WO2017124304A1 - Amino acid-zeolite composite material, microporous-mesoporous level zeolite material converted therefrom, and preparation method therefor and use thereof - Google Patents

Abstract

Disclosed are an amino acid-zeolite composite material, a microporous-mesoporous level zeolite material converted therefrom, and a preparation method therefor and a use thereof. The amino acid-zeolite composite material comprises a zeolite structure and dispersed amino acid molecules deposited in the pore structure 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 located inside a crystal. The amino acid-zeolite composite material and the microporous-mesoporous level zeolite material converted therefrom have an extensive application prospect in protein adsorption, catalysis and/or large-scale ion exchange.

Description

Amino acid-zeolite composite material, converted microporous-mesopal layer zeolite material thereof, preparation method and use thereof Technical field

The invention relates to the technical field of zeolitic materials, in particular to an amino acid-zeolite composite material, a converted microporous-mesoporous layer zeolite material thereof, a preparation method thereof and use thereof.

Background technique

Zeolites, ie molecular sieves in the narrow sense, are generally defined as aluminosilicates having a microporous structure. They generate periodic channels by forming a three-dimensional four-joined skeleton between the tetrahedrons of [TO ₄ ] ([SiO ₄ ], [AlO ₄ ] or [PO ₄ ], etc.) by sharing the vertices. Zeolites possess high specific surface area, thermal stability, chemical stability and mechanical stability due to inorganic crystals having a uniform microporous structure. Together with more than 200 zeolite structures that have been discovered, zeolite materials have adjustable acid sites, pore sizes, and hydrophilicity, and are widely used in the fields of catalysis, adsorption, and ion exchange. However, zeolites are only characterized by microporous (usually less than 1 nm) properties, which limit their steric hindrance and diffusion limitations for slightly larger molecules. For example, the smallest water-soluble protein size has been above 2 nm, and the traditional zeolite structure cannot achieve the payload and application of the protein. In the past decade, a new class of zeolitic materials has expanded mesoporous structure in addition to its inherent microporous structure. The microporous-mesoporous layer zeolite material overcomes the diffusion limitation of molecules with large diameter and greatly expands the application range of zeolite materials, and can be used in fields where conventional zeolite materials cannot be realized, such as protein adsorption, macromolecular catalysis, transition metals. Breakthroughs such as ion exchange. At the same time, due to the preservation of the stability, crystal form, and long-range order of the inorganic zeolite material, the application effect in these fields is significantly better than that of the organic mesoporous material and the amorphous silica molecular sieve material. The hierarchical pore structure also provides an ideal contact space for further loading of the active material or for functional modification, better preserving the self-characteristics of the adsorbed material.

It is precisely because of the great advantages of microporous-mesoporous molecular sieves with hierarchical structure that the research on such structures has shown an exponential growth trend in the past decade. According to the review of the latest Chem. Sci. Rev., 2015, 44, 7234, the preparation method of the hierarchical structure zeolite material can be divided into a direct preparation method and a post-treatment method. The post-treatment method 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, and to produce a hierarchical structure by sacrificing partial crystallinity and solid mass. For example, a series of patents published by Rive Technology, Inc. in the United States, US 20150182953 A1, US 20130183231 A1, US 20130183229 A1, US 20110171121 A1, US 8685875 B2, etc. all adopt a post-treatment strategy of removing T atoms in the skeleton by acid and alkali. Forcibly dissolving the atoms in the skeleton will inevitably destroy the structure and mechanical properties of the molecular sieve, and the damage usually occurs in the weak part of the crystal. The pores are usually on the surface of the crystal, not integrated with the crystal structure, and the uniformity of the pores cannot be guaranteed. In order to reduce crystallinity and solidity The degree of loss of body yield, they improved the post-treatment method, adding surfactant to the treatment liquid, but the addition of surfactant increased the treatment cost, and the added surfactant also needs to be removed by calcination, increasing the process. Energy consumption and pollutant emissions. According to a review by Chem. Soc. Rev., 2013, 42, 3671, this strategy usually only deals with zeolites with a Si/Al ratio between 10 and 100, and for a higher order factor of porous zeolite, Si/ The range of Al is narrower. Although the formation of mesopores increases the accessibility of some slightly larger molecules in such molecular sieves to nearly 1, these are based on the destruction of the core framework of the zeolite, which has a 5-80% reduction in acidic sites. Therefore, the limitations of the post-processing method are very large.

The direct preparation method is mostly carried out by using a templating agent, and is divided into a hard template and a soft template. The templating agent used includes a carbon material, a surfactant material, and a polymer material. In US Pat. No. 6,998,104 B2, 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 CN103265050A, a carbon source (sucrose, fructose, furfural) and a silicon source are treated by hydrothermal carbonization. The mixed solution obtains a carbon-silicon composite bulk material, which is subjected to high-temperature carbonization, crystallization, and calcination to obtain a multi-stage pore zeolite molecular sieve microsphere. However, carbon templating agents such as pearl carbon black and carbon nanotubes have high cost and high hydrophobicity, and are not compatible with the hydrothermal synthesis method required for zeolitic materials. The templating agent can only be removed by calcination and cannot be recovered. For the process of surfactant as a pore-forming agent, since the macromolecular template mechanism of the surfactant competes with the crystal growth mechanism of the hydrothermally synthesized zeolite, the ordinary surfactant can only form amorphous silica/zeolite composite. The material, unable to form a zeolite with a hierarchical structure, requires a specially designed surfactant, such as by covalent attachment, using organosilane groups to increase the interaction of the growing zeolite with the pore-forming surfactant. Patent US 20130184147 A1 utilizes a dual template strategy of a surfactant as a pore former to synthesize hierarchical micropores having regular or irregularly arranged mesopores by a specially designed chloride salt surfactant containing a plurality of quaternary amines - Mesoporous zeolite molecular sieve; patent CN104402020A also synthesizes micro-double-porosity beta molecular sieve through specially designed octaammonium-based Bola surfactant. Patent CN103214003B introduces N,N-dimethyl-N-[3-(trimethoxysilyl)propyl]octadecyl ammonium chloride (TPOAC) into the synthesis of Y zeolite molecular sieves, organosilane-terminated siloxanes The base is hydrolyzed to a silanol group, the chemical bond is bonded to the surface skeleton of the zeolite, and the other alkyl end is polymerized to participate in reaming, thereby obtaining a mesoporous Y-type zeolite molecular sieve. Due to the special structure of the mesoporous surfactant templating agent used, custom synthesis is required, the synthesis step is cumbersome and the cost is high; even if a specially designed surfactant templating agent such as organosilane is used, it is difficult to obtain a large crystal, which is generally obtained. Nanoparticle aggregates, nanowires, etc., have low mechanical strength; and usually employ a dual templating agent strategy that works with traditional zeolite templating agents. The two high-cost templating agents consumed by the dual templating agent strategy are required at the end of the synthesis. It is very environmentally friendly; the addition of surfactants leads to easy foaming during the synthesis of zeolite, and the synthesis process is difficult to enlarge. Using a polymer material as a template, the polyether-polyamine or polyethyleneimine is silylated in WO 2014146128, and as a mesoporous pore-forming agent, it is added to the zeolite synthesis liquid to obtain a MOR containing intergranular 2-5 nm mesopores. Zeolite with improved catalyst properties can. However, most of the polymer templating agents are expensive and difficult to synthesize, and it is difficult to control the hydrothermal growth on the surface of the templating agent. The polymer is easily degraded in the synthesis, and it is difficult to form a three-dimensionally connected microporous-mesoporous structure. Industrial amplification is directly applied. It can be seen that the current direct preparation method for synthesizing the zeolite of the hierarchical structure adopts the formed solid template agent, which is expensive and difficult to synthesize, and is hydrothermally grown on the surface of the formed template agent such as carbon nanotubes and polymer template. It is difficult to control, and it is difficult to form a three-dimensionally connected microporous-mesa-porous structure, which is difficult to directly apply for industrial amplification.

