CN114229865A - Seed crystal-free rapid aging crystallization synthesis method of ZSM-5 micro mesoporous molecular sieve - Google Patents
Seed crystal-free rapid aging crystallization synthesis method of ZSM-5 micro mesoporous molecular sieve Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 46
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002425 crystallisation Methods 0.000 title claims abstract description 29
- 230000032683 aging Effects 0.000 title claims abstract description 17
- 230000008025 crystallization Effects 0.000 title claims description 25
- 238000001308 synthesis method Methods 0.000 title abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 239000013078 crystal Substances 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 238000009826 distribution Methods 0.000 claims abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 239000010703 silicon Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 16
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 14
- 229910001868 water Inorganic materials 0.000 claims description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 16
- 238000003786 synthesis reaction Methods 0.000 abstract description 16
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010457 zeolite Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 238000010899 nucleation Methods 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Organic Chemistry (AREA)
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention provides a seed crystal-free rapid aging crystallization method of a ZSM-5 micro-mesoporous zeolite molecular sieve, belonging to the synthesis field of ZSM-5 type molecular sieves. The synthesis method comprises the steps of uniformly stirring an aluminum source, a structure directing agent, a silicon source and deionized water, stirring and aging for 10-40 min at the rotation speed of 1000-1600 r/min in the environment of 40-80 ℃ to obtain a precursor solution, crystallizing for 0.5-2.5 h at the temperature of 150-185 ℃, washing, drying and roasting to obtain the product. The ZSM-5 molecular sieve obtained by the method has the average grain size of 200-350 nm and the specific surface area of 400-600 m2The average pore size is 7.0-7.3 nm, the pore size distribution is mainly concentrated in 2.3-4.2 nm, and the pore volume is 0.29-0.41 ml/g. The synthesis method does not need to add seed crystals, is simple and quick to synthesize, and the obtained ZSM-5 molecular sieve contains micro mesopores, has high crystallinity, regular appearance and high yield, and obviously improves the synthesis efficiency of the micro mesopore ZSM-5 molecular sieve and reduces the cost.
Description
Technical Field
The invention belongs to the field of synthesis of ZSM-5 type molecular sieves, and particularly relates to a simple, rapid, green and environment-friendly seed crystal-free rapid aging and crystallization synthesis method of a ZSM-5 micro mesoporous molecular sieve.
Background
ZSM-5 zeolite has wide application in petrochemical industry and environmental catalysis due to its unique three-dimensional framework structure, double-cross-linked pore system, excellent thermal stability, strong acidity, water vapor stability and shape selectivity, and a series of new petrochemical catalysis processes are developed. However, the pore size of the pure microporous molecular sieve limits the larger molecules from entering the pore canal and contacting with the active center, which leads to mass transfer limitation, and the obtained mesoporous ZSM-5 molecular sieve integrates the good catalytic performance of the microporous zeolite and the excellent mass transfer performance of the mesoporous molecular sieve by introducing a mesoporous structure into the ZSM-5 molecular sieve. The catalyst is beneficial to the rapid diffusion of reaction molecules to or from a catalytic active center, can effectively improve the catalytic effect, and prolongs the service life of the catalyst.
At present, a plurality of methods for synthesizing the mesoporous ZSM-5 molecular sieve exist, but the nucleation and crystallization of the product usually require relatively long aging time and crystallization time, such as 12-24 hours or even longer time, which not only greatly reduces the synthesis efficiency, but also increases the energy consumption, so that the synthesis method has higher cost in large-scale application. Therefore, the method has the advantages of shortening the crystallization time, improving the yield and reducing the synthesis cost, and is significant for scientific research and industrial application.
