CN114380302A - Hierarchical pore ZSM-5 molecular sieve and preparation method and application thereof - Google Patents

Hierarchical pore ZSM-5 molecular sieve and preparation method and application thereof Download PDF

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CN114380302A
CN114380302A CN202210093826.1A CN202210093826A CN114380302A CN 114380302 A CN114380302 A CN 114380302A CN 202210093826 A CN202210093826 A CN 202210093826A CN 114380302 A CN114380302 A CN 114380302A
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molecular sieve
hierarchical pore
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pore zsm
silicon source
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CN114380302B (en
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于吉红
刘滢昊
李俊延
王星星
闫文付
白璞
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Luoyang Jianlong Micro Nano New Materials Co ltd
Jilin University
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Jilin University
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Abstract

The invention provides a hierarchical pore ZSM-5 molecular sieve, and a preparation method and application thereof, and relates to the technical field of functional materials. The invention is based on the amorphous molecular sieve seed crystal auxiliary method to prepare the hierarchical pore ZSM-5 molecular sieve, and utilizes the characteristic that the amorphous molecular sieve seed crystal can instantly provide a large number of growth or crystallization sites to initiate multi-point crystallization in precursor polymer particles at the initial stage of crystallization, thereby causing the migration of nutrient substances near the growth sites and finally forming the through mesopores leading to the interior of the crystal grains. The method provided by the invention is simple and convenient to operate, environment-friendly and low in cost; the prepared hierarchical pore ZSM-5 molecular sieve has a stable crystal skeleton structure and an excellent hierarchical pore structure, and the stability and the diffusion performance of the hierarchical pore ZSM-5 molecular sieve are greatly improved, so that the excellent service life and the excellent propylene selectivity are shown in the reaction of preparing the olefin from the methanol.

Description

Hierarchical pore ZSM-5 molecular sieve and preparation method and application thereof
Technical Field
The invention relates to the technical field of functional materials, in particular to a hierarchical pore ZSM-5 molecular sieve and a preparation method and application thereof.
Background
The molecular sieve material has excellent thermal stability, hydrothermal stability, adjustable acidity and unique shape selectivity, and has wide and important application in heterogeneous catalysis. The ZSM-5 molecular sieve has three-dimensional ten-membered ring cross channels and a full-range silicon-aluminum ratio (Si/Al) of 1 to infinity, and has the function of being difficult to replace in important fields of methanol-to-gasoline, methanol-to-olefin (MTO), alkane isomerization or cracking, alkane dehydrogenation-to-olefin, aromatization, toluene disproportionation and the like. The methanol-to-olefin is a chemical technology for producing high-value low-carbon olefin by using methanol as a substrate, and particularly, propylene in the product is a high value-added product which plays a very important role in industry, so that the development of the methanol-to-olefin process is of great significance. However, the conventional molecular sieve has a significant limitation of short lifetime in many catalytic reactions because the single and narrow microporous pore channel greatly limits the diffusion rate of molecules therein and also reduces the accessibility, releasability and availability of active sites.
The hierarchical pore molecular sieve integrates the intrinsic characteristics of the traditional molecular sieve and the excellent diffusion performance brought by the mesoporous structure, effectively relieves the problems of diffusion limitation of microporous channels, low accessibility of active sites, low releasability, low utilization rate and the like, and is widely concerned by researchers. Currently, the preparation methods of hierarchical pore molecular sieves can be divided into two categories: one is a top-down post-treatment method, and the other is a bottom-up in situ synthesis method. Wherein, the top-down post-treatment method is to etch the traditional molecular sieve by acid or alkali to remove part of the framework to manufacture the mesoporous structure, the principle is simple, the operation is easy, and the cost is lower, so the method is already applied in industry; however, the method often cannot control the degree of framework removal, is easy to excessively remove to cause the collapse problem of the framework structure of the molecular sieve, cannot control the silica-alumina ratio of the product hierarchical pore molecular sieve, and also can greatly reduce the yield of the product. The in-situ synthesis from bottom to top mostly depends on a hard template method or a soft template method, and in addition, a hierarchical pore molecular sieve is prepared by adding certain organic molecules as growth regulators to change the growth kinetic path of molecular sieve crystallization. The hard template method is to use carbon nanometer particle, carbon nanometer rod or cellulose to occupy space to limit the growth of molecular sieve and to eliminate hard template through high temperature calcination to obtain hierarchical porous molecular sieve. The method is simple to operate, but the hard template and a molecular sieve growth system are different in hydrophilicity and hydrophobicity, so that the problem of phase separation often exists, and the mesopores cannot be effectively manufactured. The soft template method uses some nitrogen-containing long carbon chain organic matters, surfactants, organic silane or cationic polymers and the like as soft templates, effectively solves the problem of phase separation by using the interaction of the soft templates and the growing molecular sieve, and can accurately control the appearance, size and volume of mesopores due to the designability of the soft templates. In addition, the growth regulators themselves are expensive and difficult to be put to practical use.
The method for synthesizing the molecular sieve by the aid of the seed crystals has attracted wide attention due to the advantages of low cost, high yield, short crystallization time and the like. However, the molecular sieve seed crystals adopted in the method are usually seed crystals with complete crystal frameworks, and only nano molecular sieves or polycrystalline hierarchical pore molecular sieves formed by aggregating small particles can be obtained, wherein the industrial application of the nano molecular sieves is limited due to the difficulty in separating the molecular sieves from catalytic reaction liquid, and the polycrystalline hierarchical pore molecular sieves are prone to further aggregate in the reaction due to fragile aggregate polycrystalline structures, so that mesoporous structures disappear.
