZSM-5 structure in the absence of template. Mater. Lett.,2008.62:462-465 ] also synthesized hollow silica-alumina spheres of nanometer size by a template-free method. The technology for synthesizing the hollow sphere comprises a dry spraying method, a gas phase transfer method, an ultrasonic cavitation method and the like. Further, a layer-by-layer (LbL) self-assembly method in which polyelectrolytes having opposite charges are electrostatically charged is also applied to the synthesis of hollow spheres. The B-Silicalite material is synthesized by replacing partial Si atoms with B atoms into a molecular sieve framework, and is considered to be capable of improving the acidity of the material and further improving the catalytic activity of the material.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the preparation method of the B @ HS hollow sphere molecular sieve, which has simple synthesis steps and easily controlled operation process, wherein the B @ HS hollow sphere molecular sieve with a uniform and compact shell is synthesized by a dry glue conversion method DGC, so that the shell of the hollow sphere molecular sieve is kept and has a ZSM-5 microporous structure, and B atoms easily enter a framework of the hollow sphere molecular sieve.
In order to realize the purpose, the invention is realized by the following technical scheme:
a preparation method of a B @ HS hollow sphere molecular sieve comprises the following steps:
1) TEOS, TPAOH, acetone, H 3 BO 3 Mixing deionized water according to the molar ratio of (0.5-2.0), (0.1-0.5), (0.1-3), (0.1-0.4) and (1-5) to prepare a solution, wherein the pH value of the solution is 8-10;
2) transferring the solution into a crystallization kettle, and crystallizing for 1-2 days at 160-180 ℃;
3) carrying out suction filtration, washing and drying on the crystallized slurry, and then extracting by using an organic solvent to remove the template agent to obtain a spherical B-Silicalite molecular sieve;
4) mixing TPAOH and deionized water according to a molar ratio of (0.1-0.5) to (1-5) to prepare a solution, wherein the pH value of the solution is 8-10, then dropwise adding the prepared solution into the spherical B-Silicalite molecular sieve dry glue obtained in the step 3) under the condition of reduced pressure suction filtration, carrying out suction filtration and wetting, transferring to a crystallization kettle for crystallization, and crystallizing at 160-180 ℃ for 1-2 days;
5) And filtering and washing the crystallized slurry, drying, and extracting by using an organic solvent to remove the template agent to obtain the B @ HS hollow sphere molecular sieve.
In the step 3), the washing is carried out under the condition of reduced pressure suction filtration until the pH value of the washing liquid is 6.5-7.5.
In the step 3), the drying is carried out for 6-12 h at the temperature of 60-80 ℃.
In the step 3), the organic solvent comprises at least one of ethanol, acetone and propionaldehyde; the specific process for removing the template agent comprises the following steps: the preparation method comprises the steps of forming a mixed solution by using an organic solvent and water, refluxing a precursor of the B-Silicalite under normal pressure, filtering, washing and drying obtained white solid after 2 hours, and finally roasting at 200 ℃ for more than 4 hours.
The organic solvent and water form a mixed solution: the volume ratio of the organic solvent to the water is (5:1) - (10: 1).
And 5) washing under the condition of reduced pressure suction filtration until the pH value of the washing liquid reaches 7.0 +/-0.5.
The properties of the spherical B-Silicalite molecular sieve obtained in the step 5) are as follows: the particle diameter is 500-800 nm, and the specific surface area is 150m 2 /g～350m 2 The total pore volume is 0.1mL/g to 0.3mL/g, the average pore diameter is 0.45 nm to 0.60nm, and the relative crystallinity is 90 percent to 100 percent.
Compared with the prior art, the invention has the beneficial effects that:
The method has simple synthesis steps and easy control of the operation process, can ensure that the shell of the hollow sphere molecular sieve keeps a ZSM-5 microporous structure, and compared with the traditional boron-loaded catalyst, the B @ HS synthesized by the method has the advantages that B atoms easily enter the framework of the hollow sphere molecular sieve to form four-coordination framework boron which is not easy to lose in the chemical reaction process. Compared with the Silicalite-1 molecular sieve of pure silicon, the molecular sieve improves the acidity of the material; compared with ZSM-5 molecular sieve, it is weaker in acidity, and is especially suitable for catalytic reaction catalyst using weak acid center as active center.
The method for preparing the hollow sphere comprises the following two steps: firstly, synthesizing a microporous solid sphere B-Silicalite. Next, the B-Silicalite was converted to B @ HS hollow spheres by the DGC method by directly introducing tetrapropylammonium hydroxide template, which is typically the template used to synthesize the zeolite molecular sieve with MFI topology.