On the other hand, in order to obtain an organic-zeolite composite, almost all efforts are made on a conventional microporous zeolite for a crystalline zeolite material, for example, J. Phys. Chem. C, 2015, 119 In the article 8736-8747, L-dopamine is adsorbed on beta zeolite with a pore size of about 0.66 nm to form an amino acid-zeolite composite, and the polymerization of the L-dopamine is slowed down by the restriction of amino acids through the pores. The amino acid-zeolite composite as a nano drug is beneficial to the possibility of L-dopamine as a treatment for Parkinson's disease; however, due to the pore limitation of the traditional beta zeolite, the phenylalanine immobilization amount is less than 10% by weight, although the amino acid The adsorption induces the deformation of the zeolite to a certain extent to better accommodate the amino acid, but the nature of the physical adsorption is unchanged, and the zeolite after the removal of the amino acid remains the characteristic of the original microporous zeolite. Further, as Bull. Korean Chem. Soc., 2013, 34(8), 2367, L-lysine is immobilized on 4A zeolite and used as an amino acid-zeolite composite catalyst for synthesizing an α,β-unsaturated carbonyl compound. However, since the pore size of the 4A zeolite is small, only 0.41 nm, the loading of the zeolite on the amino acid is only 13% by weight under neutral conditions. Among the above amino acid-zeolite composites, there is only a microporous structure and no mesoporous structure, and the size, type, and loading amount of the amino acid capable of loading are greatly limited.

Another researcher's effort is to use amorphous, rather than mesoporous molecular sieves with a stable crystal structure. For example, Acta Chim. Slov., 2015, 62, 95–102 immobilized a proline derivative on an amorphous mesoporous molecular sieve MCM-41, which is an aminolysis reaction of styrene oxide. Played a very good catalytic role. The invention patent CN101724619A provides an application of a functionalized ionic liquid modified mesoporous molecular sieve in enzyme immobilization. The invention patent CN102499477A discloses a cigarette filter rod additive with harm reduction effect and a preparation and application method thereof, wherein one or more amino acids are used as active components, and silica gel, activated carbon, alumina, molecular sieve or the like is used as a carrier to pass through the surface. The chemical reaction supports the active component on the surface of the carrier to obtain a supported amino acid material, which can effectively reduce the content of hydrocyanic acid and volatile hydroxy compound in the cigarette smoke by 20-40%. In the above amino acid-inorganic mesoporous composite material, the mesoporous material has an amorphous structure, poor thermal stability, poor hydrothermal stability, and the mesoporous structure will collapse and the pore mesopores disappear in the presence of temperature rise, impact, and water vapor, thereby adapting The range is extremely limited and the stability of use is greatly limited.

Summary of the invention

The invention utilizes a special interaction between an amino acid and a zeolite structure to obtain an amino acid-zeolite composite material having a wide range of uses, which is simply converted in one step to obtain a microporous mesoporous layer zeolite material having a high grade hierarchical structure, and a preparation method thereof Simple, energy efficient and versatile.

According to a first aspect of the present invention, there is provided an amino acid-zeolite composite comprising a zeolite structure and dispersed amino acid molecules residing in a pore structure of the above zeolite structure, the zeolite structure comprising a microporous structure and a mesoporous structure, and At least a portion of the above mesoporous structure is located inside the crystal.

As a further improvement of the present invention, the above mesoporous structures are all located inside the crystal.

As a further improvement of the present invention, the above amino acid-zeolite composite material further includes a macroporous structure.

As a further improvement of the present invention, the above amino acid is selected from the group consisting of a hydrophilic amino acid and/or a non-standard zwitterionic amino acid.

As a further improved aspect of the present invention, the above hydrophilic amino acid is selected from the group consisting of lysine (Lys), arginine (Arg), histidine (His), tyrosine (Tyr), serine (Ser), and sul One or more of (Thr), cysteine (Cys), asparagine (Asn), glutamine (Gln), aspartic acid (Asp), and glutamic acid (Glu) The above non-standard zwitterionic amino acid is selected from the group consisting of betaine, L-carnitine, ectoine, sodium laurylaminopropionate, sodium lauryl dimethylmethylene dicarboxylate, Na-acyl lysine, Na -methyl-Na-lauroyl lysine, N-acyl sarcosine, N-acyl glutamic acid, N-acyl sarcosine, N-alkyl aspartic acid-β-alkyl ester, N- One or more of acylglutamic acid diester and di(octylaminoethyl)glycine.

As a further improvement of the present invention, the above zeolite structure is selected from the group consisting of LTA, FAU, SOD, CAN, BEA, CHA, RTH, EMT, MFI, MEL, MOR or EON type zeolites.

As a further improvement of the present invention, the loading of the zeolite in the above amino acid-zeolite composite is between 1% and 30% based on the total mass of the above amino acid-zeolite composite.

As a further improvement of the present invention, the loading of the zeolite in the above amino acid-zeolite composite is between 5% and 20% based on the total mass of the above amino acid-zeolite composite.

As a further improvement of the present invention, the above amino acid interacts with the zeolite structure by hydrogen bonding and/or electrostatic interaction.

According to a second aspect of the present invention, there is provided a microporous-mesoporous layer zeolitic material, comprising a zeolite structure comprising a microporous structure and a mesoporous structure, and at least a portion of said mesoporous structure is located Inside the crystal.

As a further improvement of the present invention, the above mesoporous structures are all located inside the crystal.

As a further improvement of the present invention, the above microporous mesoporous layer zeolitic material further comprises a macroporous structure.

As a further improvement of the present invention, the above zeolite structure is selected from the group consisting of LTA, FAU, SOD, CAN, BEA, CHA, RTH, EMT, MFI, MEL, MOR or EON type zeolites.

As a further improvement of the present invention, the above microporous mesoporous grade zeolite material has an adsorption effect on biomacromolecules and/or large ions, and the solid loading is achieved by the total mass of the above microporous mesoporous grade zeolite material. 17% or more, preferably 27% or more.

As a further improvement of the present invention, the above microporous mesoporous layer zeolite material has an adsorption effect on catalase, and the relative activity of the adsorbed catalase is above 90%.

As a further improvement of the present invention, the mesoporous structure has a mesoporous pore size distribution of 10-50 nm and an average pore size distribution of 16-20 nm.

As a further improvement of the present invention, the above microporous mesoporous grade zeolite material has a BET specific surface area of 90 m ² /g or more.

According to a third aspect of the present invention, there is provided a process for the preparation of an amino acid-zeolite composite in which an amino acid is introduced as an additive, and the obtained amino acid-zeolite composite comprises a zeolite structure and a zeolite structure. A dispersed amino acid molecule in the pore structure, the zeolite structure comprising a microporous structure and a mesoporous structure, and at least a portion of the mesoporous structure is located inside the crystal.

As a further improvement of the present invention, the above amino acid is selected from the group consisting of a hydrophilic amino acid and/or a non-standard zwitterionic amino acid.

As a further improvement of the present invention, the above zeolite synthesis raw material comprises a silicon source, an aluminum source and a base, and optionally a hetero atom and/or a metal source.

As a further improvement of the present invention, the synthesis reaction is carried out at a temperature of from 0 to 300 ° C and a pressure of from atmospheric pressure to 20 bar.

As a further improved solution of the present invention, the above method comprises the following steps:

a) introducing an amino acid as an additive into a zeolite synthesis feedstock comprising a silicon source, an aluminum source and a base, and optionally a heteroatom and/or a metal source, at a temperature between 0 and 300 ° C and a pressure at atmospheric pressure to Synthesis reaction between 20bar;

b) Solid-liquid separation of the mixture of step a) and drying of the solid product to obtain the above amino acid-zeolite composite.

According to a fourth aspect of the present invention, there is provided a process for the preparation of a microporous mesoporous grade zeolite material comprising washing the amino acid-zeolite composite of the first aspect to obtain the above microporous mesoporous grade A zeolitic material comprising a zeolite structure comprising a microporous structure and a mesoporous structure, and at least a portion of said mesoporous structure is located inside the crystal.

As a further improved solution of the present invention, washing is carried out using water.

According to a fifth aspect of the invention, the invention provides the use of an amino acid-zeolite composite according to the first aspect as a catalyst, adsorbent or ion exchanger.

According to a sixth aspect of the invention, the invention provides the use of a microporous mesoporous grade zeolite material according to the second aspect as a catalyst, adsorbent or ion exchanger.