Disclosure of Invention
The invention aims to provide a hierarchical pore ZSM-5 molecular sieve, a preparation method and application thereof, and the method provided by the invention is simple and convenient to operate, environment-friendly and low in cost; the hierarchical pore ZSM-5 molecular sieve prepared by the amorphous molecular sieve seed crystal auxiliary method has a stable crystal skeleton structure and an excellent hierarchical pore structure, and the stability and the diffusion performance of the molecular sieve are greatly improved, so that the molecular sieve has an excellent service life and excellent propylene selectivity in a methanol-to-olefin reaction.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a hierarchical pore ZSM-5 molecular sieve, which comprises the following steps:
providing amorphous molecular sieve seed crystals;
mixing the amorphous molecular sieve seed crystal, a first silicon source, a first microporous template agent, a first aluminum source, a mineralizer and water to obtain a first mixed feed liquid, and performing hydrothermal crystallization reaction to obtain a hydrothermal crystallization reaction product;
and sequentially carrying out first washing, first drying and first calcining treatment on the hydrothermal crystallization reaction product to obtain the hierarchical pore ZSM-5 molecular sieve.
Preferably, the first silicon source comprises silica sol or tetraethyl orthosilicate, the first microporous templating agent comprises tetrapropylammonium hydroxide or tetrapropylammonium bromide, the first aluminum source comprises sodium metaaluminate, aluminum sulfate, or aluminum chloride, and the mineralizer comprises sodium hydroxide or potassium hydroxide.
Preferably, the amount of the first silicon source is SiO2The amount of the first aluminum source is calculated as Al2O3And the components in the first mixed feed liquid meet the following requirements: the molar ratio of the first silicon source, the first microporous template agent, the first aluminum source, the mineralizer and the water is 1: (0.01-0.03): (0.002-0.02): (0.15-0.40): (15-30);
the first silicon source is SiO2And the mass of the amorphous molecular sieve seed crystal is not more than 13 wt% of the mass of the first silicon source.
Preferably, the temperature of the hydrothermal crystallization reaction is 120-170 ℃ and the time is 1-5 days.
Preferably, the preparation method of the amorphous molecular sieve seed crystal comprises the following steps:
mixing a second silicon source, a second microporous template agent, a second aluminum source, L-lysine and water to obtain a second mixed feed liquid, and carrying out hydrothermal reaction to obtain a hydrothermal reaction product;
and sequentially carrying out second washing, second drying and second calcining treatment on the hydrothermal reaction product to obtain amorphous molecular sieve seed crystals.
Preferably, the second silicon source comprises tetraethyl orthosilicate, the second microporous templating agent comprises tetrapropylammonium hydroxide or tetrapropylammonium bromide, and the second aluminum source comprises sodium metaaluminate, aluminum sulfate, or aluminum chloride.
Preferably, the amount of the second silicon source is SiO2The amount of the second aluminum source is calculated as Al2O3And the components in the second mixed feed liquid meet the following requirements: the molar ratio of the second silicon source, the second microporous template agent, the second aluminum source, L-lysine and water is 1: (0.30-0.50): (0.002-0.05): (0.25-0.45): (5-15).
Preferably, the first calcination treatment further comprises:
mixing the first calcined product obtained after the first calcination treatment, ammonium chloride and water to obtain a third mixed feed liquid, and performing ammonium exchange treatment to obtain an ammonium exchange product;
and sequentially carrying out third washing, third drying and third calcining treatment on the ammonium exchange product to obtain the hierarchical pore ZSM-5 molecular sieve.
The invention provides the hierarchical pore ZSM-5 molecular sieve prepared by the preparation method in the technical scheme, wherein the granularity of the hierarchical pore ZSM-5 molecular sieve is 80-200 nm.
The invention provides application of the hierarchical pore ZSM-5 molecular sieve in the technical scheme as a catalyst for preparing olefin from methanol.
