CN111757851B - Microporous-mesoporous hierarchical zeolite material and preparation method and application thereof - Google Patents

Microporous-mesoporous hierarchical zeolite material and preparation method and application thereof Download PDF

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CN111757851B
CN111757851B CN201880090184.1A CN201880090184A CN111757851B CN 111757851 B CN111757851 B CN 111757851B CN 201880090184 A CN201880090184 A CN 201880090184A CN 111757851 B CN111757851 B CN 111757851B
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zeolite
mesoporous
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CN111757851A (en
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洪梅
陈超
董磊
王彦顶
张健
陈柱文
钱微
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Peking University Shenzhen Graduate School
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Abstract

A micropore-mesopore level zeolite material and a preparation method and application thereof, wherein the preparation method comprises the following steps: introducing a negative ion precursor serving as an organic mesoporous agent into a zeolite synthetic liquid containing a silicon source and an aluminum source, wherein the negative ion precursor can form stable organic negative ions in the zeolite synthetic liquid, the organic negative ions serve as a nucleophilic reagent to attack Si-O/Al-O sites in a zeolite framework, so that the framework is partially dissolved to form intragranular mesopores, and thus a micropore-mesopore level zeolite material is obtained, and the micropore-mesopore level zeolite material comprises a zeolite structure and an optional dispersed negative ion precursor inhabiting in pores of the zeolite structure, wherein the zeolite structure comprises a micropore structure and a mesopore structure, and at least part of the mesopore structure is positioned in a crystal. Provides a brand new mechanism, avoids the problems of phase separation, complex synthesis steps, high cost and the like, does not need to remove a template through calcination in the post-treatment, and can obtain the hierarchical pore zeolite only through deionized water washing.

Description

Microporous-mesoporous hierarchical zeolite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of zeolite materials, in particular to a micropore-mesopore level zeolite material and a preparation method and application thereof.
Background
Zeolite (Zeolite) is a Zeolite formed from [ TO4]([SiO4]、[AlO4]Or [ PO ]4]Etc.) form three-dimensional four-connected framework with periodic pore channel aluminosilicate crystals by sharing vertex. Because the zeolite has a uniform pore channel structure, internal adjustable acid sites, excellent shape-selective selectivity, high specific surface area, thermal stability, chemical stability and mechanical stability, and the zeolite has wide application in the fields of catalysis, adsorption, ion exchange and the like. Most of zeolite needs to be synthesized under the condition of organic amine or quaternary ammonium as a structure directing agent, but the aperture of the traditional microporous zeolite is small, usually less than 1nm, and can seriously hinder the diffusion of macromolecules in zeolite pore channels in a catalytic reaction, so that the blockage and carbon deposition effects of the zeolite pore channels are easily caused, and the service life of the catalyst is greatly reduced. In order to solve the above diffusion limitation problem in the last decade, a mesoporous structure has been introduced on the basis of microporous zeolite to form a novel zeolite system having both micropores and mesopores. The hierarchical pore structure zeolite not only retains the excellent characteristics of the traditional zeolite, but also overcomes the diffusion limitation of molecules with larger size by the existing mesoporous structure, greatly expands the application range of the zeolite material, and can realize breakthrough in the fields which can not be realized by the traditional zeolite material, such as protein adsorption, macromolecular catalysis, transition metal ion exchange and the like.
Due to the great advantages of microporous-mesoporous molecular sieves with hierarchical structures, synthetic methods for such structures have also been greatly developed in the last decade. The preparation method mainly comprises two main categories, namely a top-down synthesis strategy and a bottom-up post-treatment strategy. Top-down synthesis, also known as post-treatment, typically employs extreme conditions of strong acid or base, even radiation, to force the T atoms in the zeolite framework to dissolve out and remove, creating a hierarchical structure by sacrificing some of the crystallinity and solid mass. The method is simple to operate and convenient for industrialization, but the T atoms are separated from the framework by dissolution, which inevitably causes great damage to the crystallinity and mechanical properties of the zeolite framework, and the obtained pore channel structure is not easy to control, so that the post-treatment method has great limitation.
The bottom-up synthesis method includes a hard template method and a soft template method. The hard template method mainly uses some carbon materials including pearl carbon black, carbon nanotubes, etc. to produce a mesoporous structure by occupying the space inside the zeolite and finally removing the template by calcination. In patent US 6998104B 2, carbon aerosol is used as a pore-making agent to obtain microporous-mesoporous zeolite with a mesoporous range of 6-10 nm; in patent CN 103265050 a, a mixed solution of a carbon source (sucrose, fructose, furfural) and a silicon source is subjected to hydrothermal carbonization treatment to obtain a hierarchical pore zeolite molecular sieve microsphere. This method also has a great disadvantage in that it uses a template which is expensive to produce and requires the final removal of the template by calcination, consumes a large amount of energy, and does not meet the requirements of green chemistry and industrialization. The soft template method mainly uses a surfactant and a high molecular material. For surfactants as porogens, the self-assembly of the surfactant in the zeolite synthesis solution will generally compete with the nucleation growth of the zeolite, thereby easily causing phase separation to give a mixture of microporous zeolite and amorphous silica. The structure of the traditional surfactant is modified, such as introduction of an organosilane group, a plurality of quaternary amine groups and the like, so that the interaction force of the surfactant and a zeolite framework can be enhanced, the generation of phase separation is avoided, hydrophobic long-chain alkane occupies the internal space of the zeolite, and the hierarchical pore zeolite can be obtained by calcining. Patent CN103214003B introduces N, N-dimethyl-N- [3- (trimethoxysilane) propyl ] octadecyl ammonium chloride (TPOAC) into the synthesis of Y-type zeolite molecular sieve, thereby obtaining mesoporous Y-type zeolite molecular sieve; patent CN104402020A is also a micro-diplopore beta molecular sieve synthesized by specially designed eight ammonium head Bola type surfactant. The high molecular material can also be used as a mesoporous agent to generate zeolite with a hierarchical structure, and in patent CN1749162B, the microporous and mesoporous composite pore structure zeolite is successfully synthesized by using high molecular polyquaternary ammonium as a template. The mesoporous molecular sieve is a mesoscopic template regardless of a surfactant or a macromolecule, is encapsulated in a mesoporous pore passage through a physical steric hindrance effect, and has the disadvantages of high synthesis cost and difficult amplification of a synthesis process due to a special template structure. Therefore, the current synthesis methods all have certain limitations.
