CN107512728B - Preparation method of FAU type zeolite molecular sieve with card-inserted structure and hierarchical pores - Google Patents
Preparation method of FAU type zeolite molecular sieve with card-inserted structure and hierarchical pores Download PDFInfo
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Abstract
The invention discloses a preparation method of a 'card-inserting' structure hierarchical pore FAU type zeolite molecular sieve, belonging to the technical field of inorganic chemistry. Firstly, dissolving an inorganic alkali source and an aluminum source in deionized water, then slowly adding a silicon source, fully and uniformly stirring to obtain uniform sol, and then carrying out hydrothermal crystallization treatment on the sol to obtain the FAU-type zeolite molecular sieve with the hierarchical pore of the card-inserting structure. The invention synthesizes the FAU-type zeolite molecular sieve with a card-inserting structure and multiple pores under the condition of no organic template agent and inorganic salt additive, greatly reduces the synthesis cost, and has simple and environment-friendly preparation method. In addition, the FAU type zeolite molecular sieve with a card-inserting structure has the characteristics of obvious micropore, mesopore and macropore structures, large external surface area, strong acidity and good stability, and has wide application prospect in the aspects of washing aids, hard water softening, catalysts, adsorbents, catalyst carriers and the like.
Description
Technical Field
The invention belongs to the technical field of synthesis of inorganic porous materials, and particularly relates to a method for preparing a low-cost, green and rapid hierarchical porous FAU type zeolite molecular sieve with a plug-in card structure.
Background
The Faujasite (FAU) molecular sieve has three-dimensional twelve-membered ring channel structure with micropore diameter of about 0.74 nm and relatively low framework Si/Al ratio, and comprises X-type molecular sieve and Y-type molecular sieve, wherein SiO is2/Al2O3With a ratio of less than 3 being X-type molecular sieve, SiO2/Al2O3The ratio of the molecular sieve to the molecular sieve is 3-6. Of the low-silicon typeThe X-type molecular sieve has good ion exchange and adsorption capacity, and is an industrially important detergent auxiliary agent and hard water softener. The high-silicon type Y-type molecular sieve is the most widely used Fluid Catalytic Cracking (FCC) catalyst in the petroleum processing field. It is well known that the performance and application of molecular sieves are closely related to their morphology and structure size. For example, zeolite molecular sieves of self-supporting nanosheet structure (referred to as "plugged-in-card" structure) generally have a relatively high external surface area and exhibit excellent reactivity in macromolecular catalytic reactions. At present, the preparation of the self-supporting nano-sheet structure zeolite molecular sieve mostly adopts a soft template method. For example, Inayat et al use organosilane [3- (trimethoxysilyl) propyl]Hexadecyl dimethyl ammonium chloride (TPHAC) is used as a template to prepare the X-type zeolite molecular sieve with a 'card-in-card' (house-of-cards-like) morphology, wherein the 'card-in-card' zeolite is composed of X zeolite sheets which are arranged in a triangular shape. However, organosilane surfactants are expensive and the removal by sintering causes environmental pollution, which hinders large-scale industrial application. In order to reduce the industrial preparation cost of the molecular sieve with a card-inserting structure, the Chinese invention patent discloses a method for preparing N-methylpyrrolidone (C) by using organic micromolecules5H9NO, NMP) as a structure directing agent to prepare the ZSM-5 zeolite molecular sieve with the multilevel pore 'card-inserting' structure. The preparation method avoids using expensive long-chain organic amine template agent, reduces the synthesis cost, but still can not avoid using organic compounds. Recently, a.inayat et al uses zinc nitrate or lithium carbonate as an inorganic salt additive to modify the shape of the X-type molecular sieve to prepare the sheet-structured X-type molecular sieve, but the synthesis cost is not low due to the use of a large amount of inorganic salts such as lithium salt and zinc salt, which is not beneficial to industrial production.
Aiming at the problems and defects in the prior art, the invention provides an economical, environment-friendly and rapid preparation method of the FAU-type molecular sieve with the hierarchical pore in the structure of the card-in-card, aiming at further reducing the synthesis cost and energy consumption and promoting the large-scale production of the FAU-type zeolite molecular sieve with the hierarchical pore in the structure of the card-in-card.
