WO2019214022A1 - 一种微孔-介孔层级沸石材料及其制备方法和用途 - Google Patents

一种微孔-介孔层级沸石材料及其制备方法和用途 Download PDF

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WO2019214022A1
WO2019214022A1 PCT/CN2018/093555 CN2018093555W WO2019214022A1 WO 2019214022 A1 WO2019214022 A1 WO 2019214022A1 CN 2018093555 W CN2018093555 W CN 2018093555W WO 2019214022 A1 WO2019214022 A1 WO 2019214022A1
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mesoporous
zeolite
microporous
anion
organic
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French (fr)
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洪梅
陈超
董磊
王彦顶
张健
陈柱文
钱微
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北京大学深圳研究生院
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/14—Base exchange silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof

Definitions

  • the invention relates to the technical field of zeolitic materials, in particular to a microporous-mesoporal grade zeolite material, a preparation method thereof and use thereof.
  • Zeolite is an aluminosilicate crystal having a periodic channel formed by a three-dimensional four-joined skeleton formed by a common apex between tetrahedrons of [TO 4 ] ([SiO 4 ], [AlO 4 ] or [PO 4 ], etc.). Due to its uniform pore structure, inherently adjustable acidic sites, excellent shape selectivity and high specific surface area, thermal stability, chemical stability and mechanical stability, zeolites are catalyzed, adsorbed and ion exchanged. The field has a wide range of applications.
  • zeolites need to be synthesized under the action of organic amines or quaternary ammonium as a structure directing agent, but the conventional microporous zeolite has a small pore size, usually less than 1 nm, which seriously hinders the diffusion of macromolecules inside the zeolite pores in the catalytic reaction. It is easy to cause blockage and carbon deposition effect of the zeolite pores, and the catalyst life is greatly reduced.
  • a mesoporous structure has been introduced on the basis of microporous zeolite to form a novel zeolite system having both micropores and mesopores.
  • the multi-stage pore structure zeolite not only retains the excellent characteristics of the traditional zeolite, but also has a mesoporous structure that overcomes the diffusion limitation of the large-diameter molecules, greatly expanding the application range of the zeolite material, and can not be realized in the conventional zeolite material.
  • the fields such as protein adsorption, macromolecular catalysis, and transition metal ion exchange have achieved breakthroughs.
  • the preparation methods are mainly divided into two categories, namely, a top-down synthesis strategy and a bottom-up post-processing strategy.
  • the top-down synthesis method also known as the post-treatment method, usually uses a strong acid or a strong base, or even an extreme condition of radiation, to forcibly dissolve and remove the T atom in the zeolite skeleton, by sacrificing partial crystallinity and solid mass.
  • Hierarchical structure This method is simple in operation and convenient for industrialization.
  • the bottom-up synthesis method includes a hard template method and a soft template method.
  • the hard templating method mainly uses some carbon materials, including pearl carbon black, carbon nanotubes, etc., to occupy a mesoporous structure by occupying a space inside the zeolite and finally removing the template by calcination.
  • a microporous mesoporous zeolite having a mesoporous range of 6-10 nm is obtained by using a carbon aerosol as a pore former; in the patent CN 103265050 A, a carbon source (sucrose, fructose, furfural) is treated by hydrothermal carbonization.
  • a mixed solution of silicon sources gives multistage pore zeolite molecular sieve microspheres.
  • the method used in this method has a high production cost and requires the final removal of the template by calcination, which consumes a large amount of energy and does not meet the requirements of green chemistry and industrialization, so the method also has great drawbacks.
  • the soft templating method mainly uses a surfactant and a polymer material.
  • surfactants as porogens the self-assembly of surfactants in zeolite synthesates typically competes with zeolite nucleation growth, which tends to result in phase separation resulting in a mixture of microporous zeolite and amorphous silica.
  • Structural modification of traditional surfactants such as the introduction of organosilane groups, multiple quaternary amine groups, etc., can enhance the interaction between the surfactant and the zeolite framework, avoiding the generation of phase separation, and occupying hydrophobic long-chain alkanes.
  • a multistage zeolite is obtained by calcination.
  • Patent CN103214003B introduces N,N-dimethyl-N-[3-(trimethicone)propyl]octadecyl ammonium chloride (TPOAC) into the synthesis of Y zeolite molecular sieve to obtain mesoporous Y type Zeolite molecular sieve; patent CN104402020A also synthesizes micro-double-porosity beta molecular sieve through specially designed octaammonium-based Bola surfactant.
  • the polymer material can also be used as a mesoporous agent to produce a zeolite with a hierarchical structure.
  • a microporous mesoporous composite pore structure zeolite is successfully synthesized using a high molecular polyquaternium as a template. Whether it is a surfactant or a polymer, it is a mesoscopic template, and is encapsulated in a mesoporous channel by physical steric hindrance. Due to the special structure of the template, the synthesis cost is relatively large, and the synthesis process is difficult to enlarge. Therefore, the current synthetic methods have certain limitations.
  • the invention utilizes an organic small molecule (negative ion precursor) as a mesoporous agent, can form a stable negative ion in the zeolite synthesis liquid to chemically cause mesopores, and the method of the invention is simple and energy-saving, and the template agent is cheap and easy to obtain, and is obtained.
  • the microporous mesoporous zeolite is widely used.
  • the present invention provides a method for preparing a microporous-mesoporous layer zeolitic material, which comprises introducing an anion precursor as an organic mesoporous agent in a zeolite synthesis liquid comprising a silicon source and an aluminum source, the anion
  • the precursor is capable of forming a stable organic anion in the above zeolite synthesis solution, and the organic anion acts as a nucleophile to attack the Si-O/Al-O site in the zeolite framework, and the skeleton portion is dissolved to form a mesopores to obtain micropores.
  • a mesoporous graded zeolitic material comprising a zeolite structure and optionally a dispersed anion precursor residing in the pores of said zeolite structure, said zeolite structure comprising a microporous structure and a mesoporous structure, and at least a portion of said mesoporous structure is located Inside the crystal.
  • the above organic negative ions are selected from one or more of an oxygen anion, a nitrogen anion, and a carbon anion.
  • the above oxygen anion is derived from an organic acid or a hydroxy compound as a negative ion precursor; more preferably, the organic acid is selected from one or more of isopropyl acid, trifluoroacetic acid, and benzenesulfonic acid, and the above hydroxy compound is selected. From one or more of phenol, hexafluoroisopropanol, hydroxybenzotriazole.
  • the above nitrogen anion is derived from an aza compound as a negative ion precursor; more preferably, the above aza compound is selected from 1H-1,2,3-triazole, 4H-1,2,4-triazole One or more.
  • the above carbanion is derived from a carbon compound as a negative ion precursor; more preferably, the above carbon compound is nitromethane.
  • the mesoporous structures are all located inside the crystal.
  • the mesoporous structure has a pore diameter of 2 to 50 nm.
  • the above method comprises the following steps:
  • step b) The mixture of step a) is subjected to solid-liquid separation, and the solid product is dried to obtain the above microporous mesoporous layer zeolite material.
  • a microporous-mesoporous grade zeolitic material comprising a zeolite structure and optionally a dispersed anion precursor resident in a pore of said zeolite structure, said zeolite structure comprising micropores
  • the structure and mesoporous structure, and at least part of the above mesoporous structure is located inside the crystal, and the microporous-mesoporous grade zeolite material is prepared by the following method:
  • An anion precursor is introduced as an organic mesoporous agent in a zeolite synthesis liquid comprising a silicon source and an aluminum source, and the negative ion precursor is capable of forming a stable organic anion in the zeolite synthesis solution, and the organic anion acts as a nucleophile to attack the zeolite skeleton
  • the Si-O/Al-O sites in the medium dissolve the skeleton portion to form intragranular mesopores to obtain the above-mentioned microporous-mesoporous layer zeolite material.
  • the above organic negative ions are selected from one or more of an oxygen anion, a nitrogen anion, and a carbon anion.
