CN103818920A - Method for preparing Si-Al ordered mesoporous molecular sieve - Google Patents
Method for preparing Si-Al ordered mesoporous molecular sieve Download PDFInfo
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- CN103818920A CN103818920A CN201310727385.7A CN201310727385A CN103818920A CN 103818920 A CN103818920 A CN 103818920A CN 201310727385 A CN201310727385 A CN 201310727385A CN 103818920 A CN103818920 A CN 103818920A
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Abstract
The invention discloses a method for preparing a Si-Al ordered mesoporous molecular sieve, which comprises the following steps: carrying out extraction by using waste coal ash generated in a heat-engine plant as the raw material to obtain a solution containing silicon and aluminium; using CTAB (Cetyltrimethyl Ammonium Bromide) as a template agent; adding ethanol and water to rapidly synthesize a semi-finished product at room temperature; placing the semi-finished product in a muffle furnace for calcining to remove the template agent; cooling, so that the product is obtained, wherein the molar ratio of the CTAB to the water to the ethanol to the total amount of the silicon and the aluminium in the solution is (0.4-0.6):(300-500):(50-60):1. According to the method disclosed by the invention, the industrial waste coal ash is used as the raw material, so that the experimental cost is greatly reduced, the comprehensive utilization field of the coal ash is expanded, meanwhile, the pollution of the coal ash is reduced and the environment is protected.
Description
Technical field
The present invention relates to a kind of method of ordered mesoporous molecular sieve, particularly relating to a kind of is the method that raw material is prepared Si-Al ordered mesoporous molecular sieve from thermal power plant's flyash.
Background technology
Due to the well-regulated pore passage structure of mesopore molecular sieve, narrow pore size distribution, adjustable pore size, high specific surface area, therefore there is important application prospect in the field such as petrochemical complex, Industrial Catalysis, and in mesoporous material family, because the mesoporous molecule of Si-Al is the pore passage structure of homogeneous, high hydrothermal stability, is subject to people's favor more.At present, although Si-Al mesopore molecular sieve has application widely, but current product can not meet market demand, it is tetraethyl orthosilicate (TEOS) that silicon-based mesoporous material raw material used is prepared in traditional laboratory, it is expensive, be unfavorable for large-scale production application, and building-up process adopts hydrothermal method to carry out more, process is very complicated comparatively.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of cost method of preparing Si-Al ordered mesoporous molecular sieve low, easy and simple to handle.
A method of preparing Si-Al ordered mesoporous molecular sieve, comprises the steps:
Obtain take the discarded flyash of thermal power plant as raw material abstraction the solution that contains silicon and aluminium, take CTAB(cetyl trimethylammonium bromide) be template, add second alcohol and water at room temperature to synthesize fast basic products, described basic products is placed in to retort furnace calcining and removes template, obtain product after cooling; Wherein, in described CTAB, water, ethanol and solution, the mol ratio of sial total amount is (0.4-0.6): (300-500): (50-60): 1.
The method of preparing Si-Al ordered mesoporous molecular sieve of the present invention, comprises the steps:
(1) extraction silicon and aluminum source: the flyash that is 1:1.2 by mass ratio and NaOH mixing are placed in crucible and send into retort furnace, at 550-600 ℃ of calcining 1-2 hour; After sample after calcining is cooling, takes out and grind, add deionized water, the mass ratio of wherein said flyash and water is 1:4, at room temperature stirs 10-24 hour; Solution centrifugal after stirring is separated, get supernatant liquid as silicon and aluminum source solution, the solid obtaining is for the preparation of the micro porous molecular sieve of NaX, NaSOD;
(2) prepare Si-Al molecular sieve basic products: configuration CTAB solution, add water, dehydrated alcohol, under whipped state, add described silicon and aluminum source solution to obtain mixing solutions, described in described mixing solutions, in CTAB, water, ethanol and solution, the mol ratio of sial total amount is (0.4-0.6): (300-500): (50-60): 1; Adopt the pH value of acid-conditioning solution to 9-10, continue to stir 2-4 hour, stop stirring, suction filtration, washing, dry, obtain basic products;
(3) product aftertreatment: described basic products, at 550-600 ℃ of calcining 6-8h, is obtained to product after cooling.
