CN1884074A - Method for synthesizing ultra-stable ordered mesoporous Si-Al molecular sieve - Google Patents
Method for synthesizing ultra-stable ordered mesoporous Si-Al molecular sieve Download PDFInfo
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Abstract
The invention discloses a siallite molecular sieve synthesizing method of super-stable sequent dielectric hole, which is characterized by the following: adopting sintered dielectric hole SBA-15 molecular sieve as hard mould; placing the hard mould in the diluent of micro-hole zeolitic priority mould agent; suspending in the glycerin to proceed second crystallizing synthesis to obtain dielectric hole molecular sieve with thick hole wall; possessing high-condensed silicon material and little hydroxyl group on the surface or in the inner part of hole wall. The hole wall contains five-ring micro-structure unit with micro-hole zeolite, which possesses super-strong water-heat stability.
Description
Technical field
The invention belongs to technical field of inorganic nanometer material, specially refer to ordered mesoporous Si-Al molecular sieve technology of preparing with superpower hydrothermal stability.
Background technology
Ordered mesoporous molecular sieve has high specific surface, regularly arranged and regulatable duct (2-50nm), this makes them in the many fields such as catalysis, absorption and assembling to macromolecular substance wide application prospect be arranged, thereby has just caused people's common concern since it comes out.But, to compare in micro-pore zeolite, the silicon species condensation in the mesoporous molecular sieve framework is incomplete, and there are a large amount of hydroxyls in hole wall surface and inside, so their hydrothermal stability is lower.In addition, the acidity of pure silicon base mesopore molecular sieve very a little less than.These deficiencies are seriously restricting its application in fields such as catalysis, petrochemical complex and chemical industry.
The condensation level that increases the silicon species of pore wall thickness and raising skeleton is two kinds of effective ways that improve and improve the mesopore molecular sieve hydrothermal stability.Is template as Stucky study group with three block macromolecular polymkeric substance, (Science, 1998,279,548-552) in the strongly-acid medium, synthesized the SBA-15 mesopore molecular sieve.Compare with MCM-41, because the pore wall thickness of molecular sieve increases (3-6nm), thereby hydrothermal stability is improved significantly.This molecular sieve is handled 24 hours in boiling water after, the orderly meso-hole structure of its six side still remains intact.Xiao study group (Angew.Chem.Int.Ed., 2003,42,3633-3637; Chem.Eur.J., 2004,10,5911-5922) utilizing fluorocarbon (FC-4) and three block superpolymer P123 is the synthetic pore wall thickness JLU-20 mesopore molecular sieve suitable with SBA-15 of template.Because the silicon species height in this framework of molecular sieve concentrates, it is handled in boiling water and still keeps the orderly meso-hole structure of six sides after 80 hours.Although obtain to a certain degree improvement with the hydrothermal stability of these two kinds of method synthetic mesopore molecular sieves, because the hole wall of products therefrom remains based on unformed, thereby its hydrothermal stability is far away from micro-pore zeolite.
The hole wall of the microstructure unit of micro-pore zeolite being introduced mesopore molecular sieve is the another kind of effective way that improves and improve the mesopore molecular sieve hydrothermal stability.Pinnavaia study group utilizes the presoma of zeolites such as Y, ZSM-5 and Beta to be silicon and aluminium source (J.Am.Chem.Soc., 2000,122,8791-8792; Angew.Chem.Int.Ed., 2001,40,1255-1258), be template with the CTABr cats product, under alkaline condition, synthesized Al-MSU-S, Al-MSU-S respectively
(MFI)And Al-MSU-S
(BEA)Although the pore wall thickness of these molecular sieves is less than 2nm, owing to introduced the microstructure unit of micro-pore zeolite in their framework of molecular sieve, so these mesopore molecular sieves are handled after 5 hours in 800 ℃ high-temperature steam and are still maintained ordered meso-porous structure.Xiao study group is silicon and aluminium source (Chem.Mater., 2002,14,1144-1148 with ZSM-5 and Beta guiding agent for zeolite respectively; J.Phys.Chem.B., 2003,107,7551-7556), be template with three block macromolecular polymkeric substance 123, under acidic conditions, synthesized two kinds of mesopore molecular sieves of MAS-9 and MAS-7.The pore wall thickness and the SBA-15 of these two kinds of molecular sieves are suitable, but owing to introduced the microstructure unit of micro-pore zeolite in the hole wall, thereby they can be stablized in boiling water 120 hours.Although the hydrothermal stability of MAS-9 and MAS-7 is higher than SBA-15 significantly, their degree of order obviously descends and its hydrothermal stability still is not so good as micro-pore zeolite.