  • the above oxygen anion is derived from an organic acid or a hydroxy compound as a negative ion precursor; more preferably, the organic acid is selected from one or more of isopropyl acid, trifluoroacetic acid, and benzenesulfonic acid, and the above hydroxy compound is selected. From one or more of phenol, hexafluoroisopropanol, hydroxybenzotriazole.
  • the above nitrogen anion is derived from an aza compound as a negative ion precursor; more preferably, the above aza compound is selected from 1H-1,2,3-triazole, 4H-1,2,4-triazole One or more.
  • the above carbanion is derived from a carbon compound as a negative ion precursor; more preferably, the above carbon compound is nitromethane.
  • the mesoporous structures are all located inside the crystal.
  • the mesoporous structure has a pore diameter of 2 to 50 nm.
  • the invention provides the use of the microporous mesoporous grade zeolite material of the above second aspect as a catalyst, adsorbent or ion exchanger.
  • the method of the present invention utilizes an organic small molecule (negative ion precursor) as a mesoporous agent to synthesize a microporous-mesopal grade zeolite, and proposes a completely new mechanism.
  • the method avoids the problems that the hard template and the soft template method are easy to produce phase separation, the synthesis step is complicated, and the cost is expensive in the prior art, and the post-treatment does not need to remove the template by calcination, and the multi-stage hole can be obtained only by washing with deionized water. Zeolite. By recycling the washing liquid, organic small molecules can be recycled many times, saving costs and meeting the requirements of green chemistry.
  • Example 1 is a (a) XRD diffraction pattern of the microporous-mesoporous grade zeolite material prepared in Example 1; (b) nitrogen adsorption-desorption isotherm; (c) mesoporous pore size distribution curve; (d) scanning electron micrograph And (e) transmission electron micrographs;
  • Example 2 is a (a) XRD diffraction pattern of the microporous-mesoporous grade zeolite material prepared in Example 2; (b) nitrogen adsorption-desorption isotherm; (c) mesoporous pore size distribution curve; (d) scanning electron micrograph And (e) transmission electron micrographs;
  • Example 3 is a (a) XRD diffraction pattern of the microporous mesoporous grade zeolite material prepared in Example 3; (b) nitrogen adsorption-desorption isotherm; (c) mesoporous pore size distribution curve; and (d) scanning electron microscopy photo;
  • Example 4 is a (a) XRD diffraction pattern of the microporous mesoporous grade zeolite material prepared in Example 4; (b) nitrogen adsorption-desorption isotherm; (c) mesoporous pore size distribution curve; and (d) scanning electron microscopy photo;
  • Figure 5 is a (a) XRD diffraction pattern of the microporous mesoporous grade zeolite material prepared in Example 5; (b) nitrogen adsorption-desorption isotherm; (c) mesoporous pore size distribution curve; and (d) scanning electron microscopy photo;
  • Figure 6 is a (a) XRD diffraction pattern of the microporous mesoporous grade zeolite material prepared in Example 6; (b) nitrogen adsorption-desorption isotherm; (c) mesoporous pore size distribution curve; and (d) scanning electron microscopy photo;
  • Figure 7 is a (a) XRD diffraction pattern of the microporous mesoporous grade zeolite material prepared in Example 7; (b) nitrogen adsorption-desorption isotherm; (c) mesoporous pore size distribution curve; and (d) transmission electron microscopy photo;
  • Figure 8 is a (a) XRD diffraction pattern of the microporous mesoporous grade zeolite material prepared in Example 8; (b) nitrogen adsorption-desorption isotherm; (c) mesoporous pore size distribution curve; and (d) transmission electron microscopy photo;
  • Example 9 is a sample 1 of Example 1, a sample 2 of Example 2, a sample 4 of Example 4, and a sample 6 of Example 6 for a microporous-mesoporal level LTA type zeolite material for adsorption of trypsin Learning curve
  • Figure 10 is a graph showing the conversion of furfural of Sample 7 in Example 7 and Sample 8 in Example 8.
  • microporous mesoporous grade zeolite material of the present invention its preparation method and use will be described in more detail below.
  • the technical and scientific terms used in the detailed description have the same meaning as understood by those skilled in the art, unless otherwise defined.
  • the present invention develops a novel strategy for synthesizing microporous-mesoporous zeolite crystals having a hierarchical structure.
  • the present invention utilizes small organic molecules (negative ion precursors) as mesoporous agents to form stable anions in zeolite synthesis liquids.
  • chemically mesoporous, negative ion precursors include, but are not limited to, oxygen anions, nitrogen anions, and carbanions, which form an anion that acts as a nucleophile to attack the Si-O/Al-O sites in the zeolite framework through the SN 2 process. Point, thereby in-line etching to dissolve the skeleton portion to form intragranular mesopores.
  • the preparation method of the invention is simple and energy-saving, the templating agent is cheap and easy to obtain, and the prepared microporous mesoporous zeolite is widely used.
  • the microporous mesoporous grade zeolite material of the present invention is prepared by introducing an anion precursor as an organic mesoporous agent in a zeolite synthesis liquid comprising a silicon source and an aluminum source, wherein the negative ion precursor can be A stable organic anion is formed in the zeolite synthesis solution, and the organic anion acts as a nucleophile to attack the Si-O/Al-O site in the zeolite framework, and the skeleton portion is dissolved to form a mesoporous mesoporous to obtain a microporous-mesoporous zeolite.
  • a material comprising a zeolite structure and optionally a dispersed anion precursor hosted in a pore of said zeolite structure, said zeolite structure comprising a microporous structure and a mesoporous structure, and at least a portion of said mesoporous structure is located inside said crystal.
  • the organic small molecule can be removed by water washing. Therefore, depending on the degree of water washing, the microporous mesoporous layer zeolite material prepared by the present invention may have dispersed anions hosted in the pores of the above zeolite structure.
  • the precursor there may also be no such dispersed negative ion precursors that reside in the pores of the above zeolite structure, which is what is meant by "optionally present”.
  • organic negative ions include, but are not limited to, oxygen anions, nitrogen anions, and carbon anions.
  • oxygen anion may be derived from an organic acid or a hydroxy compound as an 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 phenol, One or more of hexafluoroisopropanol and hydroxyphenylpropane triazole.
  • the nitrogen anion may be derived from an aza compound as a negative ion precursor; for example, the aza compound may be selected from one or more of 1H-1,2,3-triazole, 4H-1,2,4-triazole.
  • the carbanion may be derived from a carbon compound as a negative ion precursor; for example, the carbon compound may be nitromethane.
  • Such an organic small molecule (negative ion precursor) has a pKa ⁇ -13.5, which can form a stable negative ion in the zeolite synthesis liquid, and attack the Si-O/Al-O sites in the zeolite framework by SN 2 nucleophilic reaction to form a zeolite crystal.
  • Mesoporous structure is derived from an aza compound as a negative ion precursor; for example, the aza compound may be selected from one or more of 1H-1,2,3-triazole, 4H-1,2,4-triazole.
  • the carbanion may be
  • 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 from 2 to 50 nm, for example, from 2 to 10 nm, from 2 to 20 nm, from 5 to 30 nm, from 10 to 30 nm, from 15 to 40 nm, from 20 to 45 nm, from 25 to 50 nm, and the like.
  • the method of the invention comprises the following steps:
  • step b) solid-liquid separation of the mixture of step a) and drying of the solid product to obtain the above microporous mesoporous grade zeolite material.
  • the zeolite structure may be selected from any of the zeolite structures known to date. According to the contents of the International Zeolite Association's Structural Professional Committee on its website http://www.iza-online.org/, more than two hundred zeolite framework structures have been identified to date.
  • the preferred zeolite structure can be synthesized in the absence of organics, ie, in the presence of a microporous pore-forming agent, including but not limited to, such as LTA, FAU, SOD, CAN, BEA, CHA. , RTH, EMT, MFI, MEL, MOR, EON, etc.
  • the synthetic raw material (present in the zeolite synthetic liquid) of the microporous-mesoporal grade zeolitic material of the present invention comprises a silicon source, an aluminum source, a base, etc.
  • the silicon source may be, but not limited to, silica sol, silicon oxide, tetraethyl orthosilicate Ester, sodium metasilicate, n-butyl silicate, silicon carbide, etc.