Disclosure of Invention
The invention uses organic small molecule (anion precursor) as mesoporous agent, which can form stable anion in zeolite synthetic liquid to chemically generate mesopore.
According to a first aspect of the present invention, a method for preparing a microporous-mesoporous-level zeolite material is provided, wherein a negative ion precursor is introduced into a zeolite synthetic solution comprising a silicon source and an aluminum source as an organic mesoporizing agent, the negative ion precursor is capable of forming stable organic negative ions in the zeolite synthetic solution, the organic negative ions serve as a nucleophile to attack Si-O/Al-O sites in a zeolite framework, so that the framework is partially dissolved to form intragranular mesopores, and a microporous-mesoporous-level zeolite material is obtained, the microporous-mesoporous-level zeolite material comprises a zeolite structure and an optional dispersed negative ion precursor inhabiting in pore channels of the zeolite structure, the zeolite structure comprises a microporous structure and a mesoporous structure, and at least part of the mesoporous structure is located in crystals.
Preferably, the organic anion is selected from one or more of an oxygen anion, a nitrogen anion and a carbon anion.
Preferably, the oxygen anion is derived from an organic acid or a hydroxyl compound as an anion precursor; more preferably, the organic acid is selected from one or more of isopropyl acid, trifluoroacetic acid and benzenesulfonic acid, and the hydroxy compound is selected from one or more of phenol, hexafluoroisopropanol and hydroxy phenylpropyl triazole.
Preferably, the nitrogen negative ion is derived from an aza compound as a negative ion precursor; more preferably, the aza compound is selected from one or more of 1H-1,2, 3-triazole and 4H-1,2, 4-triazole.
Preferably, the above-mentioned carbanion is derived from a carbanion compound as a negative ion precursor; more preferably, the above carbon-hybrid compound is nitromethane.
Preferably, the mesoporous structure is located entirely within the crystal.
Preferably, the pore diameter of the mesoporous structure is 2 to 50 nm.
Preferably, the above method comprises the steps of:
a) introducing a negative ion precursor serving as an organic mesoporous agent into a zeolite synthetic liquid containing a silicon source and an aluminum source, and carrying out synthetic reaction at the temperature of 0-300 ℃ and the pressure of normal pressure to 20 bar;
b) carrying out solid-liquid separation on the mixture obtained in the step a), and drying a solid product to obtain the microporous-mesoporous level zeolite material.
According to a second aspect of the present invention, the present invention provides a microporous-mesoporous level zeolitic material comprising a zeolitic structure and optionally a dispersed negative ion precursor residing in the channels of said zeolitic structure, said zeolitic structure comprising a microporous structure and a mesoporous structure, and at least part of said mesoporous structure being located inside the crystals, said microporous-mesoporous level zeolitic material being prepared by:
introducing a negative ion precursor as an organic mesoporous agent into a zeolite synthetic liquid containing a silicon source and an aluminum source, wherein the negative ion precursor can form stable organic negative ions in the zeolite synthetic liquid, and the organic negative ions are used as a nucleophilic reagent to attack Si-O/Al-O sites in a zeolite framework so as to dissolve part of the framework to form intragranular mesopores, thereby obtaining the microporous-mesoporous hierarchical zeolite material.
Preferably, the organic anion is selected from one or more of an oxygen anion, a nitrogen anion and a carbon anion.
Preferably, the oxygen anion is derived from an organic acid or a hydroxyl compound as an anion precursor; more preferably, the organic acid is selected from one or more of isopropyl acid, trifluoroacetic acid and benzenesulfonic acid, and the hydroxy compound is selected from one or more of phenol, hexafluoroisopropanol and hydroxy phenylpropyl triazole.
Preferably, the nitrogen negative ion is derived from an aza compound as a negative ion precursor; more preferably, the aza compound is selected from one or more of 1H-1,2, 3-triazole and 4H-1,2, 4-triazole.
Preferably, the above-mentioned carbanion is derived from a carbanion compound as a negative ion precursor; more preferably, the above carbon-hybrid compound is nitromethane.
Preferably, the mesoporous structure is located entirely within the crystal.
Preferably, the pore diameter of the mesoporous structure is 2 to 50 nm.
According to a third aspect of the present invention, the present invention provides the use of the microporous-mesoporous layered zeolitic material of the second aspect described above as a catalyst, adsorbent, or ion exchanger.
Compared with the method for synthesizing the hierarchical pore zeolite in the prior art, the method of the invention utilizes organic micromolecules (negative ion precursors) as mesoporous agents to synthesize the microporous-mesoporous hierarchical zeolite, and provides a brand new mechanism. The method avoids the problems that in the prior art, a hard template method and a soft template method are easy to generate phase separation, the synthesis steps are complex, the cost is high and the like, and the hierarchical pore zeolite can be obtained only by washing with deionized water without removing the template through calcination in the post-treatment. By recycling the washing liquid, the organic micromolecules can be recycled for many times, so that the cost is saved, and the washing liquid also meets the requirement of green chemistry.