The method of preparing Si-Al ordered mesoporous molecular sieve of the present invention, wherein described in step (3), the temperature rise rate of retort furnace is 2 ℃/min.
The method of preparing Si-Al ordered mesoporous molecular sieve of the present invention, wherein the described drying process in step (2) is: dried overnight in 80 ℃ of baking ovens.
The SI-AL ordered mesoporous molecular sieve that the method for the invention prepares.
The method of preparing Si-Al ordered mesoporous molecular sieve of the present invention, wherein said Si-Al ordered mesoporous molecular sieve is observed through X-ray diffraction method, has the strong diffraction peak of feature in the low-angle 1-3 of an XRD ° left and right; High-resolution-ration transmission electric-lens can directly be observed its ordered porous feature; Described Si-Al ordered mesoporous molecular sieve adopts low temperature nitrogen adsorption-desorption method to observe, and specific surface area is approximately 300-800m
2/ g.
The method difference from prior art that the present invention prepares Si-Al ordered mesoporous molecular sieve is:
With trade waste powdered coal ash; greatly reduce experimental cost; expand the comprehensive utilization field of flyash; reduced flyash pollution simultaneously, protected environment, prepare in mesopore molecular sieve process, have advantages of easy and simple to handle, the cycle is short; the product obtaining presents ordered porous; even aperture distribution, specific surface area is larger, and in this process, can also obtain NaX, the micro porous molecular sieve material of NaSOD type.
Below in conjunction with accompanying drawing, the method for the Si-Al of preparation ordered mesoporous molecular sieve of the present invention is described further.
Accompanying drawing explanation
Fig. 1 is the Small angle XRD phenogram of the product obtaining of the method for the Si-Al of preparation ordered mesoporous molecular sieve of the present invention;
Fig. 2 is the low temperature nitrogen adsorption-desorption graphic representation of the product obtaining of the method for the Si-Al of preparation ordered mesoporous molecular sieve of the present invention;
Fig. 3 is the high resolution TEM phenogram of the product obtaining of the method for the Si-Al of preparation ordered mesoporous molecular sieve of the present invention.
Embodiment
Embodiment 1
(1) extraction silicon and aluminum source:
The flyash that is 1:1.2 by mass ratio and NaOH mixing were placed in crucible and send into retort furnace, 550 ℃ of calcinings 2 hours;
After sample after calcining is cooling, takes out and grind, be placed in round-bottomed flask, add deionized water, the mass ratio of wherein said flyash and water is 1:4, at room temperature stirs 24 hours;
Solution after stirring is proceeded to centrifugation in centrifuge tube, get supernatant liquid as silicon and aluminum source solution for standby, the solid obtaining is for the preparation of the micro porous molecular sieve of NaX, NaSOD; Sial content in extraction liquid can be measured by atomic absorption spectrometry, is extracted the total mole number of silicon and aluminium in liquid;
(2) prepare Si-Al molecular sieve basic products: configuration CTAB solution, add water, dehydrated alcohol, under whipped state, add described silicon and aluminum source solution to obtain mixing solutions, described in described mixing solutions, in CTAB, water, ethanol and solution, the mol ratio of sial total amount (the mole number sum of the mole number of silicon and aluminium in solution) is CTAB:H2O:EtOH:Si-Al=0.41:344:53:1; Adopt the pH value to 9 of acid-conditioning solution, continue to stir 2 hours, stop stirring, suction filtration, washing, obtains white solid, and dried overnight in 80 ℃ of baking ovens, obtains basic products;
(3) product aftertreatment: at 550 ℃ of calcining 6h, the temperature rise rate of retort furnace is 2 ℃/min, obtains product after cooling by described basic products.