  • the aluminum source may be, but not limited to, aluminum foil, aluminum powder, aluminum chloride, sodium metaaluminate, aluminum sulfate, aluminum nitrate, aluminum isopropoxide, Boehmite, aluminum hydroxide, etc.
  • the alkali may be, but not limited to, sodium hydroxide, potassium hydroxide, ammonium hydroxide, calcium hydroxide, aluminum hydroxide, silver hydroxide, lead hydroxide, zinc hydroxide, hydroxide Bismuth, potassium carbonate, sodium carbonate, ammonia, hydrazine,
  • the above microporous mesoporous grade zeolite material was subjected to XRD measurement using a Rigaku D/Max-2200 PC X-ray diffractometer. The spectrum is shown in Fig. 1a, and the LTA type zeolite can be clearly seen on the obtained powder diffraction pattern. All the characteristic peaks of the structure confirmed that the obtained solid was a crystalline LTA zeolite.
  • the above microporous mesoporous grade zeolite material was subjected to nitrogen adsorption desorption measurement at 77 K temperature by Micromeritics Tristar II 3020.
  • the adsorption desorption isotherm is shown in Fig. 1b, and the obtained adsorption isotherm was type IV, and the resulting desorption was obtained.
  • the isotherm forms a H3 hysteresis loop, which does not reach saturation at high P/P 0 pressure, proving the presence of mesopores.
  • the obtained nitrogen adsorption desorption isotherm was calculated by the BJH method, and the correlation diagram between the obtained dV/dlog(D) pore volume and the average pore diameter D p is shown in Fig.
  • the elemental content of the microporous mesoporous grade zeolite material was measured by HORIBA Jobin Yvon's inductively coupled plasma atomic emission spectrometry JY 2000-2 to obtain a Si/Al ratio of 1.15.
  • microporous mesoporous grade zeolite material was subjected to XRD measurement using a D/Max-2200 PC X-ray diffractometer of Rigaku, and the spectrum is shown in Fig. 2a, and the LTA type zeolite was clearly observed on the obtained powder diffraction pattern. All the characteristic peaks of the structure confirmed that the obtained solid was a crystalline LTA zeolite.
  • the above microporous mesoporous grade zeolite material was subjected to nitrogen adsorption desorption measurement at 77 K temperature.
  • the adsorption desorption isotherm was listed in Fig. 2b, and the obtained adsorption isotherm was type IV, and the resulting desorption isotherm formed H3 type hysteresis.
  • Line, the obtained nitrogen adsorption desorption isotherm is calculated by BJH method, and the correlation diagram between the obtained dV/dlog(D) pore volume and the average pore diameter D p is shown in Fig. 2c, and the obtained microporous-mesoporous grade zeolite material can be seen.
  • the pore peak is around 18 nm.
  • the Brunauer-Emmett-Teller specific surface area calculation of the adsorption data obtained in Fig. 2b gave the mesoporous BET specific surface area of the above microporous mesoporous grade zeolite material of 89 m 2 /g.
  • microporous-mesoporous grade zeolite material was subjected to XRD measurement using a D/Max-2200 PC X-ray diffractometer of Rigaku, and the spectrum is shown in Fig. 3a, and the LTA type zeolite was clearly observed on the obtained powder diffraction pattern. All the characteristic peaks of the structure confirmed that the obtained solid was a crystalline LTA zeolite.
  • the above microporous mesoporous grade zeolite material was subjected to nitrogen adsorption desorption measurement at 77 K temperature.
  • the adsorption desorption isotherm was listed in Fig. 3b, and the obtained adsorption isotherm was type IV, and the resulting desorption isotherm formed H3 type hysteresis.
  • Line, the obtained nitrogen adsorption desorption isotherm is calculated by BJH method, and the correlation diagram between the obtained dV/dlog(D) pore volume and the average pore diameter D p is shown in Fig. 3c, and the obtained microporous-mesoporous grade zeolite material can be seen.
  • the hole is around 14 nm.
  • the Brunauer-Emmett-Teller specific surface area calculation of the adsorption data obtained in Fig. 3b gave the mesoporous BET specific surface area of the above microporous mesoporous grade zeolite material of 132 m 2 /g.
  • microporous mesoporous grade zeolite material was subjected to XRD measurement using a Rigaku D/Max-2200 PC X-ray diffractometer, and the spectrum is shown in Fig. 4a, and the LTA type zeolite was clearly observed on the obtained powder diffraction pattern. All the characteristic peaks of the structure confirmed that the obtained solid was a crystalline LTA zeolite.
  • the above microporous mesoporous grade zeolite material was subjected to nitrogen adsorption desorption measurement at 77 K temperature.
  • the adsorption desorption isotherm was listed in Fig. 4b, and the obtained adsorption isotherm was type IV, and the resulting desorption isotherm formed H3 type hysteresis.
  • Line, the obtained nitrogen adsorption desorption isotherm was calculated by BJH method, and the correlation diagram between the obtained dV/dlog(D) pore volume and the average pore diameter D p is shown in Fig. 4c, and the obtained microporous-mesoporous grade zeolite material was observed.
  • the hole is around 14 nm.
  • the Brunauer-Emmett-Teller specific surface area calculation of the adsorption data obtained in Fig. 4b gave the mesoporous BET specific surface area of the above microporous mesoporous grade zeolite material of 103 m 2 /g.
  • microporous mesoporous grade zeolite material was subjected to XRD measurement using a D/Max-2200 PC X-ray diffractometer of Rigaku, and the spectrum is shown in Fig. 5a, and the LTA type zeolite was clearly observed on the obtained powder diffraction pattern. All the characteristic peaks of the structure confirmed that the obtained solid was a crystalline LTA zeolite.
  • the above microporous mesoporous grade zeolite material was subjected to nitrogen adsorption desorption measurement at 77K temperature, and the adsorption desorption isotherm was listed in Fig. 5b, and the obtained adsorption isotherm was type IV, and the resulting desorption isotherm formed H3 type hysteresis.
  • Line, the obtained nitrogen adsorption desorption isotherm was calculated by BJH method, and the correlation diagram between the obtained dV/dlog(D) pore volume and the average pore diameter D p is shown in Fig. 5c, and the obtained microporous-mesoporous grade zeolite material was observed.
  • the pore peak is around 18 nm.
  • the Brunauer-Emmett-Teller specific surface area calculation of the adsorption data obtained in Fig. 5b gave the mesoporous BET specific surface area of the above microporous mesoporous grade zeolite material of 70 m 2 /g.
  • microporous mesoporous grade zeolite material was subjected to XRD measurement using a D/Max-2200 PC X-ray diffractometer of Rigaku, and the spectrum is shown in Fig. 6a, and the LTA type zeolite was clearly observed on the obtained powder diffraction pattern. All the characteristic peaks of the structure confirmed that the obtained solid was a crystalline LTA zeolite.
  • the above microporous mesoporous grade zeolite material was subjected to nitrogen adsorption desorption measurement at 77 K temperature.
  • the adsorption desorption isotherm was listed in Fig. 6b, and the obtained adsorption isotherm was type IV, and the resulting desorption isotherm formed H3 type hysteresis.
  • Line, the obtained nitrogen adsorption desorption isotherm was calculated by BJH method, and the correlation diagram between the obtained dV/dlog(D) pore volume and the average pore diameter D p is shown in Fig. 6c, and the obtained microporous-mesoporous grade zeolite material was observed.
  • the pore range is around 14 nm.
  • the Brunauer-Emmett-Teller specific surface area calculation of the adsorption data obtained in Fig. 6b gave the mesoporous BET specific surface area of the above microporous mesoporous grade zeolite material of 105 m 2 /g.
  • microporous mesoporous grade zeolite material was subjected to XRD measurement using a D/Max-2200 PC X-ray diffractometer of Rigaku, and the spectrum is shown in Fig. 7a, and the FAU type zeolite was clearly observed on the obtained powder diffraction pattern. All characteristic peaks of the structure confirmed that the obtained solid was a crystalline FAU zeolite.
  • the above microporous mesoporous grade zeolite material was subjected to nitrogen adsorption desorption measurement at 77 K temperature.