Drawings
Fig. 1 is (a) an XRD diffractogram of the microporous-mesoporous level zeolite material prepared in example 1; (b) nitrogen adsorption-desorption isotherms; (c) a mesoporous pore size distribution curve; (d) scanning an electron microscope picture; and (e) transmission electron micrographs;
fig. 2 is (a) an XRD diffractogram of the microporous-mesoporous level zeolite material prepared in example 2; (b) nitrogen adsorption-desorption isotherms; (c) a mesoporous pore size distribution curve; (d) scanning an electron microscope picture; and (e) transmission electron micrographs;
fig. 3 is (a) an XRD diffractogram of the microporous-mesoporous level zeolite material prepared in example 3; (b) nitrogen adsorption-desorption isotherms; (c) a mesoporous pore size distribution curve; and (d) scanning electron micrographs;
fig. 4 is (a) an XRD diffractogram of the microporous-mesoporous level zeolite material prepared in example 4; (b) nitrogen adsorption-desorption isotherms; (c) a mesoporous pore size distribution curve; and (d) scanning electron micrographs;
fig. 5 is (a) an XRD diffractogram of the microporous-mesoporous level zeolite material prepared in example 5; (b) nitrogen adsorption-desorption isotherms; (c) a mesoporous pore size distribution curve; and (d) scanning electron micrographs;
fig. 6 is (a) an XRD diffractogram of the microporous-mesoporous level zeolite material prepared in example 6; (b) nitrogen adsorption-desorption isotherms; (c) a mesoporous pore size distribution curve; and (d) scanning electron micrographs;
fig. 7 is (a) an XRD diffractogram of the microporous-mesoporous level zeolite material prepared in example 7; (b) nitrogen adsorption-desorption isotherms; (c) a mesoporous pore size distribution curve; and (d) transmission electron micrographs;
fig. 8 is (a) an XRD diffractogram of the microporous-mesoporous level zeolite material prepared in example 8; (b) nitrogen adsorption-desorption isotherms; (c) a mesoporous pore size distribution curve; and (d) transmission electron micrographs;
fig. 9 is an adsorption kinetics curve of the LTA-type zeolite material of microporous-mesoporous levels of sample 1 in example 1, sample 2 in example 2, sample 4 in example 4, and sample 6 in example 6 for trypsin;
fig. 10 is a graph comparing furfural conversion for sample 7 in example 7 and sample 8 in example 8.
Detailed Description
The microporous-mesoporous level zeolite material of the present invention, and the preparation method and use thereof will be described in more detail below. Unless defined otherwise, technical and scientific terms used in the detailed description have the same meaning as is understood by one of ordinary skill in the art to which this invention belongs.
The invention develops a brand new strategy to synthesize microporous-mesoporous zeolite crystals with hierarchical structures, and the invention utilizes organic micromolecules (negative ion precursors) as a mesoporous-inducing agent to form stable negative ions in zeolite synthetic liquid so as to chemically induce mesopores, wherein the negative ion precursors comprise but are not limited to oxygen negative ions, nitrogen negative ions and carbon negative ion precursors, and the negative ions formed by the negative ion precursors can be used as nucleophilic reagents to attack Si-O/Al-O sites in zeolite frameworks through an SN2 process, so that on-line etching is carried out to dissolve framework parts so as to form intragranular mesopores. The preparation method is simple and energy-saving, the template agent is low in cost and easy to obtain, and the prepared microporous-mesoporous zeolite has wide application.
Specifically, the preparation method of the microporous-mesoporous level zeolite material comprises the steps of introducing a negative ion precursor serving as an organic mesoporgenic agent into a zeolite synthetic liquid containing a silicon source and an aluminum source, wherein the negative ion precursor can form stable organic negative ions in the zeolite synthetic liquid, the organic negative ions serve as a nucleophilic reagent to attack Si-O/Al-O sites in a zeolite framework, so that the framework is partially dissolved to form intragranular mesopores, and the microporous-mesoporous level zeolite material is obtained and comprises a zeolite structure and an optional dispersed negative ion precursor inhabiting pore channels of the zeolite structure, wherein the zeolite structure comprises a microporous structure and a mesoporous structure, and at least part of the mesoporous structure is positioned in a crystal.
Since small organic molecules (anion precursors) can be removed by washing with water, depending on the degree of washing with water, the microporous-mesoporous-level zeolite material prepared according to the present invention may or may not have dispersed anion precursors residing in the pores of the zeolite structure, which is defined as "optionally present".
In the present invention, the organic anion includes, but is not limited to, an oxygen anion, a nitrogen anion, and a carbon anion. Wherein, the oxygen anion can be derived from organic acid or hydroxyl compound as anion precursor; for example, the organic acid may be selected from one or more of isopropyl acid, trifluoroacetic acid and benzenesulfonic acid, and the hydroxy compound may be selected from one or more of phenol, hexafluoroisopropanol and hydroxy phenylpropyl triazole. The nitrogen negative ions can be from aza compounds as negative ion precursors; for example, the aza compound can be selected from one or more of 1H-1,2, 3-triazole and 4H-1,2, 4-triazole. The carbanion can be derived from a carbanion precursor, which is a carbon compound; for example, the carbon-carbon compound may be nitromethane. The organic small molecule (anion precursor) has pKa lower than 13.5, and can form stable anion in the zeolite synthetic liquid and attack Si-O/Al-O site in the zeolite skeleton via SN2 nucleophilic reaction to form the mesoporous structure inside the zeolite crystal.
In the microporous-mesoporous-level zeolite material of the present invention, at least a part of the mesoporous structure is located inside the crystal, however, as a preferred embodiment, the mesoporous structure is entirely located inside the crystal. The pore diameter of the mesoporous structure is generally 2 to 50nm, for example, 2 to 10nm, 2 to 20nm, 5 to 30nm, 10 to 30nm, 15 to 40nm, 20 to 45nm, 25 to 50nm, and the like.