Disclosure of Invention
The invention synthesizes the FAU type zeolite molecular sieve (HCL-FAU for short) with a card-inserting structure and multi-level pores by a one-step hydrothermal method without adding any organic template agent and inorganic salt additive. The HCL-FAU is a spheroid particle (a 'card-inserting' structure for short) formed by triangular cross stacking of FAU type zeolite nano-sheets, and the secondary particle size is about 0.5-5 mu m. The HCL-FAU has the characteristics of micropores (about 0.74 nm), mesopores (2-50 nm) and macroporous channels, has large external surface area, good stability and strong acidity, and has potential application prospects in the aspects of catalysis, adsorption, separation, ion exchange and the like.
In order to achieve the purpose, the invention provides a preparation method of a FAU type zeolite molecular sieve with a hierarchical pore 'plug-in card' structure, which comprises the following steps:
(1) dissolving an inorganic alkali source and an aluminum source in deionized water, and stirring and mixing;
(2) adding a silicon source under the stirring condition in the step (1), and stirring to form initial sol;
(3) putting the product obtained in the step (2) into a reaction kettle, sealing, and carrying out hydrothermal crystallization; and after crystallization is finished, carrying out solid-liquid separation, washing, drying and calcining in air on the solid product to obtain the FAU-type zeolite molecular sieve with the hierarchical pores in the structure of a plug-in card.
Preferably, in step (1), the inorganic alkali source is one or more of sodium oxide, sodium hydroxide, sodium carbonate and sodium bicarbonate, and sodium hydroxide is preferred. The aluminum source is one or more of sodium aluminate (sodium metaaluminate), aluminum sulfate, aluminum nitrate, pseudoboehmite, alumina, aluminum hydroxide, aluminum carbonate, aluminum isopropoxide and aluminum acetate, and preferably sodium aluminate (sodium metaaluminate).
Preferably, in the step (2), the silicon source is one or more of water glass, white carbon black, sodium silicate, silica sol, ethyl orthosilicate, silica gel and diatomite, and is preferably water glass.
Preferably, in step (2), the inorganic alkali source generates M theoretically2Measuring the amount of O, and generating Al by an aluminum source according to a theory2O3Meter, the silica source generating SiO theoretically2Metering, controlling the addition of each reactant to make the initial solutionThe glue, namely the silicon-aluminum precursor liquid has the following molar ratio relation: 1.0 to 15Na2O： 1.0Al2O3：1.8～15SiO2：40～450H2O。
Preferably, in the step (2), the silicon source is slowly added under the stirring condition in the step (1), wherein the slow adding rate of the silicon source is 0.001mol/min to 5 mol/min.
Preferably, in the step (3), the crystallization temperature is 50-90 ℃, preferably 55-75 ℃, and the crystallization time is 5-240 hours, preferably 6-72 hours.
Preferably, in the step (3), the calcination temperature is 400-700 ℃, preferably 450-550 ℃, the calcination time is 0.5-24 h, preferably 3-9 h, and the temperature rise rate is 0.2-5 ℃ min-1Preferably 1 to 2 ℃ min-1。
Compared with the prior art, the invention has the following advantages and gain effects:
(1) the FAU-type molecular sieve (HCL-FAU) with the card-inserting structure and the hierarchical pores has the advantages that the primary structure is FAU-type zeolite nanosheets, adjacent nanosheets are stacked in a triangular cross mode to form spheroids, the particle size distribution is uniform, compared with the traditional FAU-type molecular sieve, the FAU-type molecular sieve is rich in the hierarchical pore channel structures of micropores, mesopores and macropores, the external specific surface area is large, the thermal stability is good, the acidity is strong, and the FAU-type molecular sieve has wide application prospects in the fields of catalysis, adsorption, separation, ion exchange and the like.
(2) The invention is an economic, efficient and environment-friendly' card-inserting-structure hierarchical pore FAU-type zeolite molecular sieve synthesis method, and the preparation process can avoid using expensive organic template agents and/or inorganic salt additives, greatly reduce the manufacturing process cost of materials and is expected to realize large-scale commercial production.