The product that the method for the invention is obtained is observed through X-ray diffraction method, and product has diffraction peak (as shown in Figure 1) in the 2-3 ° of left and right of XRD, and the order in its duct can be described; Adopting low temperature nitrogen adsorption-desorption method to observe, is typical IV adsorption curve, and explanation is mesoporous material feature, measures the specific surface area of product, and specific surface area is 300-800m
2/ g(BET area) (as shown in Figure 2); High-resolution-ration transmission electric-lens characterizes, and high resolution tem observation presents ordered porous feature, can observe orderly duct and have (as shown in Figure 3).
A method of preparing Si-Al ordered mesoporous molecular sieve, comprises the steps:
(1) extraction silicon and aluminum source: the flyash that is 1:1.2 by mass ratio and NaOH mixing were placed in crucible and send into retort furnace, 550 ℃ of calcinings 1 hour; After sample after calcining is cooling, takes out and grind, add deionized water, the mass ratio of wherein said flyash and water is 1:4, at room temperature stirs 10 hours; Solution centrifugal after stirring is separated, get supernatant liquid as silicon and aluminum source solution, the solid obtaining is for the preparation of the micro porous molecular sieve of NaX, NaSOD; Sial content in extraction liquid can be measured by atomic absorption spectrometry, is extracted the total mole number of silicon and aluminium in liquid;
(2) prepare Si-Al molecular sieve basic products: configuration CTAB solution, add water, dehydrated alcohol, under whipped state, add described silicon and aluminum source solution to obtain mixing solutions, described in described mixing solutions, in CTAB, water, ethanol and solution, the mol ratio of sial total amount is 0.4:300:50:1; Adopt the pH value to 10 of acid-conditioning solution, continue to stir 2 hours, stop stirring, suction filtration, washing, dry, obtain basic products;
(3) product aftertreatment: described basic products, at 550 ℃ of calcining 6h, is obtained to product after cooling.
Wherein, described in step (3), the temperature rise rate of retort furnace is 2 ℃/min; Described drying process in step (2) is: dried overnight in 80 ℃ of baking ovens.
The product that the method for the invention is obtained is observed through X-ray diffraction method, and product has diffraction peak (as shown in Figure 1) in the 2-3 ° of left and right of XRD, and the order in its duct can be described; Adopting low temperature nitrogen adsorption-desorption method to observe, is typical IV adsorption curve, and explanation is mesoporous material feature, measures the specific surface area of product, and specific surface area is 300-800m
2/ g(BET area) (as shown in Figure 2); High-resolution-ration transmission electric-lens characterizes, and high resolution tem observation presents ordered porous feature, can observe orderly duct and have (as shown in Figure 3).
Embodiment 3
A method of preparing Si-Al ordered mesoporous molecular sieve, comprises the steps:
(1) extraction silicon and aluminum source: the flyash that is 1:1.2 by mass ratio and NaOH mixing were placed in crucible and send into retort furnace, 600 ℃ of calcinings 2 hours; After sample after calcining is cooling, takes out and grind, add deionized water, the mass ratio of wherein said flyash and water is 1:4, at room temperature stirs 24 hours; Solution centrifugal after stirring is separated, get supernatant liquid as silicon and aluminum source solution, the solid obtaining is for the preparation of the micro porous molecular sieve of NaX, NaSOD; Sial content in extraction liquid can be measured by atomic absorption spectrometry, is extracted the total mole number of silicon and aluminium in liquid;
(2) prepare Si-Al molecular sieve basic products: configuration CTAB solution, add water, dehydrated alcohol, under whipped state, add described silicon and aluminum source solution to obtain mixing solutions, described in described mixing solutions, in CTAB, water, ethanol and solution, the mol ratio of sial total amount is 0.6:500:60:1; Adopt the pH value to 10 of acid-conditioning solution, continue to stir 4 hours, stop stirring, suction filtration, washing, dry, obtain basic products;
(3) product aftertreatment: described basic products, at 600 ℃ of calcining 8h, is obtained to product after cooling.