The described synthetic method of above background technology is just from increasing pore wall thickness, improving the condensation level of silicon species the skeleton or introduce the microstructure unit etc. of micro-pore zeolite and ordered mesoporous molecular sieve is carried out the hydrothermal stability modification aspect single in hole wall, the gained hydrothermal stability of molecular sieve still is not so good as micro-pore zeolite, thereby still can not satisfy the needs of practical application in industry.Therefore, study and explore a kind of can preparation significant to the industrial applications that realizes mesopore molecular sieve with the synthetic route of the mesopore molecular sieve of hydrothermal stability like the micro-pore zeolite molecular sieve.
Summary of the invention
The objective of the invention is to develop a kind of pore wall thickness that can increase mesopore molecular sieve simultaneously, improve the condensation level of hole wall silicon species and the microstructure unit of micro-pore zeolite is incorporated into method in the mesopore molecular sieve hole wall, to improve and to improve its hydrothermal stability.
It is hard template with the mesoporous SBA-15 molecular sieve after the roasting that the present invention proposes a kind of, successively places the diluent neutralization of synthetic microporous zeolite precursor body to be suspended in glycerine respectively it and carries out secondary recrystallization.The main technique step is as follows:
1, synthetic microporous zeolite precursor body joins the template of synthetic microporous zeolite precursor body in the middle of the deionized water under the room temperature, treat that it dissolves fully after, in this solution, add silicon source, sodium aluminate and deionized water respectively, make the mol ratio of each reactant be: TPA
+/ Al
2O
3/ SiO
2/ Na
2O/H
2O=1: 0.055～0.275: 2.58: 0.057～2.64: 316.5.Stir and at 25 ℃ of following constant temperature 24 hours, synthetic microporous zeolite precursor body.
2, in the synthetic microporous zeolite precursor body of step 1 preparation, add the 30-150 ml deionized water, and after stirring 1～3 hour under 10-60 ℃, obtain the diluent of synthetic microporous zeolite precursor body.
3, the SBA-15 after the adding 3 gram roastings in the diluent of the presoma that step 2 prepares after stirring 0.5-3 hour under 10-60 ℃, was placed on 100-150 ℃ of following constant temperature 12～36 hours.
4, for the first time the crystallization products therefrom filter, washing and after dry 24 hours, again it is suspended in 7.5～15.0 milliliters of glycerine constant temperature 12～48 hours again under 120～150 ℃.
5, the resulting product of step 4 is filtered, and, filter the gained solid product at 80～100 ℃ of dry 12-48 hours with a large amount of deionized water wash, and in 550-800 ℃ of air atmosphere roasting 3-8 hour, must ordered mesoporous Si-Al molecular sieve.
The silicon source of being adopted among the present invention can be a kind of in methyl silicate, tetraethoxy, white carbon black, silicon sol and the water glass.
The template of the synthetic microporous zeolite precursor body that is adopted among the present invention can be a kind of in tetraethylammonium bromide, tetraethyl ammonium hydroxide, 4-propyl bromide and the TPAOH.
Ordered mesoporous Si-Al molecular sieve of the present invention is the MSAMS-2 mesopore molecular sieve, the MSAMS-4 mesopore molecular sieve.
Institute of the present invention synthetic mesopore molecular sieve has thick hole wall, silicon species condensation degree height in the skeleton, and hole wall surface and the inner hydroxyl that exists are seldom; The five-ring microstructure unit that contains micro-pore zeolite in the hole wall.These characteristics make mesopore molecular sieve have superpower hydrothermal stability.