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FIG. 1 is an X-ray diffraction pattern (XRD) of a "card-shaped" hierarchical pore FAU type molecular sieve prepared in example 1 of the present invention;
FIG. 2 shows (A) Scanning Electron Micrographs (SEM) and (B) Transmission Electron Micrographs (TEM) of a "card-shaped" hierarchical pore FAU-shaped molecular sieve prepared in example 1 of the present invention;
FIG. 3 shows an embodiment of the present invention1N of prepared card-inserted hierarchical pore FAU type molecular sieve2Adsorption/desorption isotherms;
fig. 4 is a BJH pore size distribution diagram of the "card-insertion" type hierarchical pore FAU type molecular sieve prepared in example 1 of the present invention.
Detailed Description
The invention is further described with reference to the following examples, but the scope of the invention as claimed is not limited to the scope of the embodiments presented.
Example 1
(1) Adding 0.5g of sodium hydroxide and 1.2g of sodium aluminate into 6.7g of deionized water, and stirring until a clear solution is obtained;
(2) slowly dropwise adding 3.88g of water glass (the content of effective components is SiO) into the clear solution obtained in the step (1)227.13wt％，Na2O8.74 wt%), stirring uniformly, and performing ultrasonic treatment to obtain uniform dilute colloid;
(3) putting the diluted colloid obtained in the step (2) into a hydrothermal reaction kettle, and crystallizing at the constant temperature of 75 ℃ for 48 hours, wherein the molar ratio of the reaction mixture is Na2O:Al2O3:SiO2:H2O＝1.43:1.0:2.4:70.2；
(4) After crystallization is finished, the solid product is filtered, washed, dried in a blast oven at 70 ℃ for 24h, and then calcined in air at the constant temperature of 450 ℃ for 5h (the heating rate is 1 ℃ for min)-1) And obtaining the FAU type zeolite molecular sieve with a card-inserting structure and multilevel pores.
Characterization analysis was performed on the "plug-in card" type hierarchical pore FAU type molecular sieve (HCL-FAU) synthesized in example 1.
And (3) performing phase characterization on the HCL-FAU sample by using an X-ray diffractometer. The result is shown in figure 1, the XRD spectrum of the HCL-FAU sample is completely consistent with the characteristic peak of the standard FAU type molecular sieve, and the synthesized HCL-FAU sample is the FAU type molecular sieve.
Analysis of SiO in HCL-FAU samples by X-ray fluorescence spectroscopy2/Al2O3The ratio is 2.44, and the zeolite X molecular sieve is FAU type.
And (3) performing morphology characterization on the HCL-FAU sample by using a scanning electron microscope. As shown in FIGS. 2A and 2B, the appearance of the HCL-FAU sample is that FAU zeolite nano-sheets with the thickness of about 100nm are arranged in a triangular cross mode, namely, adjacent nano-sheets are mutually crossed and stacked to form a 'card-inserting' type sphere-like particle, the secondary particle size is about 1-2 μm, and the distribution is uniform. The transmission electron microscope further proves that the synthesized HCL-FAU sample is of a card-inserting structure, and HCL-FAU has a large amount of meso-pores and macroporous pores, which is beneficial to the rapid transmission of macromolecules.
By using N2The adsorption analyzer performs microstructure analysis on the HCL-FAU sample. As shown in FIG. 3, N2The adsorption-desorption isotherm curve shows a typical type IV-adsorption isotherm, indicating that the HCL-FAU has a hierarchical pore structure characteristic, which is consistent with TEM analysis results. The BET specific surface area is about 541m by calculation2g-1Outer surface area of 100m2g-1. The BJH aperture distribution diagram of HCL-FAU is shown in figure 4, the mesoporous aperture is between 3.3 nm and 16nm, and is concentrated near 7.8 nm.
Example 2
(1) Adding 0.5g of sodium hydroxide and 1.2g of sodium aluminate into 6.7g of deionized water, and stirring until a clear solution is obtained;
(2) slowly dropwise adding 3.88g of water glass (the content of effective components is SiO) into the clear solution obtained in the step (1)227.13wt％，Na2O8.74 wt%), stirring uniformly, and performing ultrasonic treatment to obtain uniform dilute colloid;
(3) putting the diluted colloid obtained in the step (2) into a hydrothermal reaction kettle, and crystallizing at the constant temperature of 60 ℃ for 72 hours, wherein the molar ratio of the reaction mixture is Na2O:Al2O3:SiO2:H2O＝1.43:1.0:2.4:70.2；
(4) After crystallization is finished, the solid product is filtered, washed, dried in a blast oven at 70 ℃ for 24h under normal pressure, and then calcined in air at the constant temperature of 500 ℃ for 4h (the heating rate is 1 ℃ for min)-1) 2.2g of the FAU type molecular sieve with the card-inserting type hierarchical pores is obtained, and the yield is 18 percent (the mass ratio of the product to the total feed).