Compared to the prior art, the amino acid-zeolite composite of the present invention comprises a mesoporous structure and at least a portion of the mesoporous structure is located inside the crystal, preferably all of the mesoporous structure is located inside the crystal. The amino acid molecules dispersed in the hierarchical pore structure have chirality, catalytic properties, desorption, and strong interaction with biological macromolecules; and the hierarchical mesoporous-microporous structure provides suitable nesting for amino acid molecules. The pore size, morphology, curved surface, and skeletal charge and localized exchangeable positive ions capable of interacting with amino acids. Therefore, amino acid-zeolite composites have great application value in protein adsorption, catalysis and/or self-amino acid sustained release.

The amino acid-zeolite composite-loaded amino acid can be removed by washing or the like, and the zeolite structure with the amino acid removed has microporous-mesoporous pores, thereby accommodating larger molecules and reducing diffusion resistance compared to the conventional microporous zeolite. The mesopores are inside the crystal, and the mesopores are adjustable in size, so that they have a shape-selective selectivity, especially for the macromolecule selective selectivity that microporous zeolite cannot achieve, and can achieve protein adsorption, biocatalysis and/or which cannot be achieved by conventional zeolites. Or the function of large-scale ion exchange has broad application prospects.

DRAWINGS

1 is a flow chart showing a process for preparing an amino acid-zeolite composite material and a microporous mesoporous grade zeolite material according to a preferred embodiment of the present invention;

Figure 2 is an amino acid prepared in Example 1 - Zeolite composite LC @ MLTA of ¹ H-NMR and ¹³ C-NMR spectrum;

3 is a Raman spectrum of the amino acid-zeolite composite LC@MLTA prepared in Example 1;

4 is a ¹ H-NMR and ¹³ C-NMR chart of the microporous mesoporous grade zeolite material MLTA-LC prepared in Example 2;

5 is a Raman spectrum of the microporous-mesoporal graded zeolite material MLTA-LC prepared in Example 2;

6 is an XRD diffraction pattern of the microporous-mesoporous grade zeolite material MLTA-LC prepared in Example 2;

7 is a (a) nitrogen adsorption-desorption isotherm and (b) BJH pore size analysis chart of the microporous-mesoporous grade zeolite material MLTA-LC prepared in Example 2;

8 is a (a) scanning electron microscope, (b) low-resolution transmission electron microscope, and (c) high-resolution transmission electron micrograph of the microporous-mesoporous-grade zeolite material MLTA-LC prepared in Example 2 (illustrated is the corresponding fast Fourier) Transforming the FFT diffraction pattern, the curve used to help identify the mesoporous channel position and morphology);

9 is a (a) nitrogen adsorption-desorption isotherm and (b) BJH pore size analysis chart of the microporous mesoporous layer zeolite material MLTA-LCLT prepared in Example 4;

10 is a (a) scanning electron microscope, (b) low-resolution transmission electron microscope, and (c) high-resolution transmission electron micrograph of the microporous-mesoporous-grade zeolite material MLTA-LCLT prepared in Example 4 (illustrated is correspondingly fast Fourier transform FFT diffraction pattern, the curve used to help identify the mesoporous channel position and morphology);

Figure 11 is a (a) XRD diffraction pattern of the microporous mesoporous grade zeolite material MFAU-LC prepared in Example 10; (b) nitrogen adsorption-desorption isotherm; (c) scanning electron micrograph; and (d) transmission Electron micrograph

Figure 12 is a (a) XRD diffraction pattern of a conventional LTA-type zeolitic material CLTA zeolite prepared in Comparative Example 11; (b) nitrogen adsorption-desorption isotherm; (c) scanning electron micrograph; and (d) transmission electron micrograph;

Figure 13 is a (a) XRD diffraction pattern of a conventional FAU-type zeolitic material CFAU zeolite prepared in Comparative Example 12; (b) nitrogen adsorption-desorption isotherm; (c) scanning electron micrograph; and (d) transmission electron micrograph;

Figure 14 is an MLTA-LC prepared in Example 2, MLTA-LCLT prepared in Example 4, MLTA-Lys prepared in Example 6, MLTA-LysAc prepared in Example 8, and a conventional LTA-type zeolitic material CLTA prepared in Comparative Example 11. (a) adsorption kinetics curve for catalase immobilization; (b) comparison of relative activity.

detailed description

The present inventors have developed a completely new strategy for synthesizing microporous mesoporous zeolite crystals having a hierarchical structure using a non-hard template method, a non-surfactant, and a non-polymer interaction strategy. The amino acid-zeolite composite structure having a wide range of uses is obtained by a one-step method by using a special interaction between an amino acid and a zeolite structure. The amino acid-zeolite composite structure of the present invention contains a microporous structure of a zeolite, and a mesoporous structure formed by an amino acid is involved. The pore structure is located inside the crystal and also has dispersed amino acid molecules that reside in the pore structure. The amino acid molecules dispersed in the hierarchical pore structure have chirality, catalytic properties, desorption, and strong interaction with biological macromolecules; and the hierarchical mesoporous-microporous structure provides suitable nesting for amino acid molecules. The pore size, morphology, curved surface, and skeletal charge and localized exchangeable positive ions capable of interacting with amino acids. The amino acid-zeolite composite structure has great application value in protein adsorption, catalysis and sustained release of self-amino acids.

For the synthesis of microporous-mesoporous zeolite materials with hierarchical structure, the amino acids belong to soft template, the spatial structure is relatively variable and malleable, and the compatibility with hydrothermal synthesis conditions is good. The melting point of amino acids is about 230 ° C or higher, so it is very stable under the conditions of zeolite synthesis (usually less than 200 ° C), soluble in strong acids and strong bases, unlike the polymer template, it decomposes in the synthesis of layered zeolite materials, and the amino acids are It is colorless crystal, so it does not produce a change in the color of the zeolite, which is also superior to the polymer template. The interaction of amino acids with zeolites includes hydrogen bonding interactions and electrostatic interactions, which are much weaker than covalent interactions between organosilane-containing surfactants and zeolites, and do not produce micelles during synthesis. Therefore, it is easier to form a large single crystal structure, and non-surfactant participates in the formation of polycrystalline nanoparticles, and the single crystal structure has better thermal stability and hydrothermal stability. The immobilization amount of the amino acid in the amino acid-zeolite composite structure (according to the total mass of the amino acid-zeolite composite) can reach 30%. The amino acid is an ampholyte and exists in the form of a zwitter ion or a zwitterion in an aqueous solution or crystal. The so-called zwitterion means that the same amino acid molecule has an NR ₄ ⁺ positive ion capable of releasing a proton and can accept a proton. The COO ^- negative ion, because of this, the amino acid has good water solubility, especially the non-standard amino acid with a permanent double ion structure has moisture absorption, and the presence of the zeolite structure can stabilize the zwitterionic state of the amino acid and inhibit the non-dissociated state. Therefore, the amino acid of the amino acid-zeolite composite structure can be removed by washing, and the existing templating agent needs to be removed by calcination or pickling. Therefore, the process for synthesizing the microporous-mesoporous zeolite material of the present invention is more energy-saving and environmentally friendly than the prior art. The amino acid does not foam during the synthesis of the zeolite to cause volume expansion of the synthetic liquid. Therefore, the process for synthesizing the microporous-mesoporous zeolite material of the present invention is easier to enlarge than the prior art.

The zeolite structure with amino acid removed has microporous-mesoporous pores, which can accommodate larger molecules and reduce diffusion resistance compared to conventional microporous zeolites. Its mesopores are inside the crystal, and the mesopores are adjustable in size, which has a shape selective selectivity, especially for the macromolecule selective selectivity that microporous zeolite cannot achieve, and also has an adjustable acidic site and an adjustable pro /hydrophobic, retained crystalline structure and stability, exchangeable ions, and the ability to be exchanged for alkali catalysts with alkali or alkaline earth metals. It can improve the performance of zeolite in traditional fields, such as catalysis, adsorption, ion exchange, and can realize the functions of protein adsorption, biocatalysis and large-scale ion exchange which cannot be realized by traditional zeolite, and has broad application prospects.

The amino acid-zeolite composite structure of the present invention and its converted microporous-mesoporous zeolite material 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.