The invention provides a preparation method of a hierarchical pore ZSM-5 molecular sieve, which comprises the following steps: providing amorphous molecular sieve seed crystals; a preparation method of a hierarchical pore ZSM-5 molecular sieve comprises the following steps: providing amorphous molecular sieve seed crystals; mixing the amorphous molecular sieve seed crystal, a first silicon source, a first microporous template agent, a first aluminum source, a mineralizer and water to obtain a first mixed feed liquid, and performing hydrothermal crystallization reaction to obtain a hydrothermal crystallization reaction product; and sequentially carrying out first washing, first drying and first calcining treatment on the hydrothermal crystallization reaction product to obtain the hierarchical pore ZSM-5 molecular sieve. The method provided by the invention can efficiently manufacture mesopores, is environment-friendly and has low cost. Meanwhile, the amorphous molecular sieve seed crystal has a microporous structure of the molecular sieve to a certain degree, so that growth sites can be provided and the generation of the molecular sieve can be guided like the traditional seed crystal, meanwhile, because the amorphous molecular sieve seed crystal has smaller particles and higher defect density, a large number of growth or crystallization sites can be provided instantly, multi-point crystallization in precursor polymer particles at the initial stage of crystallization is initiated, further, nutrient substances near the growth sites are migrated, finally, penetrating mesopores leading to the inside of the crystal grains are formed, and the obtained multi-level pore ZSM-5 molecular sieve has a single crystal structure, so that the stability is good. Therefore, the invention enables the molecular sieve crystal to grow a hierarchical pore structure by regulating and controlling the growth behavior of the molecular sieve crystal, and the hierarchical pore structure does not depend on the limited-area growth effect of the mesoporous template agent, so the subsequent mesoporous template agent removing process is not needed, the corresponding energy consumption, the generation of toxic waste gas and the damage to the framework are avoided, and the acid or alkali etching for damaging the framework is not neededAnd can greatly reduce the dosage of the first micropore template (such as the first micropore template and SiO)2The mole ratio of the first silicon source is less than or equal to 0.03), the one-step synthesis method is simple and convenient to operate, and the yield of the molecular sieve is high (>85％)。
The multistage pore ZSM-5 molecular sieve prepared by the method provided by the invention has the advantages that the crystal grains are highly monodisperse, the granularity is within the range of 80-200 nm, the crystal grains are rich in penetrating mesopores leading to the inside, the crystal grains of the molecular sieve are of a single crystal structure, all silicon and aluminum on the molecular sieve are in a four-coordination form on a framework, and the structure is stable. The stable crystal skeleton structure and the excellent hierarchical pore structure of the hierarchical pore ZSM-5 molecular sieve greatly improve the stability and the diffusion performance of the hierarchical pore ZSM-5 molecular sieve, so that the excellent service life and the excellent propylene selectivity are shown in the reaction of preparing the olefin from the methanol, and the application prospect is wide. The results of the examples show that the multistage pore ZSM-5 molecular sieve provided by the invention has the service life of 552.71 hours (conversion rate) in the reaction of preparing olefin from methanol>80%, 500 ℃, WHSV: the first 444 hours and the second 2 hours-11h after 444 hours-1) High selectivity of propylene, a high value product(s) ((>40%) and no significant decay in propylene selectivity throughout the course of the reaction, the propylene/ethylene molar ratio (P/E value) was higher than 3.5 for up to 551.7 hours (125.6 hours to 677.3 hours), and the overall trend of the P/E value rose throughout the course of the reaction.
Drawings
FIG. 1 is an XRD spectrum and TEM photograph of amorphous molecular sieve seed crystals prepared in example 1;
FIG. 2 is an XRD spectrum of an H-type hierarchical pore ZSM-5 molecular sieve prepared in example 1;
FIG. 3 is a TEM image of an H-type multi-stage pore ZSM-5 molecular sieve prepared in example 1;
FIG. 4 is a high power TEM image of an H-type multi-stage pore ZSM-5 molecular sieve prepared in example 1;
FIG. 5 is a selected area electron diffraction pattern corresponding to the entire crystal of FIG. 4;
FIG. 6 is the N of the H-type multi-stage pore ZSM-5 molecular sieve prepared in example 12Adsorption/desorption isotherm plot;
FIG. 7 is a graph showing the catalytic effect of the H-type multi-stage pore ZSM-5 molecular sieve prepared in example 1 in a methanol to olefin reaction;
FIG. 8 is an XRD spectrum of an H-type multi-stage pore ZSM-5 molecular sieve prepared in example 2;
FIG. 9 is a TEM image of an H-type multi-stage pore ZSM-5 molecular sieve prepared in example 2;
FIG. 10 is an XRD spectrum of an H-type multi-stage pore ZSM-5 molecular sieve prepared in example 3;
FIG. 11 is a TEM image of an H-type multi-stage pore ZSM-5 molecular sieve prepared in example 3;
FIG. 12 is an XRD spectrum of an H-type multi-stage pore ZSM-5 molecular sieve prepared in example 4;
FIG. 13 is a TEM image of an H-type multi-stage pore ZSM-5 molecular sieve prepared in example 4;
FIG. 14 is an XRD spectrum of an H-type ZSM-5 molecular sieve prepared in comparative example 1;
FIG. 15 is an SEM image of an H-type ZSM-5 molecular sieve prepared in comparative example 1;
FIG. 16 is a TEM image of an H-type ZSM-5 molecular sieve prepared in comparative example 1;
FIG. 17 is an XRD spectrum of an H-type ZSM-5 molecular sieve prepared in comparative example 2;
FIG. 18 is a TEM image of an H-type ZSM-5 molecular sieve prepared in comparative example 2.
Detailed Description
The invention provides a preparation method of a hierarchical pore ZSM-5 molecular sieve, which comprises the following steps:
providing amorphous molecular sieve seed crystals;
mixing the amorphous molecular sieve seed crystal, a first silicon source, a first microporous template agent, a first aluminum source, a mineralizer and water to obtain a first mixed feed liquid, and performing hydrothermal crystallization reaction to obtain a hydrothermal crystallization reaction product;
and sequentially carrying out first washing, first drying and first calcining treatment on the hydrothermal crystallization reaction product to obtain the hierarchical pore ZSM-5 molecular sieve.
The invention first provides amorphous molecular sieve seeds. In the present invention, the method for preparing amorphous molecular sieve seeds preferably comprises the following steps:
mixing a second silicon source, a second microporous template agent, a second aluminum source, L-lysine and water to obtain a second mixed feed liquid, and carrying out hydrothermal reaction to obtain a hydrothermal reaction product;
and sequentially carrying out second washing, second drying and second calcining treatment on the hydrothermal reaction product to obtain amorphous molecular sieve seed crystals.