In a preferred embodiment, the method of the invention comprises the steps of:
a) introducing a negative ion precursor serving as an organic mesoporous agent into a zeolite synthetic liquid containing a silicon source and an aluminum source, and carrying out synthetic reaction at the temperature of 0-300 ℃ and the pressure of normal pressure to 20 bar;
b) carrying out solid-liquid separation on the mixture obtained in the step a), and drying a solid product to obtain the microporous-mesoporous level zeolite material.
In the present invention, the zeolite structure may be selected from any zeolite structure known so far. According to the structure proprietary commission of the international zeolite association at its website http: iza-online.org/published, two hundred more zeolitic framework structures have been identified so far. To avoid subsequent calcination processes, preferred zeolite structures may be synthesized in the absence of organics, i.e., may be crystallized in the absence of microporous pore formers, including but not limited to, LTA, FAU, SOD, CAN, BEA, CHA, RTH, EMT, MFI, MEL, MOR, EON, and the like.
The synthesis raw material (existing in the zeolite synthesis solution) of the microporous-mesoporous level zeolite material of the present invention includes a silicon source, an aluminum source, an alkali, etc., wherein the silicon source may be, but is not limited to, silica sol, silicon oxide, tetraethyl orthosilicate, sodium metasilicate, n-butyl silicate, silicon carbide, etc., the aluminum source may be, but is not limited to, aluminum foil, aluminum powder, aluminum chloride, sodium metaaluminate, aluminum sulfate, aluminum nitrate, aluminum isopropoxide, pseudoboehmite, aluminum hydroxide, etc., and the alkali may be, but is not limited to, sodium hydroxide, potassium hydroxide, ammonium hydroxide, calcium hydroxide, aluminum hydroxide, silver hydroxide, lead hydroxide, zinc hydroxide, cesium hydroxide, potassium carbonate, sodium carbonate, ammonia, hydrazine, hydroxylamine, liquid ammonia, etc.
The technical solutions and effects of the present invention are described in detail by the following specific examples, and it should be understood that the examples are only illustrative and should not be construed as limiting the scope of the present invention.
Example 1 Synthesis of microporous-mesoporous layered LTA Zeolite by trifluoroacetic acid as a mesoporous agent
Dissolving 12.54ml of silica sol (25%) in 10ml of deionized water, mechanically stirring for more than 15 minutes to uniformly disperse the silica sol, and marking the silica sol as a silicon source; 2.0g of sodium hydroxide and 4.1g of sodium metaaluminate are dissolved in 35ml of deionized water, stirred for 10 minutes to clarify and then 2.85g of trifluoroacetic acid are added. And finally, adding the solution into a silicon source, continuously stirring, aging at room temperature for 3 hours, then starting heating, and reacting at 100 ℃ for 18 hours. And after the reaction is finished, collecting reaction liquid for centrifugal treatment, washing with water to collect white solid, and drying at 60 ℃ to obtain the hierarchical porous LTA zeolite.
XRD measurement is carried out on the microporous-mesoporous level zeolite material by adopting a D/Max-2200 PC X-ray diffractometer of Rigaku company, a spectrogram is shown in figure 1a, all characteristic peaks of an LTA type zeolite structure can be clearly seen on an obtained powder diffraction pattern, and the obtained solid is proved to be LTA zeolite in a crystalline state.
Performing nitrogen adsorption and desorption measurement at 77K on the microporous-mesoporous level zeolite material by adopting Tristar II 3020 of Micromeritics company, wherein the adsorption and desorption isotherms are listed in figure 1b, the obtained adsorption isotherm is IV type, and forms an H3 type hysteresis loop with the obtained desorption isotherm, and the P/P ratio is high0Under the pressure, the mesoporous silicon material does not reach saturation, and the existence of mesopores is proved. Calculating the obtained nitrogen adsorption and desorption isotherm by a BJH method, and obtaining dV/dlog (D) pore volume and average pore diameter DpThe correlation diagram is shown in fig. 1c, and it can be seen that the mesopores of the obtained microporous-mesopore level zeolite material are in the range of 9-20 nm. Brunauer-Emmett-Teller specific surface area calculation is carried out on the adsorption data obtained in the figure 1b, and the BET specific surface area of the microporous-mesoporous level zeolite material is 113m2G, mesoporous pore volume of 0.05cm3(ii) in terms of/g. The content of the elements in the microporous-mesoporous level zeolite material is measured by using an inductively coupled plasma atomic emission spectrum JY 2000-2 of HORIBA JobinYvon corporation, and the Si/Al ratio is 1.15.
Scanning Electron Microscope (SEM) observation of the non-gold-coated sample is carried out on the micropore-mesopore level zeolite material by adopting JSM-7800F of JEOL company, and shown in figure 1d, obvious LTA crystal form and mesopore structure can be seen. The result of transmission electron microscope observation of the microporous-mesoporous hierarchical zeolite material is shown in fig. 1e, and an obvious mesoporous structure can be seen.
Example 2 Synthesis of microporous-mesoporous layered LTA Zeolite Using p-Toluenesulfonic acid as a mesoporous agent
Dissolving 12.54ml of silica sol (25%) in 10ml of deionized water, mechanically stirring for more than 15 minutes to uniformly disperse the silica sol, and marking the silica sol as a silicon source; 2.0g of sodium hydroxide and 4.1g of sodium metaaluminate are dissolved in 35ml of deionized water, stirred for 10 minutes to clarify and then 2.353g of p-toluenesulfonic acid are added. And finally, adding the solution into a silicon source, continuously stirring, aging at room temperature for 3 hours, then starting heating, and reacting at 100 ℃ for 18 hours. And after the reaction is finished, collecting reaction liquid for centrifugal treatment, washing with water to collect white solid, and drying at 60 ℃ to obtain the hierarchical porous LTA zeolite.