In a broad sense, the present invention is based on the recognition that zeolite solids and amino acids have strong interactions and mutually matching shape characteristics. The addition of amino acids in the early stages of zeolite synthesis can interfere with the morphology and charge characteristics of the synthesized zeolite, in order to be able to The amino acid added is well accommodated, and the van der Waals force in the pores is lowered, and the synthesized zeolite has microporous-mesoporous properties. At the same time, due to the interaction of the amino acids themselves and the amino acid-zeolite interaction, a three-dimensional grid material with a distinct hierarchical structure is formed, which has strong stability. Since the amino acid is uniformly distributed in the composite structure, Achieve better amino acid functions, such as catalysis, protein adsorption and so on. And the amino acid can also be released slowly under desorption conditions.

Strong interactions between zeolite solids and amino acids are electrostatic interactions and ionic bond interactions, rather than covalent interactions. Thus, the amino acids in the amino acid-zeolite composite are readily removed by washing, preferably by water washing, rather than by conventional high temperature calcination. If the organic amino acid moiety is removed in the amino acid-zeolite composite, a layered inorganic zeolite having microporous mesopores is obtained, the mesopores are tunable, and thus the macromolecule can enter the catalyst having an acidic site; The positive ions can also be exchanged for basic catalysts by alkali ions. The obtained layered inorganic zeolite with microporous mesopores has better catalytic, adsorption and ion exchange properties than the conventional microporous zeolite structure, especially for some molecules which are not realized by conventional zeolite structures such as molecules or ions having large diameters. Or ion range.

The present invention proposes for the first time to introduce an amino acid into the zeolite synthesis process, through electrostatic interaction and stereo configuration between amino acid and zeolite nutrient solution, amino acid and zeolite nano precursor, amino acid and amino acid, zeolite nutrient solution and zeolite nano precursor. The effect is to construct an amino acid-zeolite composite with a three-dimensional structure. In addition to the microporous structure of the zeolite, the organic-inorganic composite material also has a mesoporous structure due to the function of the amino acid as a mesoporous agent. In the hierarchical pores of the zeolite, it plays a very good supporting function. After removing the organic amino acid, the obtained inorganic material is a microporous mesoporous zeolite having a hierarchical structure, and the mesoporous size of the material can be adjusted by zeolite synthesis conditions or by ion exchange after synthesis, and the mesopores are located in the crystal. . Such a layered zeolite material having at least two levels of pore structure exhibits better macromolecular accessibility and has broad prospects for applications that are limited by conventional zeolite pore diffusion or steric hindrance, including macromolecular catalysis, adsorption, and the like; At the same time, it can be ion exchanged by a large diameter, and can be used as an ion exchanger. If it is exchanged with an alkali ion or an alkali metal ion, it can be converted into a basic catalyst.

The method of the present invention avoids the use of expensive hard templating agents relative to the porous carbon, surfactant materials, and polymeric materials of the above-described background art, and avoids the high cost associated with the use of surfactants, and Process amplification problems such as foaming in production avoid the use of expensive silylating agents and overcome the disadvantages of the organic templating agent-zeolite composite itself. By adopting the amino acid structure ubiquitous in nature, the amino acid-zeolite composite material is obtained in one step without additional reagents, and has an extremely wide use. The zeolitic material after removal of the amino acid has a layer of microporous-mesoporous interwoven pores, which can be used as a catalyst, adsorption and ion exchange for high value-added products.

It is commendable that the graded microporous mesoporous zeolite material we obtained has a larger specific surface area and pore volume than conventional microporous zeolite materials, and has a relatively uniform mesopores. In one embodiment, the microporous mesoporous LTA type zeolite material of the present invention has a specific surface area of 141 m ² /g and a mesoporous pore volume of 0.07 cm ³ /g under the same test conditions, while conventional micropores. The zeolite material is too small to effectively adsorb nitrogen molecules, and the obtained specific surface area is less than 2 m ² /g, and the mesoporous pore volume is zero. It is worth mentioning that, in some embodiments, the hierarchical microporous-mesoporous zeolite material has a uniform mesoporous distribution, the main distribution range is in the range of 16-20 nm, and the distribution is narrow, and the invention is wider than the prior art. The distribution of mesoporous structures, as well as the addition of super macromolecules or polymeric pore-enlarging agents, can achieve a pore size range of greater than 10 nm.

Even more commendable is that the layered microporous mesoporous zeolite material we have also has a macroporous structure with a larger specific surface area and pore volume. In another embodiment, the microporous-mesoporous LTA of the present invention. The zeolitic material contains a distinct macroporous structure and has a large pore specific surface area of 230 m ² /g, a large pore volume of 0.86 cm ³ /g, a large pore average pore diameter of 320 nm, and a macroporous porosity as measured by mercury intrusion method. 64%.

In the present invention, the term "zeolite" breaks through the definition of a zeolitic material in the conventional sense, and a conventional zeolite is defined as an aluminosilicate having micropores, which is generally used commercially as an adsorbent and a catalyst. The pore size of the zeolite structure of the present invention breaks through the range of micropores and can be considered as a molecular sieve in a broad sense. The pore size of the material is in accordance with the International Classification of Pure and Applied Chemistry (IUPAC), that is, the pore size of the microporous material is less than 2 nm, the pore diameter of the mesoporous material is between 2 and 50 nm, and the pore diameter of the macroporous material is greater than 50 nm. The term "macromolecule" refers to a molecule whose kinetic diameter is larger than the intrinsic pore size of the zeolitic material. Similarly, "large-diameter ion" refers to its ion diameter or hydrated ion diameter than the intrinsic pore size of the zeolitic material. Large ions. For example, for the LTA type zeolite, the "macromolecule" or "large diameter ion" referred to in the present invention has a larger diameter than the LTA type zeolite intrinsic maximum pore diameter of 0.41 nm; and as for the FAU type zeolite, the present invention The size of the "macromolecule" or "large-diameter ion" referred to is larger than the intrinsic maximum pore diameter of the FAU-type zeolite of 0.74 nm.

In the present invention, the term "amino acid" refers to a generic term for a class of organic compounds containing an amino group and a carboxyl group, and may be a protein amino acid, a non-protein amino acid or an amino acid-like compound, and there are currently about 500 amino acids known. The term "surfactant" refers to an amphiphilic structure containing both a hydrophobic group (tail) and a hydrophilic group (head), thereby reducing liquid-liquid or liquid-solid surface tension or interfacial tension to a certain concentration. , a class of organic compounds that form micelles. It will be apparent that the amino acids used in the present invention, especially small molecule amino acids, have hydrophobic groups that are too small and do not have a critical micelle concentration and are therefore not in the scope of surfactants.