According to the invention, a second silicon source, a second microporous template agent, a second aluminum source, L-lysine and water are mixed to obtain a second mixed feed liquid, and a hydrothermal reaction is carried out to obtain a hydrothermal reaction product. In the present invention, the second silicon source preferably comprises tetraethyl orthosilicate, the second microporous templating agent preferably comprises tetrapropylammonium hydroxide or tetrapropylammonium bromide, more preferably tetrapropylammonium hydroxide (TPAOH), and the second aluminum source preferably comprises sodium metaaluminate, aluminum sulfate or aluminum chloride, more preferably sodium metaaluminate. In the present invention, the L-lysine functions to provide a concentrated gel system to reduce the size of the product and to increase the solubility of aluminum by coordinating with aluminum species. In the invention, the amount of the second silicon source is SiO2The amount of the second aluminum source is calculated as Al2O3And the components in the second mixed feed liquid meet the following requirements: the molar ratio of the second silicon source, the second microporous template agent, the second aluminum source, the L-lysine and the water is preferably 1: (0.30-0.50): (0.002-0.05): (0.25-0.45): (5-15), more preferably 1: 0.45: 0.003: 0.4: 9. in the present invention, the manner of mixing the second silicon source, the second microporous template, the second aluminum source, and the L lysine with water preferably includes: mixing a second silicon source, a second micropore template agent and water, and stirring until a single-phase uniform system is obtained; adding a second aluminum source aqueous solution into the obtained system, and uniformly stirring; and then adding an aqueous solution of L-lysine into the obtained system, and uniformly stirring to obtain a second mixed feed liquid. In the invention, the temperature of the hydrothermal reaction is preferably 70-120 ℃, and more preferably 80-90 ℃; the time is preferably 12 to 24 hours, and more preferably 18 to 22 hours. According to the invention, the second mixed feed liquid is preferably placed in a reaction kettle to carry out the hydrothermal reaction.
After the hydrothermal reaction product is obtained, the hydrothermal reaction product is sequentially subjected to second washing, second drying and second calcining treatment to obtain amorphous molecular sieve seed crystals. In the present invention, the detergent used for the second washing is preferably water; the second washing method is not particularly limited, and may be a method known to those skilled in the art, and specifically may be centrifugal washing or filtration washing. The second drying is not specially limited, and the materials can be fully dried; in the present invention, the temperature of the second drying is preferably 150 ℃ or lower. In the invention, the temperature of the second calcination treatment is preferably 450-700 ℃, and more preferably 550-600 ℃; the time is preferably 5-10 h, more preferably 6-8 h; the second calcination treatment is preferably performed in an air atmosphere. The invention removes the residual second microporous template and L lysine through a second calcination treatment.
The particle size of the amorphous molecular sieve seed crystal is preferably less than 20nm, and more preferably 5-15 nm.
After amorphous molecular sieve seed crystals are obtained, the amorphous molecular sieve seed crystals, a first silicon source, a first microporous template agent, a first aluminum source, a mineralizer and water are mixed to obtain a first mixed feed liquid, and a hydrothermal crystallization reaction is carried out to obtain a hydrothermal crystallization reaction product. In the present invention, the first silicon source preferably comprises silica sol or tetraethyl orthosilicate, more preferably silica sol; the first microporous template preferably comprises tetrapropylammonium hydroxide or tetrapropylammonium bromide, more preferably tetrapropylammonium hydroxide; the first aluminum source preferably comprises sodium metaaluminate, aluminum sulfate or aluminum chloride, more preferably sodium metaaluminate; the mineralizer preferably comprises sodium hydroxide or potassium hydroxide, more preferably sodium hydroxide. In the invention, the amount of the first silicon source is SiO2The amount of the first aluminum source is calculated as Al2O3And the components in the first mixed feed liquid meet the following requirements: the mole ratio of the first silicon source, the first microporous template agent, the first aluminum source, the mineralizer and the water is preferably 1: (0.01-0.03): (0.002-0.02): (0.15-0.40): (15-30), more preferably 1: 0.02: 0.003: 0.325: 15; the first silicon source is SiO2The mass of the amorphous molecular sieve seed crystals is preferably not more than 13 wt% of the mass of the first silicon source, and the amorphous molecular sieve seed crystalsThe mass of the crystal seed of the shaped molecular sieve is more preferably 8-13 wt% of the mass of the first silicon source. In the present invention, the mixing manner of the amorphous molecular sieve seed crystal, the first silicon source, the first microporous template, the first aluminum source, the mineralizer and water preferably includes: mixing a first silicon source, a first micropore template and water, and uniformly stirring; adding amorphous molecular sieve seed crystals into the obtained system, and uniformly stirring; and then adding the aqueous solution of the first aluminum source and the mineralizer into the obtained system, and uniformly stirring. In the invention, the temperature of the hydrothermal crystallization reaction is preferably 120-170 ℃, and more preferably 120-140 ℃; the time is preferably 1 to 5 days, and more preferably 3 days. According to the invention, the first mixed feed liquid is preferably placed in a reaction kettle for the hydrothermal crystallization reaction.