  • the adsorption desorption isotherm was listed in Fig. 7b, and the obtained adsorption isotherm was type IV, and the resulting desorption isotherm formed H3 type hysteresis.
  • Line, the obtained nitrogen adsorption desorption isotherm was calculated by BJH method, and the correlation diagram between the obtained dV/dlog(D) pore volume and the average pore diameter D p is shown in Fig. 7c, and the obtained microporous-mesoporous grade zeolite material was observed.
  • the pores are around 31 nm.
  • the Brunauer-Emmett-Teller specific surface area calculation of the adsorption data obtained in Fig. 7b gave the mesoporous BET specific surface area of the above microporous mesoporous grade zeolite material of 600 m 2 /g.
  • the above microporous mesoporous grade zeolite material was observed by transmission electron microscopy. As shown in Fig. 7d, the apparent FAU crystal form and mesoporous structure were observed.
  • Example 8 Synthesis of microporous-mesoporous grade FAU zeolite using 1,2,4-triazole as a mesoporous agent
  • microporous mesoporous grade zeolite material was subjected to XRD measurement using a Rigaku D/Max-2200 PC X-ray diffractometer, and the spectrum is shown in Fig. 8a, and the FAU type zeolite was clearly observed on the obtained powder diffraction pattern. All characteristic peaks of the structure confirmed that the obtained solid was a crystalline FAU zeolite.
  • the above microporous mesoporous grade zeolite material was subjected to nitrogen adsorption desorption measurement at 77 K temperature.
  • the adsorption desorption isotherm was listed in Fig. 8b, and the obtained adsorption isotherm was type IV, and the resulting desorption isotherm formed H3 type hysteresis.
  • Line, the obtained nitrogen adsorption desorption isotherm was calculated by BJH method, and the correlation diagram between the obtained dV/dlog(D) pore volume and the average pore diameter D p is shown in Fig. 8c, and the obtained microporous-mesoporous grade zeolite material was observed.
  • the hole is around 24 nm.
  • the Brunauer-Emmett-Teller specific surface area calculation of the adsorption data obtained in Fig. 8b gave the mesoporous BET specific surface area of the above microporous mesoporous grade zeolite material of 610 m 2 /g.
  • the above microporous mesoporous grade zeolite material was observed by transmission electron microscopy. As shown in Fig. 8d, the apparent FAU crystal form and mesoporous structure were observed.
  • Figure 9 shows Sample 1 in Example 1, Sample 2 in Example 2, Sample 4 in Example 4, Sample 6 in Example 6 Microporous-Mesoporous Grade LTA-type Zeolite Material for Trypsin
  • the adsorption kinetics curves were 246, 243, 242, and 236 mg/g, respectively, and the adsorption kinetics curves of traditional microporous LTA zeolite CLTA samples against trypsin were compared.
  • the equilibrium immobilization was only 83 mg/ g.
  • microporous-mesoporous grade FAU zeolite prepared in Example 7 and Example 8 was ion-exchanged with a 0.7 M KNO 3 solution under magnetic stirring at 80 ° C for 2 hours, washed three times with water and centrifuged and dried. 2 g of the catalyst was added to 39.5 g of acetone and 6.5 g of furfural under stirring, and the temperature was raised to 100 ° C at a heating rate of 1.5 ° C per minute. The temperature was maintained for 2 hours, and the product was passed through Shimadzu GC equipped with an ion flame detector. Analysis by 2010 and HPLC.