Description of drawings
Fig. 1 is a kind of mesopore molecular sieve MSAMS-2 of the present invention and SBA-15 (A) XRD figure spectrum and (B) nitrogen adsorption/desorption isotherm.(a) SBA-15 and (b) MSAMS-2.
Fig. 2 is a kind of mesopore molecular sieve MSAMS-2 of the present invention (a) in (100) direction with (b) at the TEM photo of (110) direction.
Fig. 3 is the infrared spectrogram of MSAMS-2 of the present invention and two kinds of mesopore molecular sieves of MSAMS-4.(a) SBA-15, (b) MSAMS-2 and (c) MSAMS-4.
The XRD figure that Fig. 4 is before a kind of mesopore molecular sieve MSAMS-2 of the present invention (a) handles, (b) handled in 100 ℃ water 434 hours and (c) handled 6 hours in 800 ℃ the high-temperature steam is composed.
Fig. 5 is before a kind of mesopore molecular sieve MSAMS-2 of the present invention (a) handles, (b) handled in 100 ℃ water 434 hours and (c) nitrogen adsorption/desorption isotherm of 6 hours of processing in 800 ℃ the high-temperature steam.Thermoisopleth (b) and starting point (c) are respectively 200 and 400cm3/g.
Fig. 6 is that a kind of mesopore molecular sieve MSAMS-4 of the present invention handles the XRD figure spectrum before and after 6 hours in 800 ℃ high-temperature steam, after before (a) handling and (b) handling.
Fig. 7 is a kind of mesopore molecular sieve MSAMS-4 of the present invention handles 6 hours front and back in 800 ℃ high-temperature steam nitrogen adsorption/desorption isotherm.The starting point of thermoisopleth (b) is 200cm3/g.
Embodiment
Embodiment 1
Under the room temperature 1.44 gram 4-propyl bromides are joined in the middle of the deionized water, treat that it dissolves fully after, in this solution, add tetraethoxy, sodium aluminate and deionized water respectively, make the mol ratio of each reactant be: TPA
+/ Al
2O
3/ SiO
2/ Na
2O/H
2O=1: 0.055: 2.58: 0.057: 316.5.Above-mentioned solution was stirred 24 hours at 25 ℃, both obtained ZSM-5 type presoma.In the ZSM-5 presoma of preparation, add 90 ml deionized water, and after stirring 2 hours under 25 ℃, obtain the diluent of ZSM-5 type presoma.Then, the SBA-15 in the diluent of presoma after the adding 3 gram roastings, and after stirring 1 hour under 25 ℃, again reaction mixture was placed 130 ℃ of following thermostatic crystallizations 24 hours.For the first time the crystallization products therefrom filter, washing and after dry 24 hours, it is suspended in 10.0 milliliters of glycerine, and 130 ℃ of thermostatic crystallizations 48 hours.At last, for the second time the crystallization products therefrom filters, and with a large amount of deionized water wash, and filtration gained solid product is 80 ℃ of dryings 48 hours, and roasting 8 hours in 550 ℃ of air atmospheres, promptly gets the MSAMS-2 mesopore molecular sieve.
Result by little angle XRD, nitrogen adsorption/desorption isotherm and transmission electron microscope photo can learn that MSAMS-2 is the height order mesoporous structures of six sides (seeing Fig. 1 and Fig. 2).Among Fig. 1, (a) SBA-15 and (b) MSAMS-2.The result of the nitrogen absorption/desorption isotherm of SBA-15 and MSAMS-2 and BJH pore size distribution (seeing Figure 1A) shows that the aperture of MSAMS-2 is less than SBA-15.By Figure 1B, relatively the XRD figure of MSAMS-2 and SBA-15 spectrum can be found, the unit cell parameters size of two samples is consistent.Combined nitrogen absorption/desorption isotherm, BJH pore size distribution and XRD characterization result can learn that MSAMS-2 has thicker hole wall than SBA-15.The infrared spectra of SBA-15 and MSAMS-2 is seen Fig. 3 (a) and Fig. 3 (b).As can be seen from the figure, near the intensity of the infrared absorption peak of MSAMS-2 960cm-1 is significantly less than SBA-15, and this absorption peak belongs to the vibration of non-si-enriched hydroxyl, and the condensation level of the silicon species among this explanation MSAMS-2 is far above SBA-15.MSAMS-2 has tangible infrared absorption peak in the 550-600cm-1 scope, and this explanation has formed the five-ring microstructure unit of micro-pore zeolite in the hole wall of MSAMS-2.