After a hydrothermal crystallization reaction product is obtained, the hydrothermal crystallization reaction product is sequentially subjected to first washing, first drying and first calcining treatment to obtain the Na-type hierarchical porous ZSM-5 molecular sieve. In the present invention, the detergent used for the first washing is preferably water; the first washing method is not particularly limited, and may be a method known to those skilled in the art, and specifically may be a centrifugal washing or a filtration washing. The first drying is not specially limited, and the materials can be fully dried; in the present invention, the temperature of the first drying is preferably 150 ℃ or lower. In the invention, the temperature of the first calcination treatment is preferably 450-700 ℃, and more preferably 550-600 ℃; the time is preferably 5 to 10 hours, and more preferably 6 to 7 hours; the first calcination treatment is preferably performed in an air atmosphere. The invention removes the residual first microporous template agent through a first calcination treatment.
In the invention, the multi-stage hole ZSM-5 molecular sieve obtained after the first calcination treatment is a non-H type multi-stage hole ZSM-5 molecular sieve, and specifically, if the first mixed feed liquid contains sodium ions, the Na type multi-stage hole ZSM-5 molecular sieve is obtained after the first calcination treatment; and if the first mixed feed liquid contains potassium ions, performing first calcination treatment to obtain the K-type hierarchical pore ZSM-5 molecular sieve. In the present invention, the method for preparing the H-type multi-stage pore ZSM-5 molecular sieve based on the non-H-type multi-stage pore ZSM-5 molecular sieve preferably comprises the following steps:
mixing the first calcined product obtained after the first calcination treatment, ammonium chloride and water to obtain a third mixed feed liquid, and performing ammonium exchange treatment to obtain an ammonium exchange product;
and sequentially carrying out third washing, third drying and third calcining treatment on the ammonium exchange product to obtain the hierarchical pore ZSM-5 molecular sieve.
The method comprises the steps of mixing a first calcined product (namely a non-H-type hierarchical pore ZSM-5 molecular sieve) obtained after the first calcination treatment, ammonium chloride and water to obtain a third mixed feed liquid, and performing ammonium exchange treatment to obtain an ammonium exchange product. The non-H-type hierarchical pore ZSM-5 molecular sieve, the ammonium chloride and the water are preferably mixed in a mode of mixing the non-H-type hierarchical pore ZSM-5 molecular sieve with the ammonium chloride aqueous solution; the concentration of the ammonium chloride aqueous solution is preferably 0.1-1.5 mol/L, and more preferably 1 mol/L; the dosage ratio of the non-H-type hierarchical pore ZSM-5 molecular sieve to the ammonium chloride aqueous solution is preferably 1 g: (50-150) mL, more preferably 1 g: 100 mL. The temperature of the ammonium exchange treatment is preferably 70-85 ℃, and more preferably 80 ℃; the time is preferably 2-10 h, and more preferably 8 h; the ammonium exchange treatment is preferably carried out under stirring.
After obtaining the ammonium exchange product, the invention sequentially carries out third washing, third drying and third calcining treatment on the ammonium exchange product to obtain the hierarchical pore ZSM-5 molecular sieve (namely the H-type hierarchical pore ZSM-5 molecular sieve). In the present invention, the detergent used for the third washing is preferably water; the third washing method is not particularly limited, and may be a method known to those skilled in the art, and specifically may be centrifugal washing or filtration washing. The third drying is not specially limited, and the materials can be fully dried; in the present invention, the temperature of the third drying is preferably 150 ℃ or lower. In the invention, the temperature of the third calcination treatment is preferably 350-550 ℃, and more preferably 450-500 ℃; the time is preferably 4-8 h, and more preferably 6-8 h; the third calcination treatment is preferably performed in an air atmosphere. According to the invention, the ammonium ions in the material are decomposed into H through calcination by the third calcination treatment+And removing the excess ammonium salt. The invention is superiorAnd repeating the ammonium exchange treatment, the third washing, the third drying and the third calcining treatment once after the third calcining treatment to obtain the H-shaped hierarchical pore ZSM-5 molecular sieve.
The invention provides the hierarchical pore ZSM-5 molecular sieve prepared by the preparation method in the technical scheme, wherein the granularity of the hierarchical pore ZSM-5 molecular sieve is 80-200 nm. The hierarchical pore ZSM-5 molecular sieve provided by the invention is of a single crystal structure, the crystal grains are highly monodisperse, and the crystal grains have abundant penetrating mesopores leading to the inside; all silicon and aluminum on the hierarchical pore ZSM-5 molecular sieve provided by the invention are in a four-coordination form on a framework, and the structure is stable. In the embodiment of the invention, the mesoporous volume of the hierarchical pore ZSM-5 molecular sieve is 0.37cm3g-1Specific surface area of 619.9m2g-1。
The invention provides application of the H-type hierarchical pore ZSM-5 molecular sieve in the technical scheme as a catalyst for preparing olefin from methanol. The specific application method of the H-type hierarchical pore ZSM-5 molecular sieve as the methanol-to-olefin catalyst is not particularly limited, and the method known by the technical personnel in the field can be adopted. In the present invention, the reaction conditions for producing olefins from methanol preferably include: the reaction temperature is 500 ℃, and the space velocity WHSV is as follows: 2h-1(first 444h) and 1h-1(after 444h), water vapor was used as carrier gas.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing amorphous molecular sieve seed crystals by the following steps:
placing tetraethyl orthosilicate (TEOS), tetrapropylammonium hydroxide (TPAOH) aqueous solution (the mass fraction of TPAOH is 25%) and water in a beaker, and completely hydrolyzing the TEOS under the stirring condition; adding sodium metaaluminate aqueous solution into the obtained system,stirring and mixing uniformly; then adding L-lysine to the resulting systemLLysine) water solution, stirring and mixing uniformly to obtain mixed feed liquid; wherein, in terms of molar ratio, the mixed material liquid meets SiO2：Al2O3：TPAOH：H2O：L-lysine＝1.0：0.003：0.45：9：0.4；
Transferring the mixed material liquid into a reaction kettle, and carrying out hydrothermal reaction for 22h at the temperature of 90 ℃; after the reaction is finished, centrifugally washing the obtained solid product with water, drying the solid product in a 90 ℃ oven, and calcining the dried material at 550 ℃ for 6 hours in an air atmosphere to remove residual TPAOH and TPAOHLAnd lysine to obtain amorphous molecular sieve seed crystal with the particle size of 5-15 nm.