XRD measurement is carried out on the microporous-mesoporous level zeolite material by adopting a D/Max-2200 PC X-ray diffractometer of Rigaku company, a spectrogram is shown in figure 2a, all characteristic peaks of an LTA type zeolite structure can be clearly seen on an obtained powder diffraction pattern, and the obtained solid is proved to be LTA zeolite in a crystalline state.
Performing nitrogen adsorption and desorption measurement at 77K on the microporous-mesoporous level zeolite material, and adsorbingThe desorption isotherms are shown in FIG. 2b, the obtained adsorption isotherm is type IV, a hysteresis loop of type H3 is formed with the obtained desorption isotherm, the obtained nitrogen adsorption desorption isotherm is calculated by the BJH method, and the obtained dV/dlog (D) pore volume and average pore diameter DpThe correlation diagram is shown in fig. 2c, and it can be seen that the mesoporous peak of the obtained microporous-mesoporous level zeolite material is about 18 nm. Brunauer-Emmett-Teller specific surface area calculation is carried out on the adsorption data obtained in the figure 2b, and the mesoporous BET specific surface area of the micropore-mesoporous level zeolite material is 89m2/g。
Scanning Electron Microscope (SEM) observation of the non-gold-coated sample is carried out on the micropore-mesopore level zeolite material by adopting JSM-7800F of JEOL company, and shown in figure 2d, obvious LTA crystal form and mesopore structure can be seen. The result of transmission electron microscope observation of the microporous-mesoporous hierarchical zeolite material is shown in fig. 2e, and an obvious mesoporous structure can be seen.
Example 3 Synthesis of microporous-mesoporous level LTA Zeolite with Hexafluoroisopropanol as a mesogenic agent
Dissolving 12.54ml of silica sol (25%) in 10ml of deionized water, mechanically stirring for more than 15 minutes to uniformly disperse the silica sol, and marking the silica sol as a silicon source; 2.0g of sodium hydroxide and 4.1g of sodium metaaluminate are dissolved in 35ml of deionized water, stirred for 10 minutes to clarify and then 4.2g of hexafluoroisopropanol are added. And finally, adding the solution into a silicon source, continuously stirring, aging at room temperature for 3 hours, then starting heating, and reacting at 100 ℃ for 18 hours. And after the reaction is finished, collecting reaction liquid for centrifugal treatment, washing with water to collect white solid, and drying at 60 ℃ to obtain the hierarchical porous LTA zeolite.
XRD measurement is carried out on the microporous-mesoporous level zeolite material by adopting a D/Max-2200 PC X-ray diffractometer of Rigaku company, a spectrogram is shown in figure 3a, all characteristic peaks of an LTA type zeolite structure can be clearly seen on an obtained powder diffraction pattern, and the obtained solid is proved to be LTA zeolite in a crystalline state.
Performing nitrogen adsorption and desorption measurement on the microporous-mesoporous level zeolite material at the temperature of 77K, wherein an adsorption and desorption isotherm is shown in figure 3b, the obtained adsorption isotherm is IV type, an H3 type hysteresis loop is formed with the obtained desorption isotherm, and the BJH method is performed on the obtained nitrogen adsorption and desorption isothermCalculated by the method, the resulting dV/dlog (D) pore volume and mean pore diameter DpThe correlation diagram of (a) is shown in fig. 3c, and it can be seen that the mesopores of the obtained microporous-mesoporous level zeolite material are about 14 nm. Brunauer-Emmett-Teller specific surface area calculation is carried out on the adsorption data obtained in the figure 3b, and the mesoporous BET specific surface area of the micropore-mesoporous level zeolite material is 132m2/g。
Scanning Electron Microscope (SEM) observation of the non-gold-coated sample is carried out on the micropore-mesopore level zeolite material by adopting JSM-7800F of JEOL company, and shown in figure 3d, obvious LTA crystal form and mesopore structure can be seen.
Example 41 Synthesis of microporous-mesoporous hierarchical LTA Zeolite with 2, 3-triazole as a mesoporous agent
Dissolving 12.54ml of silica sol (25%) in 10ml of deionized water, mechanically stirring for more than 15 minutes to uniformly disperse the silica sol, and marking the silica sol as a silicon source; 2.0g of sodium hydroxide and 4.1g of sodium metaaluminate are dissolved in 35ml of deionized water, stirred for 10 minutes until clear and then 1.73g of 1,2, 3-triazole are added. And finally, adding the solution into a silicon source, continuously stirring, aging at room temperature for 3 hours, then starting heating, and reacting at 100 ℃ for 18 hours. And after the reaction is finished, collecting reaction liquid for centrifugal treatment, washing with water to collect white solid, and drying at 60 ℃ to obtain the hierarchical porous LTA zeolite.
XRD measurement is carried out on the microporous-mesoporous level zeolite material by adopting a D/Max-2200 PC X-ray diffractometer of Rigaku company, a spectrogram is shown in figure 4a, all characteristic peaks of an LTA type zeolite structure can be clearly seen on an obtained powder diffraction pattern, and the obtained solid is proved to be LTA zeolite in a crystalline state.