In the present invention, 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. In order to avoid subsequent calcination processes, 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., and its subordinate zeolite A, zeolite X, Y zeolite, USY zeolite, sodalite, Calcium nepheline, β molecular sieve, SAPO-34, SSZ-13, RUB-13, SSZ-50, EMC-2, ZSM-20, ZSM-5, ZSM-11, mordenite, TNU-7, and the like. It should be noted that in the art, the above various types of zeolites can be realized by controlling various kinds of raw materials, raw material dosages, and process conditions in the synthesis process, which is not difficult for those skilled in the art to realize. More preferably, the backbone structure is related to the nature of the amino acid used, for example, for a positively charged amino acid, such as arginine, histidine, lysine, preferably the backbone has a relatively large electron density and can occur with amino acids. Strongly interacting framework of zeolites. The skeletal structure charge, affinity/hydrophobicity, and stability of the zeolite are related to the ratio of silicon and aluminum (or other heteroatom) in the framework, ie, the ratio of silicon to aluminum (or the ratio of silicon to heteroatoms). The ratio of silicon to aluminum of zeolite is from 1 to infinity. For example, the ratio of silica to alumina of NaA structure in LTA type zeolite is 1; in silicite-1 of MFI type zeolite is all-silicon structure, the ratio of silicon to aluminum is infinite, and the ratio of silicon to aluminum of ZSM-5 structure Above 2.7; in the FAU type zeolite, the X-structure silicon-aluminum ratio is between 1-2, the Y-structure silicon-aluminum ratio is between 2-3, and the USY silicon-aluminum ratio is about 15. Since the valence state of silicon is tetravalent, and the valence state of aluminum is trivalent, the isomorphous substitution of aluminum with silicon produces a negatively charged zeolite framework. In order to balance the negative charge of the framework, the zeolite structure also contains free positive Ions can be exchanged. The silica-alumina ratio of the zeolite increases, the charge number of the skeleton band becomes smaller, the free positive ions become smaller, the hydrophobicity increases, the ion exchange capacity becomes smaller, the acidity becomes smaller, and the stability increases.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a preferred process flow for the preparation of an amino acid-zeolite composite and a microporous mesoporous grade zeolite material, the method comprising: a) a synthetic raw material of a mixed zeolite comprising a silicon source, an aluminum source, a base. Optionally, a hetero atom or a metal source, the silicon source may be, but not limited to, silica sol, silicon oxide, tetraethyl orthosilicate, sodium metasilicate, n-butyl silicate, silicon carbide, and the aluminum source may be but not limited to Aluminum foil, aluminum powder, aluminum chloride, sodium metaaluminate, aluminum sulfate, aluminum nitrate, aluminum isopropoxide, pseudoboehmite, aluminum hydroxide, alkali may be, but not limited to, sodium hydroxide, potassium hydroxide, hydrogen Ammonium oxide, calcium hydroxide, aluminum hydroxide, silver hydroxide, lead hydroxide, zinc hydroxide, barium hydroxide, potassium carbonate, sodium carbonate, ammonia, hydrazine, hydroxylamine, liquid ammonia, optional heteroatoms or metals It may be any atom or metal capable of substituting silicon or aluminum atoms in the zeolite framework, including but not limited to phosphorus atoms, boron atoms, germanium atoms, titanium atoms, zirconium atoms, gallium atoms, vanadium atoms, cobalt atoms, iron atoms, The hetero atom or metal source may be phosphoric acid or boron. , tetraethoxy hydrazine, tetrabutyl titanate, zirconium dichloride, gallium phosphate, ammonium metavanadate, cobalt chloride, iron nitrate; b) amino acid added to the medium obtained from step a), the amino acid The properties match the structure of the zeolite produced. For hydrophilic zeolites, the amino acids are preferably charged or polar amino acids including, but not limited to, lysine (Lys), arginine (Arg), histidine (His). ), tyrosine (Tyr), serine (Ser), threonine (Thr), cysteine (Cys), asparagine (Asn), glutamine (Gln), aspartic acid (Asp) Glutamate (Glu), betaine, L-carnitine, ectoine, sodium laurylaminopropionate, sodium lauryldimethylammonium dicarboxylate, Na-acyl lysine, Na-A ke-Na-lauroyl lysine, N-acyl sarcosine, N-acyl Glutamate, N-acylsarcosine, N-alkylaspartate-β-alkyl ester, N-acylglutamic acid diester, di(octylaminoethyl)glycine; c) suitable Hydrothermal synthesis under temperature and pressure, wherein the temperature is between 0 and 300 ° C, preferably between 4 and 200 ° C, more preferably between 50 and 180 ° C, and the pressure is between atmospheric and 20 bar; d) for step c) The obtained mixture is subjected to solid-liquid separation, and optional operation methods such as filtration, centrifugal filtration, sedimentation separation, etc., preferably centrifugal filtration; e) washing operation may continue the operation in step d, and the solvent selected for washing is preferably a polar solvent. Including but not limited to deionized water, ethanol, acetone, methanol, petroleum ether, etc., the more preferred washing solvent is water; f) drying part, drying operation can be dried by infrared lamp, dry air drying oven, vacuum drying oven Drying, double cone drying, wiped film drying, etc., drying temperature 60-300 ° C, preferably 60-100 ° C; g) optionally in the filtrate containing amino acids in the solid-liquid separation obtained from the steps d) and e) Recycling, the obtained filtrate can be separated into amino acids or adjusted for composition, as step b) liquid.

In the present invention, the amino acid structure may be any currently known amino acid, and the article in Newgely.Currently. The right and left amino acids, 240 of which are freely existable in nature. In addition to different functional groups in the backbone structure, such as α, β, γ, δ-position amino acids, they are in polarity, pH, and side chain properties (such as aliphatic groups, aromatic groups, sulfur-containing, hydroxyl-containing groups). ) and so on, there are great differences, so the interaction force of the zeolite structure is also different. For example, the side chain of arginine, histidine and lysine is positively charged, the side chain of aspartic acid and glutamic acid is negatively charged, the side chain of serine and threonine is uncharged, tryptophan, The side chain of phenylalanine has a benzene ring and is hydrophobic. In the present invention, those skilled in the art will be able to select suitable amino acids depending on the needs and the particular application in which the amino acid-zeolite composite is produced or the desired microporous mesoporous zeolite material. For example, for an LTA type molecular sieve having extremely high hydrophilicity, the ratio of silicon to aluminum is 1, preferably a charged amino acid, including but not limited to lysine, arginine, histidine, tyrosine, serine, sul More preferred are non-standard amino acids of permanent zwitterionics, including but not limited to betaine, L-carnitine, and the like, and are preferably limited to betaines, glutamine, aspartic acid, glutamic acid, glutamine, aspartic acid, glutamic acid, Ic doneo, sodium laurylaminopropionate, sodium lauryl dimethylmethylene dicarboxylate, Na-acyl lysine, Na-methyl-Na-lauroyl lysine, N-acyl Acid, N-acyl glutamic acid, N-acyl sarcosine, N-alkyl aspartic acid-β-alkyl ester, N-acyl glutamic acid diester, di(octylamino) glycine, etc. .

The present invention also relates to the use of interconnected microporous-mesoporous and optional-macroporous pore structures in layered porous zeolites, particularly for biomacromolecular adsorption properties, large ion exchange applications, and biomacromolecules or gauge diameters. Methods of loading larger ions onto the layered porous zeolite include wet impregnation, initial wet impregnation, ion exchange, evaporation, dry impregnation, physical mixing, and the like. Biomacromolecules include, but are not limited to, peptides, proteins, macromolecular drugs such as catalase, bovine serum albumin, lysozyme, insulin, cytochrome oxidase, alcohol dehydrogenase, acetaldehyde dehydrogenase, lactate dehydrogenase , amino acid oxidase, proteolytic enzymes, Carbonic anhydrase, lipoxygenase, phenolase, transaminase, amylase, aldolase, hydratase, decarboxylase, lipase, glucose-6-phosphate isomerase, mitomycin C, bomimycin, Actinomycin D, daunorubicin, doxorubicin, vinblastine, podophyllotoxin, harringtonine, L-asparaginase, adrenocortical hormone, androgen, estrogen, and others Nucleic acid, lipid, carbohydrate drug molecules. Large ions include metal ions after potassium ions in the periodic table, such as helium ions, strontium ions, magnesium ions, silver ions, tin ions, zinc ions, and the like.

Example 1 Synthesis of Amino Acid-Zeolite Composite LC@MLTA

12.54ml silica sol (Qingdao Ocean, 25%) was dissolved in 20ml deionized water, stirred for 15 minutes or more to make it evenly distributed, labeled as silicon source; 2.4g sodium hydroxide and 4.92g sodium metaaluminate were dissolved in 34ml Ionic water was stirred until clear and labeled as an aluminum source; 4.8 g of L-carnitine was dissolved in 5 ml of deionized water, sonicated and labeled as an additive. The aluminum source was added dropwise to the silicon source, stirring was continued, and heating was started after aging for 3 hours at room temperature, and the set temperature was 100 °C. The additive solution was added dropwise to the aged product of the above aluminum source and silicon source at a constant rate, and the temperature was raised to 100 ° C to start timing. After 20 hours, the mixture was centrifuged to collect a white solid, which was dried at 60 ° C to obtain 9.2 g of the product, which was an amino acid. - Zeolite composite LC@MLTA.