Preparing an H-type hierarchical pore ZSM-5 molecular sieve: the method comprises the following steps:
4.5gHS-40 silica Sol (SiO)240 percent of the amorphous molecular sieve crystal seed, 0.488g of TPAOH aqueous solution (the mass fraction of TPAOH is 25 percent) and 2.3g of water are added into a beaker, stirred and mixed uniformly, and then 0.2355g of the amorphous molecular sieve crystal seed is added into the beaker, stirred and mixed uniformly; mixing 0.0225g of sodium metaaluminate, 0.39g of sodium hydroxide and 3g of water, adding the obtained aqueous solution into the beaker, and uniformly stirring and mixing to obtain a mixed feed liquid; wherein, in terms of molar ratio, the components in the mixed feed liquid meet the following conditions: SiO 22：TPAOH：Al2O3：NaOH：H2O is 1: 0.02: 0.003: 0.325: 15, the amorphous molecular sieve seed crystal is SiO in mass213 wt% of mass; transferring the mixed material liquid into a reaction kettle, and carrying out hydrothermal crystallization reaction for 3 days at the temperature of 120 ℃; after the reaction is finished, centrifugally washing the obtained solid product with water, drying in a 90 ℃ oven, and calcining the dried material at 550 ℃ in an air atmosphere for 6 hours to remove residual TPAOH to obtain the Na-type hierarchical pore ZSM-5 molecular sieve;
dispersing 1g of the Na-type hierarchical porous ZSM-5 molecular sieve in 100mL of ammonium chloride aqueous solution with the concentration of 1mol/L, and performing ammonium exchange treatment for 8 hours at 80 ℃ under the stirring condition; then, centrifugally washing the obtained solid product with water, drying in a drying oven at 90 ℃, and calcining the dried material at 500 ℃ in an air atmosphere for 6 hours; and (3) repeatedly carrying out the ammonium exchange treatment, centrifugal washing, drying and calcination treatment on the calcined material once to obtain the H-shaped hierarchical pore ZSM-5 molecular sieve.
Fig. 1 shows XRD patterns and TEM photographs of amorphous molecular sieve seeds prepared in example 1, wherein (a) shows XRD patterns and (b) shows TEM photographs. As can be seen from FIG. 1, the amorphous molecular sieve seeds prepared in example 1 are amorphous nanoparticles, and the particle size of the individual small particles does not exceed 20 nm.
FIG. 2 is the XRD spectrum of the H-type multi-stage pore ZSM-5 molecular sieve prepared in example 1. from FIG. 2, the product prepared in example 1 is a pure phase ZSM-5 molecular sieve.
FIG. 3 is a TEM image of the H-type multi-stage pore ZSM-5 molecular sieve prepared in example 1 with a scale of 100 nm. As can be seen from FIG. 3, the H-type hierarchical pore ZSM-5 molecular sieve prepared in example 1 has good uniformity, highly monodisperse crystal grains, and good hierarchical pore morphology with a grain size in the range of 80-200 nm.
FIG. 4 is a high power TEM image of the H-type multi-stage pore ZSM-5 molecular sieve prepared in example 1, with a scale of 50 nm. As can be seen from fig. 4, the H-type hierarchical pore ZSM-5 molecular sieve prepared in example 1 has abundant mesoporous channels leading to the interior of the crystal grains.
FIG. 5 is a selected area electron diffraction pattern corresponding to the entire crystal of FIG. 4, with a scale of 2nm-1. As can be seen from FIG. 5, the H-type hierarchical pore ZSM-5 molecular sieve prepared in example 1 has a single crystal structure.