At present, the rapid synthesis of the ZSM-5 molecular sieve mainly comprises a direct synthesis method, a seed crystal method and a temperature-variable crystallization method. CN108584981A utilizes a small molecular template TPAOH to stir at 15-50 ℃ for 1-3 h, and performs static crystallization at 140-160 ℃ for 24-72 h to successfully prepare the ZSM-5 molecular sieve with mesopores, the size of the concentrated mesopores is 3-5 nm, and the product crystallinity is high. The patent application of CN110028080A discloses a method for preparing a micro-mesoporous ZSM-5 molecular sieve, which comprises the steps of treating at 20-60 ℃ for 2-12 hours to obtain dry glue, crystallizing at 50-180 ℃ for 1-12 hours to obtain an initial precursor, adding the precursor into a mixture of a silicon source, an aluminum source, alkali and a nitrogen-containing long-chain compound template agent, and crystallizing at 160-180 ℃ for 1-6 hours, wherein the size of the concentrated mesopores of the obtained molecular sieve is 5-20 nm, but the method has the disadvantages of long time for preparing seed crystals, waste of raw materials, easy generation of mixed crystals, relatively long whole aging and crystallization period and is not suitable for low cost and high-efficiency mass production. The CN 101279746A patent discloses a method for quickly synthesizing a ZSM-5 molecular sieve by adopting a variable temperature crystallization method, wherein the method comprises the steps of crystallizing in an oven at 115-125 ℃ for 1-4 hours, and then transferring to an oven at 230-250 ℃ for crystallizing for 4-8 hours, so that the synthesis conditions are easy to control, the crystal grain size is uniform, mixed crystals are not easy to generate, but the operation steps of the variable temperature crystallization are complex and the time consumption is long. Yoshioka and the like use 1-Butanol as an organic additive, stir for 18h at 25 ℃, add seed crystals, and rapidly synthesize a ZSM-5 molecular sieve within 2h of crystallization at 200 ℃, wherein the grain size distribution is 1-3 μm, (T.Yoshioka, Z.Liu, K.Iyoki, T.Sano, M.Ando, S.Sukenaga, H.Shibata, T.Okubo, T.Wakihara, Rapid Synthesis of hydrothermal Stable Stack-5 in the Presence of 1-Butanol, Chemistry Letters, 49(2020 1006) 1008), but the crystallization temperature is higher, the preparation process is complex, and the method is not beneficial to saving energy consumption and green production.
In the rapid synthesis method of the micro-mesoporous ZSM-5 molecular sieve, a plurality of problems still need to be solved. For example, the seed crystal method has the problems of long time consumption and raw material waste for preparing the seed crystal guiding agent, long aging crystallization time, high energy consumption caused by complex preparation process and the like while improving the crystallization rate and the product crystallinity; the synthesis conditions of the temperature-variable crystallization method are easy to control, but the process is complex and the energy consumption is high; and the existing method can not meet the limitation that the aging crystallization time is short and the pore diameter requirement of the micro-mesopores can not be met at the same time.
The invention improves the reaction kinetics based on the matching of a proper directing agent and the synthesis process conditions of less water and high alkalinity, thereby promoting the rapid synthesis of the micro-mesoporous ZSM-5 molecular sieve, greatly improving the crystallization and growth rate, ensuring that the synthesized crystal grains have good uniformity and can meet the requirements of related apertures. And no seed crystal is added in the synthesis process, the method is simple and rapid, low in energy consumption and high in yield, and a new scheme is provided for selective industrial production of the mesoporous ZSM-5 molecular sieve in the future.
Disclosure of Invention
Aiming at the defects of long time consumption, raw material waste, relatively long aging and crystallization time, high energy consumption caused by complex process, poor crystal development integrity and the like caused by the fact that a seed crystal guiding agent in the existing ZSM-5 micro mesoporous molecular sieve is rapidly synthesized, the technical problem to be solved by the invention is to improve the reaction kinetics based on matching of a proper guiding agent and the synthesis process conditions with less water and high alkalinity, and provide a process route which has no seed crystal, high synthesis speed, low energy consumption and high yield to synthesize the ZSM-5 micro mesoporous molecular sieve with excellent performance; and the preparation process has simple route, easy control and environmental protection. By improving the silicon-aluminum ratio and the alkalinity of the system, the nucleation rate and the crystal growth rate are accelerated, and more nucleation sites can be provided for refining crystal nuclei by violent stirring in the aging process, so that the number of the crystal nuclei in the system is increased, the uniformity of the crystal nuclei is improved, the energy barrier required by reaction is reduced, the subsequent rapid crystallization is facilitated, and the yield and the industrial production are improved.
The synthesis of ZSM-5 micro-mesoporous molecular sieve by rapid aging crystallization without seed crystal comprises the following steps:
(1) the main raw materials are sodium metaaluminate (calculated by alumina), tetrapropylammonium hydroxide, ethyl orthosilicate (calculated by silica) and water, and the molar ratio of each raw material is n (SiO)2):n(Al2O3):n(TPAOH):n(H2O)＝280～320:1～1.5:12～18:1500～2000。
(2) Mixing and stirring sodium metaaluminate and tetrapropylammonium hydroxide at room temperature for 5-20 min to obtain a clear solution;
(3) adding tetraethoxysilane into the solution in the step (2) at the ambient temperature of room temperature at the speed of 1ml/s, and stirring at 800-1000 r/min until the solution is clear;
(4) stirring and aging the solution obtained in the step (3) at the temperature of 40-80 ℃ at the rotating speed of 1000-1600 r/min for 10-40 min to form a precursor solution which is uniformly mixed;
(5) putting the precursor solution in the step (4) into a closed reaction kettle, and carrying out hydrothermal crystallization at the temperature of 150-185 ℃ for 0.5-2.5 h;
(6) and cooling to room temperature after hydrothermal crystallization, centrifuging or filtering for solid-liquid separation, washing the precipitate with deionized water for 3-5 times until the pH value is 7-8, drying under the general conditions of a ZSM-5 molecular sieve, and roasting to obtain the product.