Fig. 4 and Fig. 5 are nitrogen absorption/desorption isotherm and the XRD figure spectrums before and after the MSAMS-2 hydrothermal treatment consists.Wherein, before the respectively corresponding MSAMS-2 of curve a, b and c handles, it was handled 434 hours in 100 ℃ water and processing after 6 hours in 800 ℃ high-temperature vapor (20v%).As can be seen, the nitrogen absorption/desorption isotherm of sample and XRD figure spectrum remains unchanged substantially before and after the hydrothermal treatment consists from Fig. 4 and Fig. 5, and this explanation MSAMS-2 has superpower hydrothermal stability.The ordered mesoporous molecular sieve that can tolerate ordeal like this does not appear in the newspapers in the literature as yet.
Embodiment 2
Under the room temperature 1.14 gram tetraethylammonium bromides are joined in the middle of the deionized water, treat that it dissolves fully after, in this solution, add tetraethoxy, sodium aluminate and deionized water respectively, make the mol ratio of each reactant be: TEA
+/ Al
2O
3/ SiO
2/ Na
2O/H
2O=1: 0.055: 2.58: 0.057: 316.5.Above-mentioned solution was stirred 24 hours at 25 ℃, obtain Beta type presoma.In the Beta presoma of preparation, add 90 ml deionized water, and after stirring 2 hours under 25 ℃, obtain the diluent of Beta type presoma.Then, the SBA-15 in the diluent of presoma after the adding 3 gram roastings, and after stirring 1 hour under 25 ℃, again reaction mixture was placed 130 ℃ of following thermostatic crystallizations 24 hours.For the first time the crystallization products therefrom filter, washing and after dry 24 hours, it is suspended in 10.0 milliliters of glycerine, and 130 ℃ of thermostatic crystallizations 48 hours.At last, for the second time the crystallization products therefrom filters, and with a large amount of deionized water wash, and filtration gained solid product is 80 ℃ of dryings 48 hours, and roasting 8 hours in 550 ℃ of air atmospheres, promptly gets the MSAMS-4 mesopore molecular sieve.
The infrared spectra of SBA-15 and MSAMS-4 is seen Fig. 3 (a) and Fig. 3 (c).As can be seen from the figure, near the intensity of the infrared absorption peak of MSAMS-4 960cm1 is significantly less than SBA-15, and this absorption peak belongs to the vibration of non-si-enriched hydroxyl, and the condensation level of the silicon species among this explanation MSAMS-2 is far above SBA-15.MSAMS-4 has tangible infrared absorption peak in the 550-600cm-1 scope, and this explanation has formed the five-ring microstructure unit of micro-pore zeolite in the hole wall of MSAMS-4.
Fig. 6 and Fig. 7 are nitrogen absorption/desorption isotherm and the XRD figure spectrums before and after the MSAMS-4 hydrothermal treatment consists.Wherein, the respectively corresponding MSAMS-4 of curve a and b handles preceding and handles after 6 hours in 800 ℃ high-temperature vapor (20v%).As can be seen, the nitrogen absorption/desorption isotherm of sample and XRD figure spectrum remains unchanged substantially before and after the hydrothermal treatment consists from Fig. 6 and Fig. 7, and this explanation MSAMS-4 has superpower hydrothermal stability equally.