Drawings
Fig. 1 is an X-ray diffraction pattern (XRD pattern) of a sample of the hollow sphere molecular sieve synthesized in example 1.
FIG. 2 is a transmission electron micrograph (TEM image) of a sample of the molecular sieve synthesized in example 1.
FIG. 3 is the B NMR spectra of the solid sphere molecular sieve samples synthesized in examples 1, 2 and 3 (B) 11 NMR chart).
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings, but it should be noted that the present invention is not limited to the following embodiments.
Example 1
The preparation method of the B @ HS hollow sphere molecular sieve comprises the following steps:
12g of acetone and 0.15g of boric acid are weighed and dissolved in 30g of deionized water, after complete dissolution, 0.62ml of tetrapropylammonium hydroxide TPAOH and 2.6g of tetraethoxysilane TEOS are added into the solution, and the solution is continuously stirred for more than 2 hours at 85 ℃. Transferring the mixed solution into a crystallization kettle, and crystallizing at 170 ℃ for 48 hours. Cooling the crystallized slurry to room temperature, and washing the obtained powder under the condition of reduced pressure suction filtration until the pH value of the washing liquid is close to neutrality; drying at 70 deg.C for 10 h; and then refluxing the precursor of the B-Silicalite under normal pressure by using a mixed solution of ethanol and water, wherein the volume ratio of the ethanol to the water is 5.5:1, so as to obtain the spherical B-Silicalite molecular sieve.
Dissolving 56mL of TPAOH in 100mL of deionized water to obtain a solution, wherein the pH value of the solution is about 9, weighing 100 g of spherical B-Silicalite molecular sieve, transferring the spherical B-Silicalite molecular sieve into a Buchner funnel with filter paper, and dropwise adding the prepared solution into the raw material on the filter paper in a reduced pressure suction filtration state. After being filtered and moistened, the mixture is transferred to a crystallization kettle and crystallized for 48 hours at the temperature of 170 ℃. Cooling the crystallized slurry to room temperature, and performing vacuum filtration on the obtained powder until the pH value of the washing liquid is close to neutral; the drying is carried out for 10 hours at the temperature of 70 ℃; then, a mixed solution of ethanol and water is added, the volume ratio of the ethanol to the water is 5.5:1, the precursor of the B-Silicalite is refluxed under normal pressure, the obtained molecular sieve is labeled as B @ HS-1, and the properties are shown in Table 1. In this example, the molecular sieve is labeled B @ HS-1, and the X-ray diffraction pattern (XRD pattern) of the molecular sieve sample is shown in FIG. 1, and the transmission electron microscopy pattern (TEM pattern) is shown in FIG. 2.
Example 2
The preparation method of the B @ HS hollow sphere molecular sieve comprises the following steps:
12g of acetone and 0.15g of boric acid are weighed out and dissolved in 30g of deionized water, after complete dissolution, 0.62ml of TPAOH and 2.6g of TEOS are added to the solution and stirring is continued at 25 ℃ for about 2 h. Transferring the mixed solution into a crystallization kettle, and crystallizing at 170 ℃ for 48 hours. Cooling the crystallized slurry to room temperature, and washing the obtained powder under the condition of reduced pressure suction filtration until the pH value of the washing liquid is close to neutrality; drying for 10 hours at 70 ℃, and then refluxing the precursor of the B-Silicalite by using a mixed solution of ethanol and water (the volume ratio of the ethanol to the water is 7:1) at normal pressure to obtain the spherical B-Silicalite molecular sieve.
Dissolving 30mL of TPAOH in 40mL of deionized water to obtain a solution, wherein the pH value of the solution is about 9, weighing 50 g of spherical B-Silicalite molecular sieve, transferring the spherical B-Silicalite molecular sieve into a Buchner funnel with filter paper, and dropwise adding the prepared solution into the raw material on the filter paper in a reduced pressure suction filtration state. After being filtered and moistened, the mixture is transferred to a crystallization kettle and crystallized for 48 hours at the temperature of 170 ℃. Cooling the crystallized slurry to room temperature, and performing vacuum filtration on the obtained powder until the pH value of the washing liquid is close to neutral; the drying is carried out for 10 hours at the temperature of 70 ℃; then, the precursor of the B-Silicalite is refluxed under normal pressure by using a mixed solution (volume ratio is 7:1) composed of ethanol and water, the obtained molecular sieve is marked as B @ HS-2, and the properties are shown in Table 1.