A non-crystal seed quick ageing and crystallizing process for synthesizing ZSM-5 zeolite molecular sieve features that the Si/Al ratio and basicity of system are increased and the vigorous stirring and nucleating technology is used to increase the nucleating speed and crystal growth speed, increase the uniformity of nucleation site and crystal grains, increase the crystallizing speed and shorten synthesizing period. The synthesized molecular sieve has stable structure and good crystallinity, and single crystal grain is regular hexagonal plate-shaped; the pore size distribution is good, and the stability is high; the synthesis process is simpler, does not need high-temperature aging, has short crystallization time, is green and environment-friendly, saves cost and energy consumption, has the characteristics of good repeatability, operability and the like, and has better practicability and high industrial application value.
Drawings
FIG. 1 is an XRD spectrum of a ZSM-5 type molecular sieve synthesized in example 1;
FIG. 2 is an SEM photograph of the ZSM-5 type molecular sieve synthesized in example 1;
FIG. 3 is the N of the ZSM-5 type molecular sieve synthesized in example 42Adsorption and desorption isotherms.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
Example 1
3.8753g of tetrapropylammonium hydroxide (25 wt% of tetrapropylammonium hydroxide) and 0.0516g of sodium metaaluminate (Al) were weighed2O3Content 45 wt%), and stirring at room temperature for 20min to obtain solution (r). 6.8752g of tetraethoxysilane (SiO) are stirred at room temperature and 1000r/min2Content 28 wt%) was added to the solution (r) at a rate of 1ml/s to obtain a solution (r). And continuously stirring the solution II for 0.5h at the ambient temperature of 40 ℃ under the stirring condition of 1600r/min to form a uniform mixed precursor solution. And pouring the precursor solution into a reaction kettle, placing the reaction kettle in an oven for water bath crystallization at 180 ℃ for 1h, and taking out. Cooling to room temperature, centrifuging at 10000r/min, washing until pH is 7, drying at 95 deg.C for 8 hr, and calcining at 550 deg.C in muffle furnace for 5 hr to obtain ZSM-type 5 molecular sieves.
Example 2
4.8723g of tetrapropylammonium hydroxide and 0.0425g of sodium metaaluminate are weighed and stirred at room temperature for 5min to obtain a solution I. 6.8752g of tetraethoxysilane is added into the solution (r) at the speed of 1ml/s under the stirring condition of 1000r/min at room temperature to obtain a solution (c). And continuously stirring the solution II for 1h at the ambient temperature of 50 ℃ under the stirring condition of 1300r/min to form a uniform mixed precursor solution. And pouring the precursor solution into a reaction kettle, placing the reaction kettle in an oven for water bath crystallization at 150 ℃ for 2.5h, and taking out. After the molecular sieve is cooled to room temperature, centrifuging at the rotating speed of 9000r/min, washing until the pH value is 7, drying in a drying oven at 110 ℃ for 8h, and roasting in a muffle furnace at 550 ℃ for 4h to obtain the ZSM-5 type molecular sieve.
Example 3
3.9035g of tetrapropylammonium hydroxide and 0.0426g of sodium metaaluminate are weighed and stirred at room temperature for 10min to obtain a solution I. 6.4872g of tetraethoxysilane is added into the solution (r) at the speed of 1ml/s under the stirring condition of 800r/min at room temperature to obtain a solution (c). And continuously stirring the solution II for 0.5h at the ambient temperature of 60 ℃ under the stirring condition of 1400r/min to form uniform mixed precursor solution. Pouring the precursor solution into a reaction kettle, placing the reaction kettle in an oven for water bath crystallization at 175 ℃ for 2h, and taking out. After the molecular sieve is cooled to room temperature, centrifuging at the rotating speed of 8000r/min, washing until the pH value is 7, drying in a drying oven at the temperature of 90 ℃ for 6h, and roasting in a muffle furnace at the temperature of 550 ℃ for 6h to obtain the ZSM-5 type molecular sieve.