Embodiment 3
Under the room temperature 1.44 gram 4-propyl bromides are joined in the middle of the deionized water, treat that it dissolves fully after, in this solution, add tetraethoxy, sodium aluminate and deionized water respectively, make the mol ratio of each reactant be: TPA
+/ Al
2O
3/ SiO
2/ Na
2O/H
2O=1: 0.275: 2.58: 0.285: 316.5.Above-mentioned solution was stirred 24 hours at 25 ℃, both obtained ZSM-5 type presoma.In the ZSM-5 presoma of preparation, add 90 ml deionized water, and after stirring 1 hour under 25 ℃, obtain the diluent of ZSM-5 type presoma.Then, the SBA-15 in the diluent of presoma after the adding 3 gram roastings, and after stirring 1 hour under 25 ℃, again reaction mixture was placed 130 ℃ of following thermostatic crystallizations 36 hours.For the first time the crystallization products therefrom filter, washing and after dry 24 hours, it is suspended in 7.5 milliliters of glycerine, and 130 ℃ of thermostatic crystallizations 48 hours.At last, for the second time the crystallization products therefrom filters, and with a large amount of deionized water wash, and filtration gained solid product is 80 ℃ of dryings 48 hours, and roasting 8 hours in 550 ℃ of air atmospheres, promptly gets the MSAMS-2 mesopore molecular sieve.
Embodiment 4
Under the room temperature 1.14 gram tetraethylammonium bromides are joined in the middle of the deionized water, treat that it dissolves fully after, in this solution, add tetraethoxy, sodium aluminate and deionized water respectively, make the mol ratio of each reactant be: TEA
+/ Al
2O
3/ SiO
2/ Na
2O/H
2O=1: 0.275: 2.58: 0.285: 316.5.Above-mentioned solution was stirred 24 hours at 25 ℃, both obtained Beta type presoma.In the Beta presoma of preparation, add 90 ml deionized water, and after stirring 3 hours under 25 ℃, obtain the diluent of Beta type presoma.Then, the SBA-15 in the diluent of presoma after the adding 3 gram roastings, and after stirring 1 hour under 25 ℃, again reaction mixture was placed 130 ℃ of following thermostatic crystallizations 48 hours.For the first time the crystallization products therefrom filter, washing and after dry 24 hours, it is suspended in 10.0 milliliters of glycerine, and 130 ℃ of thermostatic crystallizations 24 hours.At last, for the second time the crystallization products therefrom filters, and with a large amount of deionized water wash, and filtration gained solid product is 80 ℃ of dryings 48 hours, and roasting 8 hours in 550 ℃ of air atmospheres, promptly gets the MSAMS-4 mesopore molecular sieve.
Embodiment 5
Under the room temperature 1.44 gram 4-propyl bromides are joined in the middle of the deionized water, treat that it dissolves fully after, in this solution, add methyl silicate, sodium aluminate and deionized water respectively, make the mol ratio of each reactant be: TPA
+/ Al
2O
3/ SiO
2/ Na
2O/H
2O=1: 0.055: 2.58: 0.057: 316.5.Above-mentioned solution was stirred 24 hours at 25 ℃, both obtained ZSM-5 type presoma.In the ZSM-5 presoma of preparation, add 90 ml deionized water, and after stirring 2 hours under 25 ℃, obtain the diluent of ZSM-5 type presoma.Then, the SBA-15 in the diluent of presoma after the adding 3 gram roastings, and after stirring 1 hour under 25 ℃, again reaction mixture was placed 130 ℃ of following thermostatic crystallizations 12 hours.For the first time the crystallization products therefrom filter, washing and after dry 24 hours, it is suspended in 10.0 milliliters of glycerine, and 130 ℃ of thermostatic crystallizations 48 hours.At last, for the second time the crystallization products therefrom filters, and with a large amount of deionized water wash, and filtration gained solid product is 80 ℃ of dryings 48 hours, and roasting 8 hours in 550 ℃ of air atmospheres, promptly gets the MSAMS-2 mesopore molecular sieve.