The above amino acid-zeolite composite LC@MLTA was measured by ¹ H-NMR and ¹³ C-NMR using a Bruker 500 MHz nuclear magnetic resonance spectrometer. The spectrum is shown in Fig. 2, and the obtained hydrogen spectrum and carbon spectrum spectrum are clear. The presence of organic amino acids in the composite structure is seen. The above amino acid-zeolite composite LC@MLTA was measured by Raman spectroscopy using HORIBA LabRAM HR800 Raman spectrometer. The spectrum is shown in Fig. 3. The obtained Raman spectrum clearly shows the structure of LTA zeolite in the composite structure. (The peak is below the Raman shift of 700 cm ^-1 ) and the structure of the compound amino acid L-carnitine (the peak is at a Raman shift of 700 cm ^-1 or more).

Example 2 Preparation of Microporous-Mesoporous Layer Zeolite Material MLTA-LC

5 g of the amino acid-zeolite composite material LC@MLTA obtained in Example 1 was stirred in 100 g of deionized water for 5 minutes, and the resulting suspension was centrifuged, and the above operation was repeated twice, and the white solid after centrifugation was collected and dried at 60 ° C. 4.1 g of product was obtained as a microporous mesoporous grade zeolitic material MLTA-LC.

The above-mentioned microporous-mesoporal grade zeolitic material MLTA-LC was measured by ¹ H-NMR and ¹³ C-NMR using a Bruker 500 MHz nuclear magnetic resonance spectrometer, and the spectrum is shown in Fig. 4, and the obtained hydrogen spectrum and carbon spectrum spectrum were obtained. It can be clearly seen that there is no organic amino acid in the structure after washing. The above-mentioned microporous-mesoporal grade zeolitic material MLTA-LC was measured by Raman spectroscopy using HORIBA LabRAM HR800 Raman spectrometer. The spectrum is shown in Fig. 5. The obtained Raman spectrum can clearly see the LTA in the composite structure. The structure of the zeolite (the peak is below the Raman shift of 700 cm ^-1 ), and the structure of the amino acid L-carnitine used (the peak at a Raman shift of 700 cm ^-1 or more) has been completely washed away.

For the above microporous mesoporous grade zeolite material MLTA-LC, Rigaku's D/Max-2200 was used. The X-ray measurement was carried out by a PC X-ray diffractometer, and the spectrum is shown in Fig. 6. All the characteristic peaks of the LTA-type zeolite structure were clearly observed on the obtained powder diffraction pattern, and it was confirmed that the obtained solid was a crystalline LTA zeolite.

The above microporous mesoporous grade zeolitic material MLTA-LC was subjected to nitrogen adsorption desorption measurement at 77 K temperature by Micromeritics Tristar II 3020, and the adsorption desorption isotherm was listed in Fig. 7A, and the obtained adsorption isotherm was type IV, and The resulting desorption isotherms form a H ₃ hysteresis loop that does not reach saturation at high P/P ₀ pressures, demonstrating the presence of mesopores. The obtained nitrogen adsorption-desorption isotherm was calculated by the BJH method, and the correlation between the obtained dV/dlog (D) pore volume and the average pore diameter D _p is shown in Fig. 7B, and the obtained microporous-mesoporous grade zeolite material MLTA-LC can be seen. The mesopore range is between 10-40 nm and the average pore diameter is 18.4 nm. Adsorption data obtained in FIG. 7B calculated Brunauer-Emmett-Teller specific surface area, to give a microporous - BET hierarchical mesoporous zeolitic material MLTA-LC specific surface area of 90m ² / g, mesopore volume 0.05cm ³ / g. The mercury intrusion experiment was carried out by using the AutoPore IV 9500 series high performance automatic large hole measuring analyzer of Mike Instruments. The macropore characteristics of the microporous mesoporous zeolite material MLTA-LC were measured to obtain the large pore specific surface area. 230 m ² /g, the macropore volume was 0.86 cm ³ /g, the macropore average pore diameter was 320 nm, and the macroporosity was 64%. The elemental content of the microporous mesoporous zeolitic material MLTA-LC was measured by HORIBA Jobin Yvon's inductively coupled plasma atomic emission spectrometry JY 2000-2 to obtain a Si/Al ratio of 1.11.

Scanning electron microscopy (SEM) observation of the uncoated gold sample was carried out on the above-mentioned microporous-mesoporal grade zeolitic material MLTA-LC using JSOL J800-7800F. As shown in Fig. 8a, the apparent LTA crystal form and mesoporous structure were observed. The above-mentioned microporous-mesoporal grade zeolitic material MLTA-LC sample was embedded in an epoxy resin, and then sliced into an embedded thin plate having a thickness of 90 nm, and was measured by TEMNAI G2F30 field emission source transmission electron microscope for TEM measurement. In Fig. 8b and Fig. 8c, a distinct polycrystalline structure and a non-ordered mesoporous pore structure are visible, and the pore structure is inside the crystal, and a distinct large pore structure is also visible.

Example 3 Synthesis of Amino Acid-Zeolite Composite LCLT@MLTA

12.54ml silica sol (Qingdao Ocean, 25%) was dissolved in 20ml deionized water, stirred for 15 minutes or more to make it evenly distributed, labeled as silicon source; 2.4g sodium hydroxide and 4.92g sodium metaaluminate were dissolved in 34ml Ionic water was stirred until clear and labeled as an aluminum source; 1.16 g of L-carnitine L-tartrate was dissolved in 5 ml of deionized water, sonicated and labeled as an additive. The remaining steps were the same as in Example 1 to give 8.7 g of the product as the amino acid-zeolite composite LCLT@MLTA.

Example 4 Preparation of Microporous-Mesoporous Layer Zeolite Material MLTA-LCLT

5 g of the amino acid-zeolite composite LCLT@MLTA obtained in Example 3 was stirred in 100 g of deionized water for 5 minutes, and the resulting suspension was centrifuged, and the above operation was repeated twice, and the white solid after centrifugation was collected and dried at 60 ° C. 4.3 g of product was obtained as a microporous mesoporous grade zeolitic material MLTA-LCLT. The remaining steps are the same as in Example 2, and the correlation diagram of the nitrogen adsorption desorption isotherm at 77K and the dV/dlog(D) pore volume calculated by the BJH method and the average pore diameter D _p are shown in Fig. 9. The pore-mesoporous grade zeolite material MLTA-LCLT has a mesoporous range of 10 to 50 nm, an average pore diameter of 16.0 nm, a BET specific surface area of 104 m ² /g, and a mesoporous pore volume of 0.07 cm ³ /g. The Si/Al ratio was 1.13.

The scanning electron microscope (SEM) and transmission electron microscope (TEM) observation images are shown in Fig. 10. The LTA crystal form and mesoporous structure are also apparent. The particles are composed of polycrystalline structures, and the non-ordered pore structure penetrates the inside of the crystal.

Example 5 Synthesis of Amino Acid-Zeolite Composite Lys@MLTA

12.54ml silica sol (Qingdao Ocean, 25%) was dissolved in 20ml deionized water, stirred for 15 minutes or more to make it evenly distributed, labeled as silicon source; 2.4g sodium hydroxide and 4.92g sodium metaaluminate were dissolved in 34ml Ionic water was stirred until clear and labeled as an aluminum source; 4.35 g of lysine was dissolved in 5 ml of deionized water, sonicated and labeled as an additive. The rest of the steps were the same as in Example 1, to give 8.26 g of the product as the amino acid-zeolite composite Lys@MLTA.

Example 6 Preparation of Microporous-Mesoporous Layer Zeolite Material MLTA-Lys

5 g of the amino acid-zeolite composite Lys@MLTA obtained in Example 5 was stirred in 100 g of deionized water for 5 minutes, and the resulting suspension was centrifuged, and the above operation was repeated twice, and the white solid after centrifugation was collected and dried at 60 ° C. 4.17 g of product was obtained as a microporous mesoporous grade zeolitic material MLTA-Lys. The remaining steps were the same as in Example 2, and the microporous-mesoporal grade zeolitic material MLTA-LCLT was obtained with a mesoporous range of 10-50 nm, an average pore diameter of 19.1 nm, a BET specific surface area of 89 m ² /g, and mesoporous pore volume. 0.07 cm ³ /g. The mercury intrusion experiment was carried out by using the AutoPore IV 9500 series high performance automatic large hole measuring analyzer from Mike Instruments. The macroporous characteristics of the microporous mesoporous zeolite material MLTA-Lys were measured to obtain the macropore specific surface area. 230 m ² /g, large pore volume was 1.01 cm ³ /g, macroporous average pore diameter was 315 nm, and macroporous porosity was 66%. The Si/Al ratio was 1.16.