Performing nitrogen adsorption and desorption measurement on the microporous-mesoporous level zeolite material at the temperature of 77K, wherein adsorption and desorption isotherms are listed in figure 4b, the obtained adsorption isotherm is type IV, an H3 hysteresis loop is formed with the obtained desorption isotherm, and the obtained nitrogen adsorption and desorption isotherm is subjected to BJH method calculation to obtain dV/dlog (D) pore volume and average pore diameter DpThe correlation diagram of (a) is shown in fig. 4c, and it can be seen that the mesopores of the obtained microporous-mesoporous level zeolite material are about 14 nm. Brunauer-Emmett-Teller specific surface area calculation is carried out on the adsorption data obtained in the figure 4b, and the microporous-mesoporous level boiling point is obtainedThe mesoporous BET specific surface area of the stone material is 103m2/g。
Scanning Electron Microscope (SEM) observation of the non-gold-coated sample is carried out on the micropore-mesopore level zeolite material by adopting JSM-7800F of JEOL company, and shown in figure 4d, obvious LTA crystal form and mesopore structure can be seen.
Example 51, 2, 4-triazole as a mesoporous agent to synthesize a microporous-mesoporous level LTA zeolite
Dissolving 12.54ml of silica sol (25%) in 10ml of deionized water, mechanically stirring for more than 15 minutes to uniformly disperse the silica sol, and marking the silica sol as a silicon source; 2.0g of sodium hydroxide and 4.1g of sodium metaaluminate are dissolved in 35ml of deionized water, stirred for 10 minutes until clear and then 1.73g of 1,2, 4-triazole are added. And finally, adding the solution into a silicon source, continuously stirring, aging at room temperature for 3 hours, then starting heating, and reacting at 100 ℃ for 18 hours. And after the reaction is finished, collecting reaction liquid for centrifugal treatment, washing with water to collect white solid, and drying at 60 ℃ to obtain the hierarchical porous LTA zeolite.
XRD measurement is carried out on the microporous-mesoporous level zeolite material by adopting a D/Max-2200 PC X-ray diffractometer of Rigaku company, a spectrogram is shown in figure 5a, all characteristic peaks of an LTA type zeolite structure can be clearly seen on an obtained powder diffraction pattern, and the obtained solid is proved to be LTA zeolite in a crystalline state.
Performing nitrogen adsorption and desorption measurement on the microporous-mesoporous level zeolite material at the temperature of 77K, wherein adsorption and desorption isotherms are listed in figure 5b, the obtained adsorption isotherm is type IV, an H3 hysteresis loop is formed with the obtained desorption isotherm, and the obtained nitrogen adsorption and desorption isotherm is subjected to BJH method calculation to obtain dV/dlog (D) pore volume and average pore diameter DpThe correlation diagram of (a) is shown in fig. 5c, and it can be seen that the mesopore peak of the obtained microporous-mesopore level zeolite material is about 18 nm. Brunauer-Emmett-Teller specific surface area calculation is carried out on the adsorption data obtained in the step 5b, and the mesoporous BET specific surface area of the micropore-mesoporous level zeolite material is 70m2/g。
Scanning Electron Microscope (SEM) observation of the non-gold-coated sample is carried out on the micropore-mesopore level zeolite material by adopting JSM-7800F of JEOL company, and shown in figure 5d, obvious LTA crystal form and mesopore structure can be seen.
Example 6 Synthesis of microporous-mesoporous layered LTA Zeolite Using nitromethane as a mesoporous agent
Dissolving 12.54ml of silica sol (25%) in 10ml of deionized water, mechanically stirring for more than 15 minutes to uniformly disperse the silica sol, and marking the silica sol as a silicon source; 2.0g of sodium hydroxide and 4.1g of sodium metaaluminate are dissolved in 35ml of deionized water, stirred for 10 minutes to clarify and then 1.526g of nitromethane are added. And finally, adding the solution into a silicon source, continuously stirring, aging at room temperature for 3 hours, then starting heating, and reacting at 100 ℃ for 18 hours. And after the reaction is finished, collecting reaction liquid for centrifugal treatment, washing with water to collect white solid, and drying at 60 ℃ to obtain the hierarchical porous LTA zeolite.
XRD measurement is carried out on the microporous-mesoporous level zeolite material by adopting a D/Max-2200 PC X-ray diffractometer of Rigaku company, a spectrogram is shown in figure 6a, all characteristic peaks of an LTA type zeolite structure can be clearly seen on an obtained powder diffraction pattern, and the obtained solid is proved to be LTA zeolite in a crystalline state.
Performing nitrogen adsorption and desorption measurement on the microporous-mesoporous level zeolite material at the temperature of 77K, wherein adsorption and desorption isotherms are listed in figure 6b, the obtained adsorption isotherm is type IV, an H3 hysteresis loop is formed with the obtained desorption isotherm, and the obtained nitrogen adsorption and desorption isotherm is subjected to BJH method calculation to obtain dV/dlog (D) pore volume and average pore diameter DpThe correlation diagram is shown in fig. 6c, and it can be seen that the mesopore range of the obtained microporous-mesopore level zeolite material is about 14 nm. Brunauer-Emmett-Teller specific surface area calculation is carried out on the adsorption data obtained in the figure 6b, and the mesoporous BET specific surface area of the micropore-mesoporous level zeolite material is 105m2/g。
Scanning Electron Microscope (SEM) observation of the non-gold-coated sample is carried out on the micropore-mesopore level zeolite material by adopting JSM-7800F of JEOL company, and shown in figure 6d, obvious LTA crystal form and mesopore structure can be seen.
Example 7 Synthesis of microporous-mesoporous level FAU zeolite with phenol as a mesogenic agent
Dissolving 1.9g of sodium hydroxide and 4.1g of sodium metaaluminate in 30ml of deionized water, stirring until the solution is clear, and marking the solution as an aluminum source; 2.35g of phenol were dissolved in 6ml of deionized water, dispersed by sonication and marked as additive. And (3) dropwise adding the aluminum source and the additive solution into the silicon source, continuously stirring, aging at room temperature for 24 hours, and then starting heating, wherein the set temperature is 90 ℃. Timing when the temperature rises to 90 ℃, centrifuging after 48 hours, collecting white solid, and drying at 60 ℃.