FIG. 6 is the N of the H-type multi-stage pore ZSM-5 molecular sieve prepared in example 12FIG. 6 shows that the H-type hierarchical pore ZSM-5 molecular sieve prepared in example 1 has a very high micropore surface area and a very rich mesopore volume, and the BET specific surface area is 619.9m2g-1The mesoporous volume is 0.37cm3g-1。
The H-type multistage pore ZSM-5 molecular sieve prepared in the example 1 is used as a catalyst to catalyze a methanol-to-olefin (MTO) reaction, and the reaction conditions comprise: the reaction temperature is 500 ℃, and the space velocity WHSV is as follows: 2h-1(first 444h) and 1h-1(after 444h) with steamIs a carrier gas. FIG. 7 is a graph of the catalytic effect of the H-type multi-stage pore ZSM-5 molecular sieve prepared in example 1 in the methanol to olefin reaction, wherein (a) is a graph of experimental results of Conversion (Conversion) and Selectivity (Selectivity), the ordinate corresponding to the square icon in (a) is the Conversion, and the ordinates corresponding to the other icons are Selectivity, wherein "ethene" corresponds to the Selectivity of ethylene, "propene" corresponds to the Selectivity of propylene, "butene" corresponds to the Selectivity of butene, "C1-C5 alkane" corresponds to the Selectivity of C1-C5 alkane, "BTX" corresponds to the Selectivity of light aromatic hydrocarbon, and "others" corresponds to the Selectivity of other hydrocarbon products; (b) the results of the experiments are shown as the molar ratio of propylene to ethylene (P/E value, P/Emolarratio) and the hydrogen transfer coefficient (HTI), wherein the ordinate of the square graph in (b) is the molar ratio of propylene to ethylene, and the ordinates of the other graphs are the hydrogen transfer coefficients, wherein C4-HTI is the hydrogen transfer coefficient represented by C four, and C5-HTI is the hydrogen transfer coefficient represented by C five, and is used for explaining the carbon deposition rate of the catalytic reaction. As can be seen from FIG. 7, the H-type multi-stage pore ZSM-5 molecular sieve prepared in example 1 has a long service life of 552.71H (conversion rate) in the reaction of catalyzing methanol to olefin>80% and space velocity WHSV: the first 444 hours and the second 2 hours-11h after 444 hours-1) High selectivity of propylene, a high value product(s) ((>40%) and no significant decrease in propylene selectivity throughout, the P/E values were higher than 3.5 for up to 551.7h (125.6 h to 677.3h), and the overall trend of the P/E values rose throughout the reaction. This shows that the H-type multi-stage pore ZSM-5 molecular sieve provided by the invention shows extremely excellent service life and excellent propylene selectivity in the reaction of preparing olefin from methanol.
Example 2
An H-type multi-stage pore ZSM-5 molecular sieve was prepared as in example 1, except that the hydrothermal crystallization reaction temperature was 140 ℃.
FIG. 8 is the XRD spectrum of the H-type multi-stage pore ZSM-5 molecular sieve prepared in example 2. from FIG. 8, the product prepared in example 2 is a pure phase ZSM-5 molecular sieve.
FIG. 9 is a TEM image of an H-type multi-stage pore ZSM-5 molecular sieve prepared in example 2, wherein the scales of (a) and (b) are 50nm and 20nm, respectively; as can be seen from fig. 9, the H-type hierarchical pore ZSM-5 molecular sieve prepared in example 2 is a hierarchical pore molecular sieve.
Example 3
An H-type multi-stage pore ZSM-5 molecular sieve was prepared according to the method of example 1, except that the mass of the aqueous TPAOH solution (mass fraction of TPAOH: 25%) was 0.244g in this example only.
FIG. 10 is the XRD spectrum of the H-type multi-stage pore ZSM-5 molecular sieve prepared in example 3. from FIG. 10, the product prepared in example 3 is a pure phase ZSM-5 molecular sieve.
FIG. 11 is a TEM image of an H-type multi-stage pore ZSM-5 molecular sieve prepared in example 3, with scales of (a) and (b) of 200nm and 50nm, respectively; as can be seen from fig. 11, the H-type hierarchical pore ZSM-5 molecular sieve prepared in example 3 is a hierarchical pore molecular sieve.
Example 4
An H-type multi-stage pore ZSM-5 molecular sieve was prepared according to the method of example 1, except that the mass of amorphous molecular sieve seed crystals was 0.09g in this example only.
FIG. 12 is the XRD spectrum of the H-type multi-stage pore ZSM-5 molecular sieve prepared in example 4. from FIG. 12, the product prepared in example 4 is a pure phase ZSM-5 molecular sieve.
FIG. 13 is a TEM image of an H-type multi-stage pore ZSM-5 molecular sieve prepared in example 4, wherein the scales of (a) and (b) are 0.5 μm and 20nm, respectively; as can be seen from fig. 13, the H-type hierarchical pore ZSM-5 molecular sieve prepared in example 4 is a hierarchical pore molecular sieve.
Comparative example 1
Placing HS-40 silica sol, tetrapropylammonium hydroxide and water in a beaker, and stirring and mixing uniformly; adding an aqueous solution of sodium metaaluminate and sodium hydroxide into the obtained system, and uniformly stirring and mixing to obtain a mixed feed liquid; wherein, in terms of molar ratio, the second mixed feed liquid meets SiO2：Al2O3：Na2O：TPAOH：H2O＝1.0：0.0056：0.03：0.3：30；
Transferring the mixed material liquid into a reaction kettle, and reacting for 2 days at 160 ℃; and after the reaction is finished, centrifugally washing the obtained solid product, drying in a 90 ℃ oven, and calcining the dried material at 550 ℃ in an air atmosphere for 6 hours to remove residual TPAOH (thermoplastic polyurethane-acrylic-epoxy) so as to obtain the traditional molecular sieve crystal seed.
The H-type ZSM-5 molecular sieve was then prepared as in example 1, except that only the seeds used in this comparative example were the seeds of the conventional molecular sieve.
FIG. 14 is an XRD spectrum of the H-type ZSM-5 molecular sieve prepared in comparative example 1. from FIG. 14, the product prepared in comparative example 1 is a pure phase ZSM-5 molecular sieve.