Example 7 Synthesis of Amino Acid-Zeolite Composite LysAc@MLTA

12.54ml silica sol (Qingdao Ocean, 25%) was dissolved in 20ml deionized water, stirred for 15 minutes or more to make it evenly distributed, labeled as silicon source; 2.4g sodium hydroxide and 4.92g sodium metaaluminate were dissolved in 34ml Ionic water was stirred until clear and labeled as an aluminum source; 6.14 g of lysine acetate was dissolved in 5 ml of deionized water, sonicated and labeled as an additive. The rest of the steps were the same as in Example 1, to give 7.96 g of product as the amino acid-zeolite composite LysAc@MLTA.

Example 8 Preparation of Microporous-Mesoporous Layer Zeolite Material MLTA-LysAc

5 g of the amino acid-zeolite composite LysAc@MLTA obtained in Example 7 was stirred in 100 g of deionized water for 5 minutes, and the resulting suspension was centrifuged, and the above operation was repeated twice, and the white solid after centrifugation was collected and dried at 60 ° C. 4.31 g of product was obtained as a microporous mesoporous grade zeolitic material MLTA-LysAc. The remaining steps were the same as in Example 2, and the microporous mesoporous grade zeolitic material MLTA-LysAc was obtained having a mesoporous range of 10 to 50 nm, an average pore diameter of 19.0 nm, a BET specific surface area of 141 m ² /g, and mesoporous pore volume. 0.07 cm ³ /g. It also contains 50-100 nm macropores with a Si/Al ratio of 1.14.

Example 9 Synthesis of Amino Acid-Zeolite Composite LC@MFAU

12.54ml silica sol (Qingdao Ocean, 25%) was dissolved in 20ml deionized water, stirred for 15 minutes or more to make it evenly distributed, labeled as silicon source; 3.16g sodium hydroxide and 0.91g sodium metaaluminate were dissolved in 30ml Ionic water was stirred until clear and labeled as an aluminum source; 1.77 g of L-carnitine was dissolved in 10 ml of deionized water, sonicated and labeled as an additive. The aluminum source was added dropwise to the silicon source, stirring was continued, and heating was started after aging for 3 hours at room temperature, and the set temperature was 100 °C. The additive solution was added dropwise to the aged product of the above aluminum source and silicon source at a constant rate, and the temperature was raised to 100 ° C to start timing. After 20 hours, the mixture was centrifuged to collect a white solid, which was dried at 60 ° C to obtain 8.6 g of the product, which was an amino acid. - Zeolite composite LC@MFAU.

Example 10 Preparation of Microporous-Mesoporous Zeolite Material MFAU-LC

5 g of the amino acid-zeolite composite LC@MFAU obtained in Example 9 was stirred in 100 g of deionized water for 5 minutes, and the resulting suspension was centrifuged, and the above operation was repeated twice, and the white solid after centrifugation was collected and dried at 60 ° C. 4.41 g of product was obtained as a microporous mesoporous grade zeolite material MFAU-LC. The remaining steps were the same as in Example 2, and a powder diffraction pattern of a microporous-mesoporal graded zeolite material MFAU-LC, a 77 K nitrogen adsorption-desorption isotherm, a scanning electron micrograph, and a transmission electron microscope photograph are shown in Fig. 11. It was proved to be a zeolite crystal FAU structure having a mesoporous range of 10 to 60 nm, an average pore diameter of 30 nm, a BET specific surface area of 572 m ² /g, and mesopores inside the crystal of FAU.

Comparative Example 11 Synthesis of Traditional LTA Zeolite Material CLTA Zeolite

12.54ml silica sol (Qingdao Ocean, 25%) was dissolved in 20ml deionized water, stirred for 15 minutes or more to make it evenly distributed, labeled as silicon source; 2.4g sodium hydroxide and 4.92g sodium metaaluminate were dissolved in 34ml Ionic water was stirred until clear and labeled as an aluminum source. The aluminum source was added dropwise to the silicon source, stirring was continued, and heating was started after aging for 3 hours at room temperature, and the set temperature was 100 °C. After the temperature was raised to 100 ° C, the time was counted. After 3 hours, the mixture was centrifuged, and a white solid was collected and dried at 60 ° C to obtain 8.22 g of a product. Washing and characterization were carried out in the same manner as in Example 2. The obtained XRD and 77K nitrogen adsorption-desorption isotherms, SEM and TEM images are shown in Fig. 12. It can be seen that the smooth LTA type crystal structure has a very small amount of nitrogen adsorption, which is close to the detection limit of the instrument, regardless of the adsorption and desorption data. No mesoporous distribution was observed in either TEM or TEM images.

Comparative Example 12 Synthesis of Traditional FAU Zeolite Material CFAU Zeolite

12.54ml silica sol (Qingdao Ocean, 25%) was dissolved in 30ml deionized water, stirred for 15 minutes or more to make it evenly distributed, labeled as silicon source; 3.16g sodium hydroxide and 0.91g sodium metaaluminate were dissolved in 30ml Ionic water was stirred until clear and labeled as an aluminum source. Adding an aluminum source to the silicon source, Stirring was continued, and heating was started after 3 hours of room temperature aging, and the set temperature was 100 °C. After the temperature was raised to 100 ° C, the time was counted. After 12 hours, the mixture was centrifuged, and a white solid was collected and dried at 60 ° C to obtain 8.1 g of a product. Washing and characterization were carried out in the same manner as in Example 2. The XRD and 77K nitrogen adsorption-desorption isotherms, SEM and TEM images are shown in Fig. 13. The smooth FAU crystal structure can be seen. The nitrogen adsorption isotherms and the desorption isotherms are basically coincident, and there is no detention loop. No mesoporous distribution was observed from either the adsorption and desorption data or the TEM image.

Test Example 1 Amino acid-zeolite composite as a chiral solid application

The amino acid-zeolite composite LC@MLTA of Example 1 was accurately weighed, the microporous mesoporous grade zeolite material MLTA-LC of Example 2, and the conventional LTA type zeolite material CLTA zeolite of Comparative Example 11 were each dispersed in 10 ml. In deionized water, the optical rotation value α is obtained by testing in an automatic polarimeter (Rudolph Autopol I) by the following formula.

[α]=100α/l*C

Where: C--solution concentration (g / 100mL); l - the length of the optical tube (dm).

Among them, LC@MLTA has an optical rotation value α of 1.3, MLTA-LC optical rotation value α is 0.1, CLTA optical rotation value α is 0, solution concentration is 1g/100mL, and optical tube length is 1dm, and the final ratio can be calculated. Optical rotation [a]. Under the same test conditions, the specific optical rotation of the amino acid-zeolite composite material LC@MLTA of Example 1 was 1.3, and the specific optical rotation of the microporous mesoporous grade zeolite material MLTA-LC of Example 2 was 0.1, Comparative Example 11 The specific optical rotation of the conventional conventional LTA type zeolite material CLTA is zero.

The amino acid-zeolite composite Lys@MLTA of Example 5 was accurately weighed, and 100 mg of each of the microporous-mesoporous grade zeolite materials MLTA-Lys prepared in Example 6 was dispersed in 10 ml of deionized water in an automatic polarimeter (Rudolph Autopol). The I) test yields optical rotation values α of 1.5 and 0.3, respectively. By the above formula, the specific optical rotation [a] of the amino acid-zeolite composite Lys@MLTA of Example 5 was calculated to be 1.5, and the specific optical rotation of the microporous-mesoporal grade zeolitic material MLTA-Lys prepared in Example 6 [ a] is 0.3.

It can be seen that the amino acid-zeolite composites have chirality and can be used as chiral solids, and thus are applied to chromatographic packings, chiral extraction columns and the like, while conventional zeolite materials have no chirality.

Test Example 2 Application of microporous-mesoporal grade zeolite materials to immobilization of biomacromolecules.