  • Figure 10 is a graph comparing the acetone and furfural conversion of Sample 8 in Example 7 and Sample 8 in Example 7 with a conventional FAU catalyst CFAU, the layered FAU zeolite prepared by the process of the present invention having a conversion of more than 8%.

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Abstract

一种微孔-介孔层级沸石材料及其制备方法和用途，其制备方法包括：在包括硅源和铝源的沸石合成液中引入负离子前驱体作为有机致介孔剂，负离子前驱体能够在沸石合成液中形成稳定的有机负离子，有机负离子作为亲核试剂进攻沸石骨架中的Si-O/Al-O位点，使骨架部分溶解形成晶内介孔，得到微孔-介孔层级沸石材料，其包括沸石结构以及任选存在的寄居在沸石结构的孔道中的分散负离子前驱体，沸石结构包括微孔结构和介孔结构，并且至少部分介孔结构位于晶体内部。提出了一种全新的机理，避免了产生相分离、合成步骤复杂及成本昂贵等问题，而且后处理不需要通过煅烧除去模板，仅仅通过去离子水水洗即可获得多级孔沸石。

Description

一种微孔-介孔层级沸石材料及其制备方法和用途 技术领域
本发明涉及沸石材料技术领域，尤其涉及一种微孔-介孔层级沸石材料及其制备方法和用途。
背景技术
沸石(Zeolite)是由[TO 4]([SiO 4]、[AlO 4]或[PO 4]等)四面体之间通过共用顶点形成三维四连接骨架具有周期性孔道的硅铝酸盐晶体。由于其具有均匀的孔道结构，内在可调的酸性位点，优良的择形选择性以及拥有高的比表面积、热稳定性、化学稳定性和机械稳定性，沸石在催化、吸附和离子交换等领域具有广泛的应用。大部分的沸石都是需要在有机胺或季铵作为结构导向剂下合成，但是传统的微孔沸石孔径较小，通常小于1nm，在催化反应中会严重阻碍大分子在沸石孔道内部的扩散，容易造成沸石孔道的堵塞和积碳效应，使催化剂寿命大大降低。近十年来，为了解决上述扩散限制问题，人们在微孔沸石的基础上引入介孔结构，从而形成同时具有微孔和介孔的新型沸石体系。这种多级孔结构沸石不仅保留了传统沸石的优良特性，而且存在的介孔结构克服了尺径较大的分子的扩散限制，大大扩展了沸石材料的应用范围，可以在传统沸石材料无法实现的领域，如蛋白吸附、大分子催化、过渡金属离子交换等应用实现突破。
正是由于具有层级结构的微孔-介孔分子筛的极大优势，近十年来对于该类结构的合成方法也得到了极大的发展。制备方法主要分为两大类，即自上而下的合成策略和自下而上的后处理策略。自上而下合成法又称为后处理法，通常是使用强酸或强碱，甚至是辐射的极端条件，将沸石骨架中的T原子强行溶出脱除，通过牺牲部分结晶度和固体质量来产生层级结构。这种方法操作简单， 便于工业化，但是通过溶解使T原子脱离骨架势必会对沸石框架的结晶度和机械性能造成极大的破坏，得到的孔道结构也不易控制，因此后处理法具有很大的局限性。
自下而上合成法包括硬模板法和软模板法。硬模板法主要使用一些碳材料，包括珍珠炭黑、碳纳米管等，通过占据沸石内部的空间，最后通过煅烧除去模板而产生介孔结构。专利US 6998104 B2中利用碳气溶胶作为制孔剂得到了介孔范围在6-10nm的微孔-介孔沸石；专利CN 103265050 A中利用水热碳化处理碳源(蔗糖、果糖、糠醛)和硅源的混合溶液得到多级孔沸石分子筛微球。这种方法使用的模板生产成本较高，并且需要最后通过煅烧除去模板，会消耗大量的能量，不符合绿色化学和工业化的要求，因此该方法也具有很大的缺陷。软模板法主要使用表面活性剂和高分子材料。对于表面活性剂作为致孔剂来说，通常表面活性剂在沸石合成液中的自组装会与沸石成核生长产生竞争，从而容易导致相分离得到微孔沸石和无定形氧化硅混合物。对传统表面活性剂进行结构修饰，如引入有机硅烷基团，多个季胺基团等，可以增强表面活性剂与沸石骨架的相互作用力，避免了相分离的产生，疏水的长链烷烃占据沸石内部空间，通过煅烧即可得到多级孔沸石。专利CN103214003B将N,N-二甲基-N-[3-(三甲氧硅)丙基]氯化十八烷基铵(TPOAC)引入到Y型沸石分子筛的合成中，从而得到介孔Y型沸石分子筛；专利CN104402020A也是通过特殊设计的八铵基头Bola型表面活性剂合成中微双孔beta分子筛。高分子材料也可以作为致介孔剂来产生层级结构的沸石，专利CN1749162B中以高分子聚季铵为模板成功合成了微孔介孔复合孔道结构沸石。不管是表面活性剂还是高分子，都是介观模板，通过物理位阻作用封装在介孔孔道中，由于模板结构特殊，合成成本比较大，合成工艺难以放大。因此，目前的合成方法均具有一定的局限性。
发明内容
本发明利用有机小分子(负离子前驱体)作为致介孔剂，可以在沸石合成 液中形成稳定的负离子从而化学致介孔，本发明的方法简单节能、模板剂成本廉价易得，并且制得的微孔-介孔沸石用途广泛。
根据本发明的第一方面，本发明提供一种微孔-介孔层级沸石材料的制备方法，在包括硅源和铝源的沸石合成液中引入负离子前驱体作为有机致介孔剂，上述负离子前驱体能够在上述沸石合成液中形成稳定的有机负离子，上述有机负离子作为亲核试剂进攻沸石骨架中的Si-O/Al-O位点，使骨架部分溶解形成晶内介孔，得到微孔-介孔层级沸石材料，其包括沸石结构以及任选存在的寄居在上述沸石结构的孔道中的分散负离子前驱体，上述沸石结构包括微孔结构和介孔结构，并且至少部分上述介孔结构位于晶体内部。
优选地，上述有机负离子选自氧负离子、氮负离子和碳负离子中的一种或多种。
优选地，上述氧负离子来自作为负离子前驱体的有机酸或羟基化合物；更优选地，上述有机酸选自异丙酸、三氟乙酸、苯磺酸中的一种或多种，上述羟基化合物选自苯酚、六氟异丙醇、羟基苯丙三唑中的一种或多种。
优选地，上述氮负离子来自作为负离子前驱体的氮杂化合物；更优选地，上述氮杂化合物选自1H-1,2,3-三氮唑、4H-1,2,4-三氮唑中的一种或多种。
优选地，上述碳负离子来自作为负离子前驱体的碳杂化合物；更优选地，上述碳杂化合物为硝基甲烷。
优选地，上述介孔结构全部位于晶体内部。
优选地，上述介孔结构的孔径介于2～50nm。
优选地，上述方法包括以下步骤：
a)将负离子前驱体作为有机致介孔剂引入包括硅源和铝源的沸石合成液中，在温度为0-300℃之间，压力为常压至20bar之间进行合成反应；
b)对步骤a)的混合物进行固液分离，并干燥固体产物得到上述微孔-介孔 层级沸石材料。
根据本发明的第二方面，本发明提供一种微孔-介孔层级沸石材料，包括沸石结构以及任选存在的寄居在上述沸石结构的孔道中的分散负离子前驱体，上述沸石结构包括微孔结构和介孔结构，并且至少部分上述介孔结构位于晶体内部，上述微孔-介孔层级沸石材料通过如下方法制备得到：
在包括硅源和铝源的沸石合成液中引入负离子前驱体作为有机致介孔剂，上述负离子前驱体能够在上述沸石合成液中形成稳定的有机负离子，上述有机负离子作为亲核试剂进攻沸石骨架中的Si-O/Al-O位点，使骨架部分溶解形成晶内介孔，得到上述微孔-介孔层级沸石材料。
优选地，上述有机负离子选自氧负离子、氮负离子和碳负离子中的一种或多种。
优选地，上述氧负离子来自作为负离子前驱体的有机酸或羟基化合物；更优选地，上述有机酸选自异丙酸、三氟乙酸、苯磺酸中的一种或多种，上述羟基化合物选自苯酚、六氟异丙醇、羟基苯丙三唑中的一种或多种。
优选地，上述氮负离子来自作为负离子前驱体的氮杂化合物；更优选地，上述氮杂化合物选自1H-1,2,3-三氮唑、4H-1,2,4-三氮唑中的一种或多种。
优选地，上述碳负离子来自作为负离子前驱体的碳杂化合物；更优选地，上述碳杂化合物为硝基甲烷。
优选地，上述介孔结构全部位于晶体内部。
优选地，上述介孔结构的孔径介于2～50nm。
根据本发明的第三方面，本发明提供上述第二方面的微孔-介孔层级沸石材料作为催化剂、吸附剂或离子交换剂的用途。