Example 3
The preparation method of the B @ HS hollow sphere molecular sieve comprises the following steps:
12g of acetone and 0.15g of boric acid are weighed out and dissolved in 30g of deionized water, after complete dissolution, 0.62ml of TPAOH and 2.6g of TEOS are added to the solution and stirring is continued at 110 ℃ for about 2 h. Transferring the mixed solution into a crystallization kettle, and crystallizing at 170 ℃ for 48 hours. Cooling the crystallized slurry to room temperature, and washing the obtained powder under the condition of reduced pressure suction filtration until the pH value of the washing liquid is close to neutrality; drying at 70 deg.C for 10 h; and then refluxing the precursor of the B-Silicalite by using a mixed solution (volume ratio is 9:1) composed of ethanol and water under normal pressure to obtain the spherical B-Silicalite molecular sieve.
Dissolving 84mL of TPAOH in 150mL of deionized water to obtain a solution, wherein the pH value of the solution is about 9, then weighing 120 g of spherical B-Silicalite molecular sieve, transferring the spherical B-Silicalite molecular sieve into a Buchner funnel with filter paper, and dropwise adding the prepared solution into the raw material on the filter paper under the condition of reduced pressure and suction filtration. After being filtered and moistened, the mixture is transferred to a crystallization kettle and crystallized for 48 hours at the temperature of 170 ℃. Cooling the crystallized slurry to room temperature, and performing vacuum filtration on the obtained powder until the pH value of the washing liquid is close to neutral; the drying is carried out for 10 hours at the temperature of 70 ℃; then, the precursor of the B-Silicalite is refluxed under normal pressure by using a mixed solution (volume ratio is 7:1) composed of ethanol and water, and the obtained molecular sieve is labeled as B @ HS-3, and the properties are shown in Table 1.
B NMR spectra of solid sphere molecular sieve samples synthesized in example 1, example 2 and example 3 (B) 11 NMR chart) is shown in fig. 3.
TABLE 1 Properties of the hollow sphere molecular sieves obtained in the examples
Claims (7)
1. A preparation method of a B @ HS hollow sphere molecular sieve is characterized by comprising the following steps:
1) TEOS, TPAOH, acetone, H 3 BO 3 Mixing deionized water according to the molar ratio of (0.5-2.0), (0.1-0.5), (0.1-3), (0.1-0.4) and (1-5) to prepare a solution, wherein the pH value of the solution is 8-10;
2) transferring the solution into a crystallization kettle, and crystallizing for 1-2 days at 160-180 ℃;
3) after suction filtration, washing and drying of the crystallized slurry, extracting by using an organic solvent to remove a template agent to obtain a spherical B-Silicalite molecular sieve;
4) mixing TPAOH and deionized water according to a molar ratio of (0.1-0.5) to (1-5) to prepare a solution, wherein the pH value of the solution is 8-10, then dropwise adding the prepared solution into the spherical B-Silicalite molecular sieve dry glue obtained in the step 3) under the condition of reduced pressure suction filtration, carrying out suction filtration and wetting, transferring to a crystallization kettle for crystallization, and crystallizing at 160-180 ℃ for 1-2 days;
5) and filtering and washing the crystallized slurry, drying, and extracting by using an organic solvent to remove the template agent to obtain the B @ HS hollow sphere molecular sieve.
2. The preparation method of the B @ HS hollow sphere molecular sieve of claim 1, wherein in the step 3), the washing is performed under a reduced pressure suction filtration condition until the pH value of a washing solution is 6.5-7.5.
3. The preparation method of the B @ HS hollow sphere molecular sieve of claim 1, wherein in the step 3), the drying is performed for 6-12 hours at 60-80 ℃.
4. The method for preparing the B @ HS hollow sphere molecular sieve according to claim 1, wherein in step 3), the organic solvent comprises at least one of ethanol, acetone, and propionaldehyde; the specific process for removing the template agent comprises the following steps: the preparation method comprises the steps of forming a mixed solution by using an organic solvent and water, refluxing a precursor of the B-Silicalite under normal pressure, filtering, washing and drying obtained white solid after 2 hours, and finally roasting at 200 ℃ for more than 4 hours.
5. The preparation method of the B @ HS hollow sphere molecular sieve according to claim 4, wherein the organic solvent and water form a mixed solution: the volume ratio of the organic solvent to the water is (5: 1) - (10: 1).
6. The preparation method of the B @ HS hollow sphere molecular sieve according to claim 1, wherein the washing in step 5) is performed under reduced pressure suction filtration until the pH value of the washing solution reaches 7.0 +/-0.5.
7. The preparation method of the B @ HS hollow sphere molecular sieve of claim 1, wherein the B @ HS hollow sphere molecular sieve obtained in step 5) has the following properties: the particle diameter is 500-800 nm, and the specific surface area is 150m 2 /g～350m 2 The total pore volume is 0.1mL/g to 0.3mL/g, the average pore diameter is 0.45 nm to 0.60 nm, and the relative crystallinity is 75 percent to 95 percent.
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