Wherein, described in step (3), the temperature rise rate of retort furnace is 2 ℃/min; Described drying process in step (2) is: dried overnight in 80 ℃ of baking ovens.
The product that the method for the invention is obtained is observed through X-ray diffraction method, and product has diffraction peak (as shown in Figure 1) in the 2-3 ° of left and right of XRD, and the order in its duct can be described; Adopting low temperature nitrogen adsorption-desorption method to observe, is typical IV adsorption curve, and explanation is mesoporous material feature, measures the specific surface area of product, and specific surface area is 300-800m
2/ g(BET area) (as shown in Figure 2); High-resolution-ration transmission electric-lens characterizes, and high resolution tem observation presents ordered porous feature, can observe orderly duct and have (as shown in Figure 3).
A method of preparing Si-Al ordered mesoporous molecular sieve, comprises the steps:
(1) extraction silicon and aluminum source: the flyash that is 1:1.2 by mass ratio and NaOH mixing were placed in crucible and send into retort furnace, 580 ℃ of calcinings 1.5 hours; After sample after calcining is cooling, takes out and grind, add deionized water, the mass ratio of wherein said flyash and water is 1:4, at room temperature stirs 15 hours; Solution centrifugal after stirring is separated, get supernatant liquid as silicon and aluminum source solution, the solid obtaining is for the preparation of the micro porous molecular sieve of NaX, NaSOD; Sial content in extraction liquid can be measured by atomic absorption spectrometry, is extracted the total mole number of silicon and aluminium in liquid;
(2) prepare Si-Al molecular sieve basic products: configuration CTAB solution, add water, dehydrated alcohol, under whipped state, add described silicon and aluminum source solution to obtain mixing solutions, described in described mixing solutions, in CTAB, water, ethanol and solution, the mol ratio of sial total amount is 0.5:400:55:1; Adopt the pH value to 10 of acid-conditioning solution, continue to stir 3 hours, stop stirring, suction filtration, washing, dry, obtain basic products;
(3) product aftertreatment: described basic products, at 580 ℃ of calcining 7h, is obtained to product after cooling.
Wherein, described in step (3), the temperature rise rate of retort furnace is 2 ℃/min; Described drying process in step (2) is: dried overnight in 80 ℃ of baking ovens.
The product that the method for the invention is obtained is observed through X-ray diffraction method, and product has diffraction peak (as shown in Figure 1) in the 2-3 ° of left and right of XRD, and the order in its duct can be described; Adopting low temperature nitrogen adsorption-desorption method to observe, is typical IV adsorption curve, and explanation is mesoporous material feature, measures the specific surface area of product, and specific surface area is 300-800m
2/ g(BET area) (as shown in Figure 2); High-resolution-ration transmission electric-lens characterizes, and high resolution tem observation presents ordered porous feature, can observe orderly duct and have (as shown in Figure 3).
Above-described embodiment is described the preferred embodiment of the present invention; not scope of the present invention is limited; design under the prerequisite of spirit not departing from the present invention; various distortion and improvement that those of ordinary skills make technical scheme of the present invention, all should fall in the definite protection domain of the claims in the present invention book.
Claims (6)
1. a method of preparing Si-Al ordered mesoporous molecular sieve, is characterized in that: comprise the steps:
Obtain take the discarded flyash of thermal power plant as raw material abstraction the solution that contains silicon and aluminium, take CTAB as template, add at room temperature synthetic basic products fast of second alcohol and water, described basic products is placed in to retort furnace calcining and removes template, obtain product after cooling; Wherein, in described CTAB, water, ethanol and solution, the mol ratio of sial total amount is (0.4-0.6): (300-500): (50-60): 1.