本发明的方法与现有技术中合成多级孔沸石的方法相比，利用有机小分子(负离子前驱体)作为致介孔剂合成微孔-介孔层级沸石，提出了一种全新的机 理。该方法避免了现有技术中硬模板和软模板法容易产生相分离、合成步骤复杂及成本昂贵等问题，而且后处理不需要通过煅烧除去模板，仅仅通过去离子水水洗即可获得多级孔沸石。通过对水洗液进行回收处理，有机小分子可以进行多次循环使用，节约了成本，同时也符合绿色化学的要求。
附图说明
图1为实施例1制备的微孔-介孔层级沸石材料的(a)XRD衍射图；(b)氮气吸附-脱附等温线；(c)介孔孔径分布曲线；(d)扫描电镜照片；和(e)透射电镜照片；
图2为实施例2制备的微孔-介孔层级沸石材料的(a)XRD衍射图；(b)氮气吸附-脱附等温线；(c)介孔孔径分布曲线；(d)扫描电镜照片；和(e)透射电镜照片；
图3为实施例3制备的微孔-介孔层级沸石材料的(a)XRD衍射图；(b)氮气吸附-脱附等温线；(c)介孔孔径分布曲线；和(d)扫描电镜照片；
图4为实施例4制备的微孔-介孔层级沸石材料的(a)XRD衍射图；(b)氮气吸附-脱附等温线；(c)介孔孔径分布曲线；和(d)扫描电镜照片；
图5为实施例5制备的微孔-介孔层级沸石材料的(a)XRD衍射图；(b)氮气吸附-脱附等温线；(c)介孔孔径分布曲线；和(d)扫描电镜照片；
图6为实施例6制备的微孔-介孔层级沸石材料的(a)XRD衍射图；(b)氮气吸附-脱附等温线；(c)介孔孔径分布曲线；和(d)扫描电镜照片；
图7为实施例7制备的微孔-介孔层级沸石材料的(a)XRD衍射图；(b)氮气吸附-脱附等温线；(c)介孔孔径分布曲线；和(d)透射电镜照片；
图8为实施例8制备的微孔-介孔层级沸石材料的(a)XRD衍射图；(b)氮气吸附-脱附等温线；(c)介孔孔径分布曲线；和(d)透射电镜照片；
图9为实施例1中的样品1，实施例2中的样品2，实施例4中的样品4，实施例6中的样品6微孔-介孔层级LTA型沸石材料对于胰蛋白酶的吸附动力学 曲线；
图10为实施例7中样品7和实施例8中的样品8的糠醛转化率对比图。
具体实施方式
下面将更详细地描述本发明的微孔-介孔层级沸石材料及其制备方法和用途。除非另外定义，否则详述中使用的技术和科学术语具有与本发明领域的技术人员理解相同的含义。
本发明开发出一种全新的策略来合成具有层级结构的微孔-介孔沸石晶体，本发明利用有机小分子(负离子前驱体)作为致介孔剂，可以在沸石合成液中形成稳定的负离子从而化学致介孔，负离子前驱体包括但不限于氧负离子、氮负离子和碳负离子前驱体，它们形成的负离子能够作为亲核试剂通过SN 2过程进攻沸石骨架中的Si-O/Al-O位点，从而在线刻蚀使骨架部分溶解形成晶内介孔。本发明的制备方法简单节能、模板剂成本廉价易得，并且制得的微孔-介孔沸石用途广泛。
具体而言，本发明的微孔-介孔层级沸石材料的制备方法是，在包括硅源和铝源的沸石合成液中引入负离子前驱体作为有机致介孔剂，上述负离子前驱体能够在上述沸石合成液中形成稳定的有机负离子，上述有机负离子作为亲核试剂进攻沸石骨架中的Si-O/Al-O位点，使骨架部分溶解形成晶内介孔，得到微孔-介孔层级沸石材料，其包括沸石结构以及任选存在的寄居在上述沸石结构的孔道中的分散负离子前驱体，上述沸石结构包括微孔结构和介孔结构，并且至少部分上述介孔结构位于晶体内部。
需要说明的是，通过水洗可以除去有机小分子(负离子前驱体)，因此，根据水洗程度不同，本发明制备的微孔-介孔层级沸石材料可能存在寄居在上述沸石结构的孔道中的分散负离子前驱体，也可能不存在这样的寄居在上述沸石结构的孔道中的分散负离子前驱体，这就是所谓“任选存在的”的含义。
本发明中，有机负离子包括但不限于氧负离子、氮负离子和碳负离子。其中，氧负离子可以来自作为负离子前驱体的有机酸或羟基化合物；例如，有机酸可以选自异丙酸、三氟乙酸、苯磺酸中的一种或多种，羟基化合物可以选自苯酚、六氟异丙醇、羟基苯丙三唑中的一种或多种。氮负离子可以来自作为负离子前驱体的氮杂化合物；例如，氮杂化合物可以选自1H-1,2,3-三氮唑、4H-1,2,4-三氮唑中的一种或多种。碳负离子可以来自作为负离子前驱体的碳杂化合物；例如，碳杂化合物可以为硝基甲烷。这样的有机小分子(负离子前驱体)的pKa<～13.5，可以在沸石合成液中形成稳定的负离子，通过SN 2亲核反应进攻沸石骨架中的Si-O/Al-O位点形成沸石晶体内介孔结构。
本发明的微孔-介孔层级沸石材料中，至少部分介孔结构位于晶体内部，然而，作为优选实施方式，介孔结构全部位于晶体内部。介孔结构的孔径一般介于2～50nm，例如，2-10nm、2-20nm、5-30nm、10-30nm、15-40nm、20-45nm、25-50nm等。
在一个优选的实施例中，本发明的方法包括以下步骤：
a)将负离子前驱体作为有机致介孔剂引入包括硅源和铝源的沸石合成液中，在温度为0-300℃之间，压力为常压至20bar之间进行合成反应；
b)对步骤a)的混合物进行固液分离，并干燥固体产物得到上述微孔-介孔层级沸石材料。
在本发明中，沸石结构可以选自目前所知的任何沸石结构。根据国际沸石协会的结构专业委员会在其网站http://www.iza-online.org/公布的内容，迄今已确认了两百多种沸石骨架结构。为了避免后续的煅烧过程，优选的沸石结构可在无有机物存在的条件下合成，即可在无微孔制孔剂存在下结晶，包含但不限于如LTA、FAU、SOD、CAN、BEA、CHA、RTH、EMT、MFI、MEL、MOR、EON等。
本发明的微孔-介孔层级沸石材料的合成原料(存在于沸石合成液中)包括 硅源、铝源、碱等，硅源可以是但不限于硅溶胶、氧化硅、原硅酸四乙酯、偏硅酸钠、硅酸正丁酯、碳化硅等，铝源可以是但不限于铝箔、铝粉、氯化铝、偏铝酸钠、硫酸铝、硝酸铝、异丙醇铝、拟薄水铝石、氢氧化铝等，碱可以是但不限于氢氧化钠、氢氧化钾、氢氧化铵、氢氧化钙、氢氧化铝、氢氧化银、氢氧化铅、氢氧化锌、氢氧化铯、碳酸钾、碳酸钠、氨水、联氨、羟氨、液氨等。
以下通过具体实施例详细说明本发明的技术方案和效果，应当理解，实施例仅是示例性的，不能理解为对本发明保护范围的限制。
实施例1三氟乙酸作致介孔剂合成微孔-介孔层级LTA沸石
将12.54ml硅溶胶(25％)溶解于10ml去离子水中，机械搅拌15分钟以上使其分散均匀，标记为硅源；将2.0g氢氧化钠以及4.1g偏铝酸钠溶解于35ml去离子水中，搅拌10分钟至澄清，随后将2.85g三氟乙酸加入。最后将上述溶液加入到硅源中，持续搅拌，室温老化3小时后开始加热，100℃下反应18小时。反应结束后收集反应液离心处理，水洗收集白色固体，60℃烘干，得到多级孔LTA沸石。
对上述微孔-介孔层级沸石材料采用Rigaku公司的D/Max-2200 PC X-射线衍射仪进行XRD测量，谱图列于图1a，所得粉末衍射图上均可清晰地看到LTA型沸石结构所有特征峰，证实所得固体为结晶态的LTA沸石。
对上述微孔-介孔层级沸石材料采用Micromeritics公司的Tristar II 3020进行77K温度下的氮气吸附脱附测量，吸附脱附等温线列于图1b，所得吸附等温线为IV型，与所得脱附等温线形成H3型滞后回线，在高的P/P 0压力下，未达到饱和，证明介孔的存在。对所得氮气吸附脱附等温线进行BJH方法计算，所得dV/dlog(D)孔体积与平均孔直径D p的关联图列于图1c，可见所得微孔-介孔层级沸石材料的介孔范围在9-20nm之间。对图1b得到的吸附数据进行Brunauer-Emmett-Teller比表面积计算，得到上述微孔-介孔层级沸石材料的BET 比表面积为113m 2/g，介孔孔容0.05cm 3/g。采用HORIBA JobinYvon公司的电感耦合等离子体原子发射光谱JY 2000-2对微孔-介孔层级沸石材料的元素含量进行测得，得到其Si/Al比为1.15。
对上述微孔-介孔层级沸石材料采用JEOL公司的JSM-7800F进行未涂金样品的扫描电子显微镜(SEM)观察，列于图1d，可见明显LTA晶型和介孔结构。对上述微孔-介孔层级沸石材料进行透射电子显微镜观察，结果列于图1e，可见明显介孔结构。
实施例2对甲苯磺酸作致介孔剂合成微孔-介孔层级LTA沸石