The sample has an X-ray powder diffraction pattern substantially the same as that of FIG. 1, a scanning photograph substantially similar to that of FIG. 2, and an X-ray fluorescence spectrum for analyzing SiO in the sample2/Al2O3A ratio of 2.44, is FAU type X zeoliteAnd (3) a molecular sieve. The nitrogen adsorption-desorption isothermal curve and the mesoporous pore size distribution are basically similar to those in the graph 3 and the graph 4, and the BET specific surface area is 385m2g-1The mesoporous aperture is between 2.9-5.7 nm and is concentrated near 4.4 nm.
Example 3
(1) Adding 0.5g of sodium hydroxide and 1.2g of sodium aluminate into 4.7g of deionized water, and stirring until a clear solution is obtained;
(2) slowly dropwise adding 3.88g of water glass (the content of effective components is SiO) into the clear solution obtained in the step (1)227.13wt％，Na2O8.74 wt%), stirring uniformly, and performing ultrasonic treatment to obtain uniform dilute colloid;
(3) putting the diluted colloid obtained in the step (2) into a hydrothermal reaction kettle, and crystallizing at the constant temperature of 75 ℃ for 48 hours, wherein the molar ratio of the reaction mixture is Na2O:Al2O3:SiO2:H2O＝1.43:1.0:2.4:54.8；
(4) After crystallization is finished, the solid product is filtered, washed, dried in a blast oven at 70 ℃ for 24h under normal pressure, and then calcined in air at the constant temperature of 450 ℃ for 4h (the heating rate is 1 ℃ for min)-1) 2.1g of the FAU type molecular sieve with the card-shaped hierarchical pores is obtained, and the yield is 20.4 percent (the mass ratio of the product to the total feed).
The sample has an X-ray powder diffraction pattern substantially the same as that of FIG. 1, a scanning photograph substantially similar to that of FIG. 2, and an X-ray fluorescence spectrum for analyzing SiO in the sample2/Al2O3The ratio is 2.44, and the zeolite X molecular sieve is FAU type.
Example 4
(1) Adding 0.6g of sodium hydroxide and 1.2g of sodium aluminate into 6.7g of deionized water, and stirring until a clear solution is obtained;
(2) slowly dropwise adding 3.88g of water glass (the content of effective components is SiO) into the clear solution obtained in the step (1)227.13wt％，Na2O8.74 wt%), stirring uniformly, and performing ultrasonic treatment to obtain uniform dilute colloid;
(3) putting the diluted colloid obtained in the step (2) into a hydrothermal reaction kettle, and crystallizing at the constant temperature of 70 ℃ for 6 hours, wherein the molar ratio of the reaction mixture is Na2O:Al2O3:SiO2:H2O＝1.6:1.0:2.4:70.2；
(4) After crystallization is finished, the solid product is filtered, washed, dried in a blast oven at 70 ℃ for 24h under normal pressure, and then calcined in air at the constant temperature of 450 ℃ for 4h (the heating rate is 1 ℃ for min)-1) 2.1g of the FAU type molecular sieve with the card-shaped hierarchical pores is obtained, and the yield is 17 percent (the mass ratio of the product to the total feed).
The sample has an X-ray powder diffraction pattern substantially the same as that of FIG. 1, a scanning photograph substantially similar to that of FIG. 2, and an X-ray fluorescence spectrum for analyzing SiO in the sample2/Al2O3The ratio is 2.44, and the zeolite X molecular sieve is FAU type.