Example 4
3.9035g of tetrapropylammonium hydroxide and 0.0426g of sodium metaaluminate are weighed and stirred at room temperature for 10min to obtain a solution I. 9.4872 silica sol is added into the solution (r) at the speed of 1ml/s under the stirring condition of 900r/min at room temperature to obtain solution (r). And continuously stirring the solution II for 1h at the ambient temperature of 80 ℃ under the stirring condition of 1000r/min to form a uniform mixed precursor solution. And pouring the precursor solution into a reaction kettle, placing the reaction kettle in an oven for water bath crystallization at 180 ℃ for 1h, and taking out. After the molecular sieve is cooled to room temperature, centrifuging at the rotating speed of 8000r/min, washing until the pH value is 7, drying in a drying oven at the temperature of 100 ℃ for 7h, and roasting in a muffle furnace at the temperature of 550 ℃ for 6h to obtain the ZSM-5 type molecular sieve.
Example 5
3.9045g of tetrapropylammonium hydroxide and 0.0226g of aluminum isopropoxide are weighed and stirred at room temperature for 8min to obtain a solution I. 9.4872 silica sol is added into the solution (r) at the speed of 1ml/s under the stirring condition of 900r/min at room temperature to obtain solution (r). And continuously stirring the solution II for 1h at the ambient temperature of 80 ℃ under the stirring condition of 1600r/min to form a uniform mixed precursor solution. And pouring the precursor solution into a reaction kettle, placing the reaction kettle in an oven for water bath crystallization at 185 ℃ for 0.5h, and taking out. After the molecular sieve is cooled to room temperature, centrifuging at a rotating speed of 9000r/min, washing until the pH value is 7, drying in an oven at 100 ℃ for 10h, and roasting in a muffle furnace at 550 ℃ for 6h to obtain the ZSM-5 type molecular sieve.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (5)
1. A method for synthesizing ZSM-5 micro-mesoporous molecular sieve by rapid aging and crystallization without crystal seeds comprises the following steps.
(1) The main raw materials are sodium metaaluminate (calculated by alumina), tetrapropylammonium hydroxide, ethyl orthosilicate (calculated by silica) and water, and the molar ratio of each raw material is n (SiO)2):n(Al2O3):n(TPAOH):n(H2O)＝280～320:1～1.5:12～18:1500～2000。
(2) Mixing and stirring sodium metaaluminate and tetrapropylammonium hydroxide at room temperature for 5-20 min to obtain a clear solution;
(3) adding tetraethoxysilane into the solution in the step (2) at the ambient temperature of room temperature at the speed of 1ml/s, and stirring at 800-1000 r/min until the solution is clear;
(4) stirring and aging the solution obtained in the step (3) at the temperature of 40-80 ℃ at the rotating speed of 1000-1600 r/min for 10-40 min to form a precursor solution which is uniformly mixed;
(5) putting the precursor solution in the step (4) into a closed reaction kettle, and carrying out hydrothermal crystallization at the temperature of 150-185 ℃ for 0.5-2.5 h;
(6) and cooling to room temperature after hydrothermal crystallization, centrifuging or filtering for solid-liquid separation, washing the precipitate with deionized water for 3-5 times until the pH value is 7-8, drying under the general conditions of a ZSM-5 molecular sieve, and roasting to obtain the product.
2. The method of claim 1, wherein the silicon source is preferably tetraethoxysilane and optionally silica sol.
3. The method for rapidly synthesizing the ZSM-5 micro mesoporous molecular sieve according to claim 1, wherein the aluminum source is preferably sodium metaaluminate and can also be aluminum isopropoxide.
4. The method of claim 1, wherein the structure directing agent is preferably tetrapropylammonium hydroxide, and optionally tetrapropylammonium bromide.
5. The method of claim 1, wherein the step of rapidly synthesizing the ZSM-5 mesoporous molecular sieve comprises: the size of the molecular sieve crystal grain is 200-350 nm, and the specific surface area is 400-600 m2The average pore size is 7.0-7.3 nm, the pore size distribution is mainly concentrated in 2.3-4.2 nm, and the pore volume is 0.29-0.41 ml/g.
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|---|---|---|---|---|
| US20110009685A1 (en) * | 2008-03-31 | 2011-01-13 | Sebastien Kremer | MFI Molecular Sieve Composition and the Method of Making the Same |
| CN102502696A (en) * | 2011-11-16 | 2012-06-20 | 大连理工大学 | Synthetic method of ZSM-5 zeolites |
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