Embodiment 6
Under the room temperature 1.14 gram tetraethylammonium bromides are joined in the middle of the deionized water, treat that it dissolves fully after, in this solution, add white carbon black, sodium aluminate and deionized water respectively, make the mol ratio of each reactant be: TEA
+/ Al
2O
3/ SiO
2/ Na
2O/H
2O=1: 0.055: 2.58: 0.057: 316.5.Above-mentioned solution was stirred 24 hours at 25 ℃, both obtained Beta type presoma.In the Beta presoma of preparation, add 90 ml deionized water, and after stirring 2 hours under 25 ℃, obtain the diluent of Beta type presoma.Then, the SBA-15 in the diluent of presoma after the adding 3 gram roastings, and after stirring 1 hour under 25 ℃, again reaction mixture was placed 130 ℃ of following thermostatic crystallizations 12 hours.For the first time the crystallization products therefrom filter, washing and after dry 24 hours, it is suspended in 10.0 milliliters of glycerine, and 150 ℃ of thermostatic crystallizations 48 hours.At last, for the second time the crystallization products therefrom filters, and with a large amount of deionized water wash, and filtration gained solid product is 80 ℃ of dryings 48 hours, and roasting 8 hours in 550 ℃ of air atmospheres, promptly gets the MSAMS-4 mesopore molecular sieve.
Embodiment 7
Under the room temperature 1.10 gram TPAOH are joined in the middle of the deionized water, treat that it dissolves fully after, in this solution, add methyl silicate, sodium aluminate and deionized water respectively, make the mol ratio of each reactant be: TPA
+/ Al
2O
3/ SiO
2/ Na
2O/H
2O=1: 0.055: 2.58: 0.057: 316.5.Above-mentioned solution was stirred 24 hours at 25 ℃, both obtained ZSM-5 type presoma.In the ZSM-5 presoma of preparation, add 90 ml deionized water, and after stirring 2 hours under 25 ℃, obtain the diluent of ZSM-5 type presoma.Then, the SBA-15 in the diluent of presoma after the adding 3 gram roastings, and after stirring 1 hour under 25 ℃, again reaction mixture was placed 130 ℃ of following thermostatic crystallizations 24 hours.For the first time the crystallization products therefrom filter, washing and after dry 24 hours, it is suspended in 10.0 milliliters of glycerine, and 130 ℃ of thermostatic crystallizations 48 hours.At last, for the second time the crystallization products therefrom filters, and with a large amount of deionized water wash, and filtration gained solid product is 80 ℃ of dryings 48 hours, and roasting 8 hours in 550 ℃ of air atmospheres, promptly gets the MSAMS-2 mesopore molecular sieve.
Embodiment 8
Under the room temperature 1.10 gram TPAOH are joined in the middle of the deionized water, treat that it dissolves fully after, in this solution, add silicon sol, sodium aluminate and deionized water respectively, make the mol ratio of each reactant be: TPA
+/ Al
2O
3/ SiO
2/ Na
2O/H
2O=1: 0.055: 2.58: 0.057: 316.5.Above-mentioned solution was stirred 24 hours at 25 ℃, both obtained ZSM-5 type presoma.In the ZSM-5 presoma of preparation, add 90 ml deionized water, and after stirring 2 hours under 25 ℃, obtain the diluent of ZSM-5 type presoma.Then, the SBA-15 in the diluent of presoma after the adding 3 gram roastings, and after stirring 1 hour under 25 ℃, again reaction mixture was placed 130 ℃ of following thermostatic crystallizations 24 hours.For the first time the crystallization products therefrom filter, washing and after dry 24 hours, it is suspended in 10.0 milliliters of glycerine, and 130 ℃ of thermostatic crystallizations 48 hours.At last, for the second time the crystallization products therefrom filters, and with a large amount of deionized water wash, and filtration gained solid product is 80 ℃ of dryings 48 hours, and roasting 8 hours in 550 ℃ of air atmospheres, promptly gets the MSAMS-2 mesopore molecular sieve.