将12.54ml硅溶胶(25％)溶解于10ml去离子水中，机械搅拌15分钟以上使其分散均匀，标记为硅源；将2.0g氢氧化钠以及4.1g偏铝酸钠溶解于35ml去离子水中，搅拌10分钟至澄清，随后将2.353g对甲苯磺酸加入。最后将上述溶液加入到硅源中，持续搅拌，室温老化3小时后开始加热，100℃下反应18小时。反应结束后收集反应液离心处理，水洗收集白色固体，60℃烘干，得到多级孔LTA沸石。
对上述微孔-介孔层级沸石材料采用Rigaku公司的D/Max-2200 PC X-射线衍射仪进行XRD测量，谱图列于图2a，所得粉末衍射图上均可清晰地看到LTA型沸石结构所有特征峰，证实所得固体为结晶态的LTA沸石。
对上述微孔-介孔层级沸石材料进行77K温度下的氮气吸附脱附测量，吸附脱附等温线列于图2b，所得吸附等温线为IV型，与所得脱附等温线形成H3型滞后回线，对所得氮气吸附脱附等温线进行BJH方法计算，所得dV/dlog(D)孔体积与平均孔直径D p的关联图列于图2c，可见所得微孔-介孔层级沸石材料的介孔峰在18nm左右。对图2b得到的吸附数据进行Brunauer-Emmett-Teller比表面积计算，得到上述微孔-介孔层级沸石材料的介孔BET比表面积为89m 2/g。
对上述微孔-介孔层级沸石材料采用JEOL公司的JSM-7800F进行未涂金样品的扫描电子显微镜(SEM)观察，列于图2d，可见明显LTA晶型和介孔结构。 对上述微孔-介孔层级沸石材料进行透射电子显微镜观察，结果列于图2e，可见明显介孔结构。
实施例3六氟异丙醇作致介孔剂合成微孔-介孔层级LTA沸石
将12.54ml硅溶胶(25％)溶解于10ml去离子水中，机械搅拌15分钟以上使其分散均匀，标记为硅源；将2.0g氢氧化钠以及4.1g偏铝酸钠溶解于35ml去离子水中，搅拌10分钟至澄清，随后将4.2g六氟异丙醇加入。最后将上述溶液加入到硅源中，持续搅拌，室温老化3小时后开始加热，100℃下反应18小时。反应结束后收集反应液离心处理，水洗收集白色固体，60℃烘干，得到多级孔LTA沸石。
对上述微孔-介孔层级沸石材料采用Rigaku公司的D/Max-2200 PC X-射线衍射仪进行XRD测量，谱图列于图3a，所得粉末衍射图上均可清晰地看到LTA型沸石结构所有特征峰，证实所得固体为结晶态的LTA沸石。
对上述微孔-介孔层级沸石材料进行77K温度下的氮气吸附脱附测量，吸附脱附等温线列于图3b，所得吸附等温线为IV型，与所得脱附等温线形成H3型滞后回线，对所得氮气吸附脱附等温线进行BJH方法计算，所得dV/dlog(D)孔体积与平均孔直径D p的关联图列于图3c，可见所得微孔-介孔层级沸石材料的介孔在14nm左右。对图3b得到的吸附数据进行Brunauer-Emmett-Teller比表面积计算，得到上述微孔-介孔层级沸石材料的介孔BET比表面积为132m 2/g。
对上述微孔-介孔层级沸石材料采用JEOL公司的JSM-7800F进行未涂金样品的扫描电子显微镜(SEM)观察，列于图3d，可见明显LTA晶型和介孔结构。
实施例4 1,2,3-三氮唑作致介孔剂合成微孔-介孔层级LTA沸石
将12.54ml硅溶胶(25％)溶解于10ml去离子水中，机械搅拌15分钟以上使其分散均匀，标记为硅源；将2.0g氢氧化钠以及4.1g偏铝酸钠溶解于35ml去离子水中，搅拌10分钟至澄清，随后将1.73g 1,2,3-三氮唑加入。最后将上述溶液加入到硅源中，持续搅拌，室温老化3小时后开始加热，100℃下反应18小 时。反应结束后收集反应液离心处理，水洗收集白色固体，60℃烘干，得到多级孔LTA沸石。
对上述微孔-介孔层级沸石材料采用Rigaku公司的D/Max-2200 PC X-射线衍射仪进行XRD测量，谱图列于图4a，所得粉末衍射图上均可清晰地看到LTA型沸石结构所有特征峰，证实所得固体为结晶态的LTA沸石。
对上述微孔-介孔层级沸石材料进行77K温度下的氮气吸附脱附测量，吸附脱附等温线列于图4b，所得吸附等温线为IV型，与所得脱附等温线形成H3型滞后回线，对所得氮气吸附脱附等温线进行BJH方法计算，所得dV/dlog(D)孔体积与平均孔直径D p的关联图列于图4c，可见所得微孔-介孔层级沸石材料的介孔在14nm左右。对图4b得到的吸附数据进行Brunauer-Emmett-Teller比表面积计算，得到上述微孔-介孔层级沸石材料的介孔BET比表面积为103m 2/g。
对上述微孔-介孔层级沸石材料采用JEOL公司的JSM-7800F进行未涂金样品的扫描电子显微镜(SEM)观察，列于图4d，可见明显LTA晶型和介孔结构。
实施例5 1,2,4-三氮唑作致介孔剂合成微孔-介孔层级LTA沸石
将12.54ml硅溶胶(25％)溶解于10ml去离子水中，机械搅拌15分钟以上使其分散均匀，标记为硅源；将2.0g氢氧化钠以及4.1g偏铝酸钠溶解于35ml去离子水中，搅拌10分钟至澄清，随后将1.73g 1,2,4-三氮唑加入。最后将上述溶液加入到硅源中，持续搅拌，室温老化3小时后开始加热，100℃下反应18小时。反应结束后收集反应液离心处理，水洗收集白色固体，60℃烘干，得到多级孔LTA沸石。
对上述微孔-介孔层级沸石材料采用Rigaku公司的D/Max-2200 PC X-射线衍射仪进行XRD测量，谱图列于图5a，所得粉末衍射图上均可清晰地看到LTA型沸石结构所有特征峰，证实所得固体为结晶态的LTA沸石。
对上述微孔-介孔层级沸石材料进行77K温度下的氮气吸附脱附测量，吸附脱附等温线列于图5b，所得吸附等温线为IV型，与所得脱附等温线形成H3型 滞后回线，对所得氮气吸附脱附等温线进行BJH方法计算，所得dV/dlog(D)孔体积与平均孔直径D p的关联图列于图5c，可见所得微孔-介孔层级沸石材料的介孔峰在18nm左右。对图5b得到的吸附数据进行Brunauer-Emmett-Teller比表面积计算，得到上述微孔-介孔层级沸石材料的介孔BET比表面积为70m 2/g。
对上述微孔-介孔层级沸石材料采用JEOL公司的JSM-7800F进行未涂金样品的扫描电子显微镜(SEM)观察，列于图5d，可见明显LTA晶型和介孔结构。
实施例6硝基甲烷作致介孔剂合成微孔-介孔层级LTA沸石
将12.54ml硅溶胶(25％)溶解于10ml去离子水中，机械搅拌15分钟以上使其分散均匀，标记为硅源；将2.0g氢氧化钠以及4.1g偏铝酸钠溶解于35ml去离子水中，搅拌10分钟至澄清，随后将1.526g硝基甲烷加入。最后将上述溶液加入到硅源中，持续搅拌，室温老化3小时后开始加热，100℃下反应18小时。反应结束后收集反应液离心处理，水洗收集白色固体，60℃烘干，得到多级孔LTA沸石。
对上述微孔-介孔层级沸石材料采用Rigaku公司的D/Max-2200 PC X-射线衍射仪进行XRD测量，谱图列于图6a，所得粉末衍射图上均可清晰地看到LTA型沸石结构所有特征峰，证实所得固体为结晶态的LTA沸石。
对上述微孔-介孔层级沸石材料进行77K温度下的氮气吸附脱附测量，吸附脱附等温线列于图6b，所得吸附等温线为IV型，与所得脱附等温线形成H3型滞后回线，对所得氮气吸附脱附等温线进行BJH方法计算，所得dV/dlog(D)孔体积与平均孔直径D p的关联图列于图6c，可见所得微孔-介孔层级沸石材料的介孔范围在14nm左右。对图6b得到的吸附数据进行Brunauer-Emmett-Teller比表面积计算，得到上述微孔-介孔层级沸石材料的介孔BET比表面积为105m 2/g。
对上述微孔-介孔层级沸石材料采用JEOL公司的JSM-7800F进行未涂金样品的扫描电子显微镜(SEM)观察，列于图6d，可见明显LTA晶型和介孔结构。
实施例7苯酚作为致介孔剂合成微孔-介孔层级FAU沸石
将1.9g氢氧化钠以及4.1g偏铝酸钠溶解于30ml去离子水中，搅拌至澄清，标记为铝源；将2.35g苯酚溶解于6ml去离子水中，超声分散，标记为添加物。将铝源和添加物溶液滴加到硅源中，持续搅拌，室温老化24小时后开始加热，设定温度为90℃。待温度升至90℃开始计时，48小时后，离心处理，收集白色固体，60℃烘干。
对上述微孔-介孔层级沸石材料采用Rigaku公司的D/Max-2200 PC X-射线衍射仪进行XRD测量，谱图列于图7a，所得粉末衍射图上均可清晰地看到FAU型沸石结构所有特征峰，证实所得固体为结晶态的FAU沸石。