XRD measurement is carried out on the microporous-mesoporous level zeolite material by adopting a D/Max-2200 PC X-ray diffractometer of Rigaku company, a spectrogram is shown in figure 7a, all characteristic peaks of an FAU type zeolite structure can be clearly seen on an obtained powder diffraction pattern, and the obtained solid is confirmed to be crystalline FAU zeolite.
Performing nitrogen adsorption and desorption measurement on the microporous-mesoporous level zeolite material at the temperature of 77K, wherein adsorption and desorption isotherms are listed in figure 7b, the obtained adsorption isotherm is type IV, an H3 hysteresis loop is formed with the obtained desorption isotherm, and the obtained nitrogen adsorption and desorption isotherm is subjected to BJH method calculation to obtain dV/dlog (D) pore volume and average pore diameter DpThe correlation diagram of (a) is shown in fig. 7c, and it can be seen that the mesopores of the obtained microporous-mesoporous level zeolite material are about 31 nm. Brunauer-Emmett-Teller specific surface area calculation is carried out on the adsorption data obtained in the step 7b, and the mesoporous BET specific surface area of the micropore-mesoporous hierarchical zeolite material is 600m2(ii) in terms of/g. The microporous-mesoporous hierarchical zeolite material was observed by a transmission electron microscope and is shown in fig. 7d, and an obvious FAU crystal form and mesoporous structure were observed.
Example 81 Synthesis of microporous-mesoporous level FAU Zeolite Using triazole as mesoporous agent
Dissolving 1.9g of sodium hydroxide and 4.1g of sodium metaaluminate in 30ml of deionized water, stirring until the solution is clear, and marking the solution as an aluminum source; 1.73g of 1,2, 4-triazole is dissolved in 6ml of deionized water, and the solution is dispersed by ultrasonic and marked as an additive. And (3) dropwise adding the aluminum source and the additive solution into the silicon source, continuously stirring, aging at room temperature for 24 hours, and then starting heating, wherein the set temperature is 90 ℃. Timing when the temperature rises to 90 ℃, centrifuging after 48 hours, collecting white solid, and drying at 60 ℃.
XRD measurement is carried out on the microporous-mesoporous level zeolite material by adopting a D/Max-2200 PC X-ray diffractometer of Rigaku company, a spectrogram is shown in figure 8a, all characteristic peaks of an FAU type zeolite structure can be clearly seen on an obtained powder diffraction pattern, and the obtained solid is confirmed to be crystalline FAU zeolite.
Performing nitrogen adsorption and desorption measurement on the microporous-mesoporous level zeolite material at the temperature of 77K, wherein adsorption and desorption isotherms are listed in figure 8b, the obtained adsorption isotherm is type IV, an H3 hysteresis loop is formed with the obtained desorption isotherm, and the obtained nitrogen adsorption and desorption isotherm is subjected to BJH method calculation to obtain dV/dlog (D) pore volume and average pore diameter DpThe correlation diagram of (a) is shown in fig. 8c, and it can be seen that the mesopores of the obtained microporous-mesoporous level zeolite material are about 24 nm. Brunauer-Emmett-Teller specific surface area calculation is carried out on the adsorption data obtained in the step 8b, and the mesoporous BET specific surface area of the microporous-mesoporous hierarchical zeolite material is 610m2(ii) in terms of/g. The microporous-mesoporous hierarchical zeolite material was observed by a transmission electron microscope, and is shown in fig. 8d, and an obvious FAU crystal form and mesoporous structure were observed.
Application example 1 microporous-mesoporous hierarchical LTA Zeolite for enzyme adsorption
80mg of fresh trypsin was dissolved in 10ml of Phosphate (PBS) buffer (pH 6.0) and stored in an ice-water bath. The supernatant was filtered through a 0.22 μm PTFE membrane, 100mg of microporous-mesoporous grade LTA zeolite material was added, and trypsin adsorption experiments were performed at 4 ℃ under magnetic stirring at 600 rpm. During the adsorption process, 300 μ l of sample is taken at different time periods and centrifuged, the trypsin concentration of the supernatant is measured on a NanoDrop 2000c (thermo scientific) instrument, and the loading of the trypsin adsorbed by the mesoporous zeolite at the time is calculated by a subtraction method.
Fig. 9 shows adsorption kinetics curves of the microporous-mesoporous hierarchical LTA-type zeolite material of example 1, sample 2, sample 4 and sample 6 in example 1, and the equilibrium immobilization amounts of the microporous-mesoporous hierarchical LTA-type zeolite material of example 6 are 246, 243, 242 and 236mg/g respectively, and are only 83mg/g compared with the adsorption kinetics curves of the conventional microporous LTA zeolite CLTA sample for trypsin.
Application example 2 microporous-mesoporous level FAU zeolite as condensation reaction catalyst of furfural and acetone
The microporous-mesoporous level FAU zeolites prepared in examples 7 and 8 were ion-exchanged with a 0.7M KNO3 solution under magnetic stirring at 80 degrees celsius for 2 hours, washed with water three times, centrifuged, and dried. Adding 2g of catalyst into 39.5g of acetone and 6.5g of furfural under stirring, heating to 100 ℃ at a heating rate of 1.5 ℃ per minute, keeping the temperature for reaction for 2 hours, and analyzing a product by GC-2010 and HPLC of the atrazine with an ionic flame detector. Figure 10 is a graph comparing acetone and furfural conversion for sample 7 in example 7 and sample 8 in example 8 with conventional FAU catalyst CFAU, with conversion of over 8% for the hierarchical FAU zeolite made by the process of the present invention.