Example 5
(1) Adding 0.5g of sodium hydroxide and 1.2g of sodium aluminate into 6.7g of deionized water, and stirring until a clear solution is obtained;
(2) 4.9g of water glass (the content of effective components is SiO) is slowly dripped into the clear solution in the step (1)227.13wt％，Na2O8.74 wt%), stirring uniformly, and performing ultrasonic treatment to obtain uniform dilute colloid;
(3) putting the diluted colloid obtained in the step (2) into a hydrothermal reaction kettle, and crystallizing at the constant temperature of 70 ℃ for 48 hours, wherein the molar ratio of the reaction mixture is Na2O:Al2O3:SiO2:H2O＝1.6:1.0:3.0:75；
(4) After crystallization is finished, the solid product is subjected to suction filtration and washing, and is dried in a forced air oven at 70 ℃ for 24 hours under normal pressure, so that 2.2g of the card-shaped hierarchical porous FAU-shaped molecular sieve is obtained, and the yield is 17% (the product accounts for the mass ratio of the total feed).
The sample has an X-ray powder diffraction pattern substantially the same as that of FIG. 1, a scanning photograph substantially similar to that of FIG. 2, and an X-ray fluorescence spectrum for analyzing SiO in the sample2/Al2O3The ratio is 3.02, and the zeolite is FAU type Y zeolite molecular sieve.
The above description is only exemplary of the present invention, and is not intended to limit the present invention in any way, and the scope of the present invention is not limited thereto.
Claims (5)
- A preparation method of a FAU type zeolite molecular sieve with a card-inserting structure and multilevel pores comprises the following specific steps:(1) adding an inorganic alkali source and an aluminum source into deionized water, stirring and mixing;(2) adding a silicon source under the stirring condition in the step (1), and stirring to form initial sol;(3) putting the product obtained in the step (2) into a reaction kettle, sealing, and carrying out hydrothermal crystallization; after crystallization is finished, carrying out solid-liquid separation, washing, drying and calcining treatment in air on the solid product to obtain the FAU type zeolite molecular sieve with the hierarchical pore of the 'plug-in card' structure; the crystallization temperature is 50-75 ℃;the silicon source is one or more of water glass, white carbon black, sodium silicate, silica sol, ethyl orthosilicate, silica gel and diatomite;the FAU-type zeolite molecular sieve with the card-inserting structure and the hierarchical pores comprises an X-type or Y-type molecular sieve, spheroidal particles formed by triangular cross stacking of FAU-type zeolite nano sheets are 0.5-5 mu m in secondary particle size, and the FAU-type zeolite molecular sieve has microporous pores, mesoporous pores and macroporous pore canals;the inorganic alkali source generates M according to theory2Measuring the amount of O, and generating Al by an aluminum source according to a theory2O3Metering of the silicon source to theoretically form SiO2The feeding mol ratio of each component in the initial sol is 1.0-15M2O：1.0Al2O3：1.8～15SiO2：40～450H2O。
- 2. The method of claim 1, wherein: the inorganic alkali source is one or more of sodium oxide, sodium hydroxide, sodium carbonate and sodium bicarbonate.
- 3. The method of claim 1, wherein the aluminum source is one or more of sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum chloride, pseudoboehmite, aluminum oxide, aluminum hydroxide, aluminum carbonate, elemental aluminum, aluminum isopropoxide, and aluminum acetate.
- 4. The method of claim 1, wherein the crystallization time is 5 to 240 hours.
- 5. The method according to claim 1, wherein the calcination temperature is 400 to 700 ℃, the calcination time is 0.5 to 24 hours, and the temperature rise rate is 0.2 to 5 ℃ for min-1。
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| CN110357123B (en) * | 2019-07-31 | 2021-05-07 | 深圳大学 | High-crystallinity hierarchical-pore nano X-type molecular sieve and preparation method thereof |
| CN111960430B (en) * | 2020-09-01 | 2022-04-01 | 常州工学院 | Synthetic method and application of high-crystallinity hierarchical-pore LSX zeolite molecular sieve |
| CN115990454B (en) * | 2021-10-20 | 2024-07-09 | 中国石油化工股份有限公司 | Modified X zeolite and preparation method and application thereof |
| CN114105165A (en) * | 2021-12-21 | 2022-03-01 | 中科催化新技术(大连)股份有限公司 | Method for recycling synthetic mother liquor of low-silica-alumina-ratio X-type molecular sieve |
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