对上述微孔-介孔层级沸石材料进行77K温度下的氮气吸附脱附测量，吸附脱附等温线列于图7b，所得吸附等温线为IV型，与所得脱附等温线形成H3型滞后回线，对所得氮气吸附脱附等温线进行BJH方法计算，所得dV/dlog(D)孔体积与平均孔直径D p的关联图列于图7c，可见所得微孔-介孔层级沸石材料的介孔在31nm左右。对图7b得到的吸附数据进行Brunauer-Emmett-Teller比表面积计算，得到上述微孔-介孔层级沸石材料的介孔BET比表面积为600m 2/g。对上述微孔-介孔层级沸石材料进行透射电子显微镜进行观察，列于图7d，可见明显FAU晶型和介孔结构。
实施例8 1,2,4-三氮唑作为致介孔剂合成微孔-介孔层级FAU沸石
将1.9g氢氧化钠以及4.1g偏铝酸钠溶解于30ml去离子水中，搅拌至澄清，标记为铝源；将1.73g 1,2,4-三氮唑溶解于6ml去离子水中，超声分散，标记为添加物。将铝源和添加物溶液滴加到硅源中，持续搅拌，室温老化24小时后开始加热，设定温度为90℃。待温度升至90℃开始计时，48小时后，离心处理，收集白色固体，60℃烘干。
对上述微孔-介孔层级沸石材料采用Rigaku公司的D/Max-2200 PC X-射线衍射仪进行XRD测量，谱图列于图8a，所得粉末衍射图上均可清晰地看到FAU 型沸石结构所有特征峰，证实所得固体为结晶态的FAU沸石。
对上述微孔-介孔层级沸石材料进行77K温度下的氮气吸附脱附测量，吸附脱附等温线列于图8b，所得吸附等温线为IV型，与所得脱附等温线形成H3型滞后回线，对所得氮气吸附脱附等温线进行BJH方法计算，所得dV/dlog(D)孔体积与平均孔直径D p的关联图列于图8c，可见所得微孔-介孔层级沸石材料的介孔在24nm左右。对图8b得到的吸附数据进行Brunauer-Emmett-Teller比表面积计算，得到上述微孔-介孔层级沸石材料的介孔BET比表面积为610m 2/g。对上述微孔-介孔层级沸石材料进行透射电子显微镜进行观察，列于图8d，可见明显FAU晶型和介孔结构。
应用例1微孔-介孔层级LTA沸石用于酶吸附
将80mg新鲜的胰蛋白酶溶解于10ml pH＝6.0的磷酸盐(PBS)缓冲液中，冰水浴保存。用0.22μm PTFE膜对上清液进行过滤，加入100mg的微孔-介孔层级LTA沸石材料，在4℃，600rpm磁力搅拌中进行胰蛋白酶吸附实验。在吸附过程中，不同时间段取300μl样品离心并取上清液在NanoDrop 2000c(Thermo Scientific)仪器上进行胰蛋白酶浓度的测量，通过减除法计算此时介孔沸石吸附的胰蛋白酶的负载量。
图9给出了实施例1中的样品1，实施例2中的样品2，实施例4中的样品4，实施例6中的样品6微孔-介孔层级LTA型沸石材料对于胰蛋白酶的吸附动力学曲线，其平衡固载量分别为246、243、242、236mg/g，并对比了传统微孔LTA沸石CLTA样品对胰蛋白酶的吸附动力学曲线，其平衡固载量仅为83mg/g。
应用例2微孔-介孔层级FAU沸石用于糠醛与丙酮的缩合反应催化剂
将实施例7和实施例8中制得的微孔-介孔层级FAU沸石用0.7M KNO 3溶液在80摄氏度磁力搅拌下离子交换2小时，水洗三次离心分离并干燥。取2g催化剂在搅拌下加入到39.5g丙酮和6.5g糠醛中，以每分钟1.5摄氏度的加热速度升温至100摄氏度，保持该温度反应2小时，产物通过配有离子火焰检测器的岛津GC-2010和HPLC进行分析。图10为实施例7中样品7和实施例8中 的样品8丙酮和糠醛转化率与传统FAU催化剂CFAU的对比图，通过本发明方法制得的层级FAU沸石具有超过8％的转化率。
以上内容是结合具体的实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干简单推演或替换，都应当视为属于本发明的保护范围。

Claims (22)

  1. 一种微孔-介孔层级沸石材料的制备方法，其特征在于，在包括硅源和铝源的沸石合成液中引入负离子前驱体作为有机致介孔剂，所述负离子前驱体能够在所述沸石合成液中形成稳定的有机负离子，所述有机负离子作为亲核试剂进攻沸石骨架中的Si-O/Al-O位点，使骨架部分溶解形成晶内介孔，得到微孔-介孔层级沸石材料，其包括沸石结构以及任选存在的寄居在所述沸石结构的孔道中的分散负离子前驱体，所述沸石结构包括微孔结构和介孔结构，并且至少部分所述介孔结构位于晶体内部。
  2. 根据权利要求1所述的制备方法，其特征在于，所述有机负离子选自氧负离子、氮负离子和碳负离子中的一种或多种。
  3. 根据权利要求2所述的制备方法，其特征在于，所述氧负离子来自作为负离子前驱体的有机酸或羟基化合物。
  4. 根据权利要求3所述的制备方法，其特征在于，所述有机酸选自异丙酸、三氟乙酸、苯磺酸中的一种或多种，所述羟基化合物选自苯酚、六氟异丙醇、羟基苯丙三唑中的一种或多种。
  5. 根据权利要求2所述的制备方法，其特征在于，所述氮负离子来自作为负离子前驱体的氮杂化合物。
  6. 根据权利要求5所述的制备方法，其特征在于，所述氮杂化合物选自1H-1,2,3-三氮唑、4H-1,2,4-三氮唑中的一种或多种。
  7. 根据权利要求2所述的制备方法，其特征在于，所述碳负离子来自作为负离子前驱体的碳杂化合物。
  8. 根据权利要求7所述的制备方法，其特征在于，所述碳杂化合物为硝基甲烷。
  9. 根据权利要求1所述的制备方法，其特征在于，所述介孔结构全部位于晶体内部。
  10. 根据权利要求1所述的制备方法，其特征在于，所述介孔结构的孔径介于2～50nm。
  11. 根据权利要求1所述的制备方法，其特征在于，所述方法包括以下步骤：
    a)将负离子前驱体作为有机致介孔剂引入包括硅源和铝源的沸石合成液中，在温度为0-300℃之间，压力为常压至20bar之间进行合成反应；
    b)对步骤a)的混合物进行固液分离，并干燥固体产物得到所述微孔-介孔层级沸石材料。
  12. 一种微孔-介孔层级沸石材料，其特征在于，所述微孔-介孔层级沸石材料包括沸石结构以及任选存在的寄居在所述沸石结构的孔道中的分散负离子前驱体，所述沸石结构包括微孔结构和介孔结构，并且至少部分所述介孔结构位于晶体内部，所述微孔-介孔层级沸石材料通过如下方法制备得到：
    在包括硅源和铝源的沸石合成液中引入负离子前驱体作为有机致介孔剂，所述负离子前驱体能够在所述沸石合成液中形成稳定的有机负离子，所述有机负离子作为亲核试剂进攻沸石骨架中的Si-O/Al-O位点，使骨架部分溶解形成晶内介孔，得到所述微孔-介孔层级沸石材料。
  13. 根据权利要求12所述的微孔-介孔层级沸石材料，其特征在于，所述有机负离子选自氧负离子、氮负离子和碳负离子中的一种或多种。
  14. 根据权利要求13所述的制备方法，其特征在于，所述氧负离子来自作为负离子前驱体的有机酸或羟基化合物。
  15. 根据权利要求14所述的制备方法，其特征在于，所述有机酸选自异丙酸、三氟乙酸、苯磺酸中的一种或多种，所述羟基化合物选自苯酚、六氟异丙醇、羟基苯丙三唑中的一种或多种。
  16. 根据权利要求13所述的制备方法，其特征在于，所述氮负离子来自作为负离子前驱体的氮杂化合物。
  17. 根据权利要求16所述的制备方法，其特征在于，所述氮杂化合物选自1H-1,2,3-三氮唑、4H-1,2,4-三氮唑中的一种或多种。
  18. 根据权利要求13所述的制备方法，其特征在于，所述碳负离子来自作为负离子前驱体的碳杂化合物。
  19. 根据权利要求18所述的制备方法，其特征在于，所述碳杂化合物为硝基甲烷。
  20. 根据权利要求12所述的微孔-介孔层级沸石材料，其特征在于，所述介孔结构全部位于晶体内部。
  21. 根据权利要求12所述的微孔-介孔层级沸石材料，其特征在于，所述介孔结构的孔径介于2～50nm。
  22. 如权利要求12所述的微孔-介孔层级沸石材料作为催化剂、吸附剂或离子交换剂的用途。
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