The foregoing is a more detailed description of the present invention that is presented in conjunction with specific embodiments, and the practice of the invention is not to be considered limited to those descriptions. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.

Claims (22)

1. A preparation method of a microporous-mesoporous hierarchical zeolite material is characterized in that a negative ion precursor is introduced into a zeolite synthetic solution containing a silicon source and an aluminum source to be used as an organic mesoporous agent to carry out a zeolite synthetic reaction, wherein the negative ion precursor is an organic small molecule, and the organic small molecule can form stable organic negative ions in the zeolite synthetic solution; performing solid-liquid separation on the mixture obtained after the reaction of the zeolite synthetic solution, washing with water and drying the solid product to obtain a microporous-mesoporous level zeolite material;
the organic negative ions are used as a nucleophilic reagent to attack Si-O/Al-O sites in a zeolite framework, so that the framework is partially dissolved to form intragranular mesopores, and a micropore-mesopore level zeolite material is obtained, wherein the micropore-mesopore level zeolite material comprises a zeolite structure and an optional dispersed negative ion precursor which is inhabited in pore channels of the zeolite structure, the zeolite structure comprises a micropore structure and a mesopore structure, and at least part of the mesopore structure is positioned in the crystal.
2. The method according to claim 1, wherein the organic anion is selected from one or more of an oxyanion, a nitrogen anion, and a carbanion.
3. The production method according to claim 2, wherein the oxyanion is derived from an organic acid or a hydroxyl compound as an anion precursor.
4. The preparation method according to claim 3, wherein the organic acid is one or more selected from the group consisting of isopropyl acid, trifluoroacetic acid and benzenesulfonic acid, and the hydroxy compound is one or more selected from the group consisting of phenol, hexafluoroisopropanol and hydroxyphenyltriazole.
5. The method according to claim 2, wherein the nitrogen negative ion is derived from an aza compound as a negative ion precursor.
6. The preparation method according to claim 5, wherein the aza compound is selected from one or more of 1H-1,2, 3-triazole and 4H-1,2, 4-triazole.
7. The method according to claim 2, wherein the carbanion is derived from a carbanion compound as a negative ion precursor.
8. The method of claim 7, wherein the carbon-carbon compound is nitromethane.
9. The method according to claim 1, wherein the mesoporous structure is located entirely within the crystal.
10. The method according to claim 1, wherein the mesoporous structure has a pore size of 2 to 50 nm.
11. The method for preparing according to claim 1, characterized in that it comprises the following steps:
a) introducing a negative ion precursor serving as an organic mesoporous agent into zeolite synthetic liquid comprising a silicon source and an aluminum source, and carrying out synthetic reaction at a temperature of 0-300 ℃ and a pressure of normal pressure to 20 bar;
b) carrying out solid-liquid separation on the mixture obtained in the step a), washing with water and drying a solid product to obtain the microporous-mesoporous level zeolite material.
12. A microporous-mesoporous level zeolitic material, characterized in that it comprises a zeolitic structure and optionally dispersed negative ion precursors hosted in the channels of said zeolitic structure, said zeolitic structure comprising a microporous structure and a mesoporous structure, and at least part of said mesoporous structure being located inside the crystals, said microporous-mesoporous level zeolitic material being prepared by:
introducing a negative ion precursor serving as an organic mesoporous agent into a zeolite synthetic liquid containing a silicon source and an aluminum source to perform a zeolite synthetic reaction, wherein the negative ion precursor is an organic small molecule which can form stable organic negative ions in the zeolite synthetic liquid; performing solid-liquid separation on the mixture obtained after the reaction of the zeolite synthetic solution, washing with water and drying the solid product to obtain a microporous-mesoporous level zeolite material; the organic negative ions are used as a nucleophilic reagent to attack Si-O/Al-O sites in a zeolite framework, so that the framework is partially dissolved to form intragranular mesopores, and the micropore-mesopore level zeolite material is obtained.
13. The microporous-mesoporous hierarchical zeolitic material according to claim 12, wherein said organic anions are selected from one or more of the group consisting of oxygen anions, nitrogen anions, and carbanions.
14. The microporous-mesoporous hierarchical zeolitic material according to claim 13, characterized in that said oxyanion is derived from an organic acid or a hydroxyl compound as anion precursor.
15. The microporous-mesoporous hierarchical zeolitic material according to claim 14, wherein said organic acid is selected from one or more of the group consisting of isopropyl acid, trifluoroacetic acid, benzenesulfonic acid, and said hydroxyl compound is selected from one or more of the group consisting of phenol, hexafluoroisopropanol, hydroxyphenyltriazole.
16. The microporous-mesoporous hierarchical zeolitic material according to claim 13, characterized in that said nitrogen negative ions come from aza compounds as negative ion precursors.
17. The microporous-mesoporous hierarchical zeolite material of claim 16, wherein the aza compound is selected from one or more of 1H-1,2, 3-triazole and 4H-1,2, 4-triazole.
18. The microporous-mesoporous hierarchical zeolitic material according to claim 13, characterized in that said carbanions are derived from a carbocompound as a precursor of an anion.
19. The microporous-mesoporous hierarchical zeolitic material according to claim 18, characterized in that said hydrocarbon compound is nitromethane.
20. The microporous-mesoporous hierarchical zeolitic material according to claim 12, characterized in that said mesoporous structure is entirely located inside the crystals.
21. The microporous-mesoporous hierarchical zeolitic material according to claim 12, characterized in that said mesoporous structure has a pore size comprised between 2 and 50 nm.
22. Use of the microporous-mesoporous hierarchical zeolitic material of claim 12 as a catalyst, adsorbent or ion exchanger.
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