2. the method for preparing Si-Al ordered mesoporous molecular sieve according to claim 1, is characterized in that: comprise the steps:
(1) extraction silicon and aluminum source: the flyash that is 1:1.2 by mass ratio and NaOH mixing are placed in crucible and send into retort furnace, at 550-600 ℃ of calcining 1-2 hour; After sample after calcining is cooling, takes out and grind, add deionized water, the mass ratio of wherein said flyash and water is 1:4, at room temperature stirs 10-24 hour; Solution centrifugal after stirring is separated, get supernatant liquid as silicon and aluminum source solution, the solid obtaining is for the preparation of the micro porous molecular sieve of NaX, NaSOD;
(2) prepare Si-Al molecular sieve basic products: configuration CTAB solution, add water, dehydrated alcohol, under whipped state, add described silicon and aluminum source solution to obtain mixing solutions, described in described mixing solutions, in CTAB, water, ethanol and solution, the mol ratio of sial total amount is (0.4-0.6): (300-500): (50-60): 1; Adopt the pH value of acid-conditioning solution to 9-10, continue to stir 2-4 hour, stop stirring, suction filtration, washing, dry, obtain basic products;
(3) product aftertreatment: described basic products, at 550-600 ℃ of calcining 6-8h, is obtained to product after cooling.
3. the method for preparing Si-Al ordered mesoporous molecular sieve according to claim 2, is characterized in that: described in step (3), the temperature rise rate of retort furnace is 2 ℃/min.
4. the method for preparing Si-Al ordered mesoporous molecular sieve according to claim 3, is characterized in that: the described drying process in step (2) is: dried overnight in 80 ℃ of baking ovens.
5. the SI-AL ordered mesoporous molecular sieve that in claim 1-4, method prepares described in any one.
6. Si-Al ordered mesoporous molecular sieve according to claim 5, is characterized in that: described Si-Al ordered mesoporous molecular sieve is observed through X-ray diffraction method, has the strong diffraction peak of feature in the low-angle 1-3 of an XRD ° left and right; High-resolution-ration transmission electric-lens can directly be observed its ordered porous feature; Described Si-Al ordered mesoporous molecular sieve adopts low temperature nitrogen adsorption-desorption method to observe, and specific surface area is 300-800m
2/ g.
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| CN112023872A (en) * | 2020-08-26 | 2020-12-04 | 昆明理工大学 | Method for synthesizing mesoporous silicon-aluminum composite material by using high-alumina fly ash |
Citations (3)
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| CN101486471A (en) * | 2009-02-27 | 2009-07-22 | 西安建筑科技大学 | Method for preparing zeolite molecular sieves having different Si/Al ratios from fly ash |
| CN102633280A (en) * | 2012-03-21 | 2012-08-15 | 淮南联合大学 | Method for synthesising mesoporous molecular sieve by utilizing pulverized fuel ash |
| CN103172080A (en) * | 2013-03-27 | 2013-06-26 | 南京理工大学 | Method for preparing mesoporous molecular sieve |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486471A (en) * | 2009-02-27 | 2009-07-22 | 西安建筑科技大学 | Method for preparing zeolite molecular sieves having different Si/Al ratios from fly ash |
| CN102633280A (en) * | 2012-03-21 | 2012-08-15 | 淮南联合大学 | Method for synthesising mesoporous molecular sieve by utilizing pulverized fuel ash |
| CN103172080A (en) * | 2013-03-27 | 2013-06-26 | 南京理工大学 | Method for preparing mesoporous molecular sieve |
Non-Patent Citations (1)
| Title |
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| HSIAO-LAN CHANG ET AL.: ""Conversion of Fly Ash into Mesoporous Aluminosilicate"", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》, vol. 38, no. 3, 22 January 1999 (1999-01-22), pages 973 - 977 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112023872A (en) * | 2020-08-26 | 2020-12-04 | 昆明理工大学 | Method for synthesizing mesoporous silicon-aluminum composite material by using high-alumina fly ash |
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