Bovine liver catalase (hydrogen peroxide oxidoreductase EC1.11.1.6) has four polypeptide chains, each of which is about 500 amino acids long, so bovine liver catalase has a molecular size of ～10 nm. Glycoproteins are widely used in industrial catalytic degradation of peroxides into water and oxygen. 50 mg of fresh catalase was dissolved in 10 ml of pH=7.2 phosphate (PBS) buffer and stored in an ice water bath. 100 mg of mesoporous zeolite material was added, and an enzyme adsorption experiment was carried out at 4 ° C, magnetic stirring at 600 rpm. During the adsorption process, 300 μl samples were centrifuged at different time points and the supernatant was taken for measurement of catalase concentration on a NanoDrop 2000c (Thermo Scientific) instrument. The peroxylysis of the mesoporous zeolite was calculated by subtraction. The amount of hydrogenase loaded. In the catalase activity test, the adsorption test procedure is similar to the above, but the sample is not sampled in the middle, and after 24 hours, the centrifuge is used to detect the concentration of the supernatant catalase, thereby calculating the hydrogen peroxide adsorbed by the mesoporous molecular sieve. The total amount of enzyme. The catalase in the mesoporous molecular sieve was formulated to a concentration of 0.05 mg/ml, and the test was carried out using a catalase kit (Beijing Suo Laibao Technology Co., Ltd., product number #BC0760), and a fresh 0.05 mg/ml was prepared. Pure catalase was used as a control to calculate relative enzyme activity. Fig. 14(a) shows MLTA-LC in Example 2, MLTA-LCLT in Example 4, MLTA-Lys in Example 6, and MLTA-LysAc microporous-mesoporal level LTA in Example 8. The adsorption kinetics of the zeolite material for bovine liver catalase, the equilibrium loadings were 241, 264, 179, 208 mg/g, respectively, and compared the traditional microporous LTA zeolite CLTA sample of Comparative Example 11 to bovine liver. The adsorption kinetics curve of catalase has an equilibrium loading of only 112 mg/g; Figure 14 (b) and the MLTA-LC of Example 2, MLTA-LCLT of Example 4, examples MLTA-Lys in 6 , catalyzed activity of MLTA-LysAc microporous-mesoporal grade LTA type zeolite material in Example 8, relative to free state catalase, immobilized hydrogen peroxide The relative activities of the enzymes were 94%, 95%, 96%, and 90%, respectively, and the activity of the bovine liver catalase immobilized on the conventional microporous LTA zeolite CLTA sample of Comparative Example 11 was compared, and its relative activity was only 82%. .

The above is a further detailed description of the present invention in connection with the specific embodiments, and the specific embodiments of the present invention are not limited to the description. It will be apparent to those skilled in the art that the present invention may be made without departing from the spirit and scope of the invention.

Claims (26)

1. An amino acid-zeolite composite comprising a zeolite structure and dispersed amino acid molecules residing in a pore structure of the zeolite structure, the zeolite structure comprising a microporous structure and a mesoporous structure, and at least a portion of the The pore structure is located inside the crystal.
2. The amino acid-zeolite composite according to claim 1, wherein the mesoporous structure is entirely located inside the crystal.
3. The amino acid-zeolite composite according to claim 1, wherein the amino acid-zeolite composite further comprises a macroporous structure.
4. The amino acid-zeolite composite according to claim 1, wherein the amino acid is selected from the group consisting of a hydrophilic amino acid and/or a non-standard zwitterionic amino acid.
5. The amino acid-zeolite composite according to claim 4, wherein the hydrophilic amino acid is selected from the group consisting of lysine, arginine, histidine, tyrosine, serine, threonine, and cysteine. One or more of acid, asparagine, glutamine, aspartic acid, and glutamic acid; the non-standard zwitterionic amino acid is selected from the group consisting of betaine, L-carnitine, ectoine, and twelve Sodium alkylaminopropionate, sodium lauryl dimethylmethylene dicarboxylate, Na-acyl lysine, Na-methyl-Na-lauroyl lysine, N-acyl sarcosine, N-acyl valley One or more of amino acid, N-acyl sarcosine, N-alkyl aspartic acid-β-alkyl ester, N-acyl glutamic acid diester, and di(octylamino) glycine .
6. The amino acid-zeolite composite according to claim 1, wherein the zeolite structure is selected from the group consisting of LTA, FAU, SOD, CAN, BEA, CHA, RTH, EMT, MFI, MEL, MOR or EON type zeolites.
7. The amino acid-zeolite composite according to claim 1, wherein the loading of the zeolite in the amino acid-zeolite composite is between 1% and 30% based on the total mass of the amino acid-zeolite composite.
8. The amino acid-zeolite composite according to claim 7, wherein the loading of the zeolite in the amino acid-zeolite composite is between 5% and 20% based on the total mass of the amino acid-zeolite composite.
9. The amino acid-zeolite composite according to claim 1, wherein the amino acid interacts with the zeolite structure by hydrogen bonding and/or electrostatic interaction.
10. A microporous-mesoporous graded zeolitic material characterized by comprising a zeolite structure comprising a microporous structure and a mesoporous structure, and at least a portion of said mesoporous structure is located inside the crystal.
11. The microporous mesoporous grade zeolite material according to claim 10, wherein the mesoporous structure is entirely located inside the crystal.
12. The microporous mesoporous grade zeolite material according to claim 10, wherein the microporous mesoporous grade zeolite material further comprises a macroporous structure.
13. The microporous mesoporous grade zeolite material according to claim 10, wherein the zeolite structure is selected from the group consisting of LTA, FAU, SOD, CAN, BEA, CHA, RTH, EMT, MFI, MEL, MOR or EON Zeolite.
14. The microporous mesoporous grade zeolite material according to claim 10, wherein the microporous mesoporous layer zeolite material has an adsorption effect on biomacromolecules and/or large ions, and the amount of solidification is as described The total mass of the microporous mesoporous layer zeolite material is more than 17%, preferably more than 27%.
15. The microporous mesoporous grade zeolite material according to claim 10, wherein the microporous mesoporous layer zeolite material has an adsorption effect on catalase, and the relative activity of the adsorbed catalase is more than 90 percent.
16. The microporous mesoporous grade zeolitic material according to claim 10, wherein the mesoporous structure has a mesoporous pore size distribution of between 10 and 50 nm and an average pore size distribution of between 16 and 20 nm.
17. The microporous mesoporous grade zeolite material according to claim 10, wherein the microporous mesoporous grade zeolite material has a BET specific surface area of 90 m ² /g or more.
18. A method for preparing an amino acid-zeolite composite, characterized in that an amino acid is added as an additive in a zeolite synthesis raw material, and the obtained amino acid-zeolite composite material comprises a zeolite structure and a dispersed amino acid residing in a pore structure of the zeolite structure. A molecule, the zeolite structure comprising a microporous structure and a mesoporous structure, and at least a portion of the mesoporous structure is located inside the crystal.
19. The method according to claim 18, wherein the amino acid is selected from the group consisting of a hydrophilic amino acid and/or a non-standard zwitterionic amino acid.
20. The method of claim 18 wherein said zeolitic synthesis feedstock comprises a source of silicon, a source of aluminum and a base, and optionally a source of heteroatoms and/or metals.
21. The method according to claim 18, wherein the synthesis reaction is carried out at a temperature between 0 and 300 ° C and a pressure between atmospheric pressure and 20 bar.
22. The method of claim 18, wherein the method comprises the steps of:

    a) introducing an amino acid as an additive into a zeolite synthesis feedstock comprising a silicon source, an aluminum source and a base, and optionally a heteroatom and/or a metal source, at a temperature between 0 and 300 ° C and a pressure at atmospheric pressure to Synthesis reaction between 20bar;

    b) solid-liquid separation of the mixture of step a) and drying of the solid product to obtain the amino acid-zeolite composite.
23. A method for preparing a microporous-mesoporal graded zeolitic material, comprising washing the amino acid-zeolite composite of claim 1 to obtain the microporous-mesoporous grade zeolitic material comprising a zeolite structure The zeolite structure includes a microporous structure and a mesoporous structure, and at least a portion of the mesoporous structure is located inside the crystal.
24. The method of claim 23 wherein the washing is carried out using water.
25. Use of the amino acid-zeolite composite of claim 1 as a catalyst, adsorbent or ion exchanger.
26. Use of the microporous mesoporous grade zeolite material of claim 10 as a catalyst, adsorbent or ion exchanger.

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