FIG. 15 is an SEM image of an H-type ZSM-5 molecular sieve prepared in comparative example 1, wherein the scales of (a) and (b) are 1 μm and 100nm, respectively; as can be seen from fig. 15, the H-type ZSM-5 molecular sieve prepared in comparative example 1 was a disordered large bulk molecular sieve crystal, and did not have a hierarchical pore structure.
FIG. 16 is a TEM image of an H-type ZSM-5 molecular sieve prepared in comparative example 1, with a scale of 200 nm; as can be seen from fig. 16, the H-type ZSM-5 molecular sieve prepared in comparative example 1 was a disordered large bulk molecular sieve crystal, and did not have a hierarchical pore structure.
Comparative example 2
The H-type ZSM-5 molecular sieve was prepared according to the method of comparative example 1, except that the conventional molecular sieve seed crystal was not added and the hydrothermal crystallization reaction temperature was 120 ℃ and the hydrothermal crystallization reaction time was 5 days.
FIG. 17 is an XRD spectrum of the H-type ZSM-5 molecular sieve prepared in comparative example 2. from FIG. 17, the product prepared in comparative example 2 is a pure phase ZSM-5 molecular sieve.
FIG. 18 is a TEM image of an H-type ZSM-5 molecular sieve prepared in comparative example 2, with a scale of 200 nm; as can be seen from fig. 18, the H-type ZSM-5 molecular sieve prepared in comparative example 2 was a bulk molecular sieve crystal, and did not have a hierarchical pore structure.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of a hierarchical pore ZSM-5 molecular sieve comprises the following steps:
providing amorphous molecular sieve seed crystals;
mixing the amorphous molecular sieve seed crystal, a first silicon source, a first microporous template agent, a first aluminum source, a mineralizer and water to obtain a first mixed feed liquid, and performing hydrothermal crystallization reaction to obtain a hydrothermal crystallization reaction product;
and sequentially carrying out first washing, first drying and first calcining treatment on the hydrothermal crystallization reaction product to obtain the hierarchical pore ZSM-5 molecular sieve.
2. The method of claim 1, wherein the first silicon source comprises silica sol or tetraethyl orthosilicate, the first microporous templating agent comprises tetrapropylammonium hydroxide or tetrapropylammonium bromide, the first aluminum source comprises sodium metaaluminate, aluminum sulfate, or aluminum chloride, and the mineralizer comprises sodium hydroxide or potassium hydroxide.
3. Preparation method according to claim 2, characterized in that the amount of substance of the first silicon source is SiO2The amount of the first aluminum source is calculated as Al2O3And the components in the first mixed feed liquid meet the following requirements: the molar ratio of the first silicon source, the first microporous template agent, the first aluminum source, the mineralizer and the water is 1: (0.01-0.03): (0.002-0.02): (0.15-0.40): (15-30);
the first silicon source is SiO2And the mass of the amorphous molecular sieve seed crystal is not more than 13 wt% of the mass of the first silicon source.
4. The method according to claim 1, wherein the temperature of the hydrothermal crystallization reaction is 120 to 170 ℃ for 1 to 5 days.
5. The method of claim 1, wherein the method of preparing amorphous molecular sieve seeds comprises the steps of:
mixing a second silicon source, a second microporous template agent, a second aluminum source, L-lysine and water to obtain a second mixed feed liquid, and carrying out hydrothermal reaction to obtain a hydrothermal reaction product;
and sequentially carrying out second washing, second drying and second calcining treatment on the hydrothermal reaction product to obtain amorphous molecular sieve seed crystals.
6. The method of claim 5, wherein the second silicon source comprises tetraethyl orthosilicate, the second microporous template agent comprises tetrapropylammonium hydroxide or tetrapropylammonium bromide, and the second aluminum source comprises sodium metaaluminate, aluminum sulfate, or aluminum chloride.
7. Preparation method according to claim 6, characterized in that the amount of the substance of the second silicon source is SiO2The amount of the second aluminum source is calculated as Al2O3And the components in the second mixed feed liquid meet the following requirements: the molar ratio of the second silicon source, the second microporous template agent, the second aluminum source, L-lysine and water is 1: (0.30-0.50): (0.002-0.05): (0.25-0.45): (5-15).
8. The method according to any one of claims 1 to 7, wherein the first calcination treatment further comprises:
mixing the first calcined product obtained after the first calcination treatment, ammonium chloride and water to obtain a third mixed feed liquid, and performing ammonium exchange treatment to obtain an ammonium exchange product;
and sequentially carrying out third washing, third drying and third calcining treatment on the ammonium exchange product to obtain the hierarchical pore ZSM-5 molecular sieve.
9. The hierarchical pore ZSM-5 molecular sieve prepared by the preparation method of any one of claims 1-8, wherein the hierarchical pore ZSM-5 molecular sieve has a particle size of 80-200 nm.
10. Use of the multigrade pore ZSM-5 molecular sieve as claimed in claim 9 as a catalyst for the production of olefins from methanol.
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CN109790040A (en) * 2017-07-14 2019-05-21 北京大学深圳研究生院 A kind of hierarchical structure porous zeotile and preparation method thereof
CN111992244A (en) * 2020-09-02 2020-11-27 西北大学 Novel methanol-to-propylene hierarchical pore ZSM-5 molecular sieve catalyst and preparation method thereof

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US6368571B1 (en) * 2000-01-28 2002-04-09 Chk Group, Inc. ZSM-5 made from siliceous ash
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