Embodiment 9
Under the room temperature 1.10 gram TPAOH are joined in the middle of the deionized water, treat that it dissolves fully after, in this solution, add water glass, sodium aluminate and deionized water respectively, make the mol ratio of each reactant be: TPA
+/ Al
2O
3/ SiO
2/ Na
2O/H
2O=1: 0.055: 2.58: 2.637: 316.5.Above-mentioned solution was stirred 24 hours at 25 ℃, both obtained ZSM-5 type presoma.In the ZSM-5 presoma of preparation, add 90 ml deionized water, and after stirring 2 hours under 25 ℃, obtain the diluent of ZSM-5 type presoma.Then, the SBA-15 in the diluent of presoma after the adding 3 gram roastings, and after stirring 1 hour under 25 ℃, again reaction mixture was placed 130 ℃ of following thermostatic crystallizations 24 hours.For the first time the crystallization products therefrom filter, washing and after dry 24 hours, it is suspended in 10.0 milliliters of glycerine, and 130 ℃ of thermostatic crystallizations 48 hours.At last, for the second time the crystallization products therefrom filters, and with a large amount of deionized water wash, and filtration gained solid product is 80 ℃ of dryings 48 hours, and roasting 8 hours in 550 ℃ of air atmospheres, promptly gets the MSAMS-2 mesopore molecular sieve.
Claims (4)
1, a kind of synthetic method of ultra-stable ordered mesoporous Si-Al molecular sieve, it is characterized in that: with the mesoporous SBA-15 molecular sieve after the roasting is hard template, successively place the diluent neutralization of synthetic microporous zeolite precursor body to be suspended in glycerine respectively it and carry out secondary recrystallization, processing step is as follows:
● synthetic microporous zeolite precursor body, under the room temperature template of synthetic microporous zeolite precursor body is joined in the middle of the deionized water, treat that it dissolves fully after, in this solution, add silicon source, sodium aluminate and deionized water respectively, make the mol ratio of each reactant be: TPA
+/ Al
2O
3/ SiO
2/ Na
2O/H
2O=1: 0.055～0.275: 2.58: 0.057～2.64: 316.5.Stir and at 25 ℃ of following constant temperature 24 hours, synthetic microporous zeolite precursor body;
● in synthetic micro-pore zeolite presoma, add the 30-150 ml deionized water, and after stirring 1～3 hour under 10-60 ℃, obtain the diluent of synthetic microporous zeolite precursor body;
● the mesoporous SBA-15 molecular sieve in the diluent of presoma after the adding 3 gram roastings after stirring 0.5-3 hour under 25 ℃, was placed on 100-150 ℃ of following constant temperature 12～36 hours;
● for the first time the crystallization products therefrom filter, washing and after dry 24 hours, again it is suspended in 7.5～15.0 milliliters of glycerine constant temperature 12～48 hours again under 120～150 ℃.
● for the second time the resulting product of crystallization filters, and with a large amount of deionized water wash, filters the gained solid product at 80～100 ℃ of dry 12-48 hours, and in 550-800 ℃ of air atmosphere roasting 3-8 hour, get ordered mesoporous Si-Al molecular sieve.
2, the preparation method of mesopore molecular sieve according to claim 1 is characterized in that the silicon source of being adopted is a kind of in white carbon black, silicon sol, methyl silicate and the water glass.
3, the preparation method of mesopore molecular sieve according to claim 1, the template that it is characterized in that synthetic microporous zeolite precursor body can be a kind of in tetraethylammonium bromide, tetraethyl ammonium hydroxide, 4-propyl bromide and the TPAOH.
4, the ultra-stable ordered mesoporous Si-Al molecular sieve of the preparation method of the described mesopore molecular sieve of claim 1 preparation is: MSAMS-2 mesopore molecular sieve or MSAMS-4 mesopore molecular sieve.
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| CN104857986A (en) * | 2015-04-20 | 2015-08-26 | 南京工业大学 | Preparation method of iron-containing MCM-41 molecular sieve membrane used for catalyzing phenol hydroxylation |
| CN106283187A (en) * | 2015-05-29 | 2017-01-04 | 武汉理工大学 | A kind of ordered big hole-mesoporous multi-stage porous Si-Al molecular sieve ZSM-5 monocrystalline with opal structural and synthetic method thereof |
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| CN1257839C (en) * | 2004-09-16 | 2006-05-31 | 华东师范大学 | Process of preparing mesoporous molecular sieve with ionic liquid as template agent |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CZ303642B6 (en) * | 2008-05-27 | 2013-01-23 | Ústav chemických procesu Akademie ved CR | Process for preparing pellets from silicate and aluminosilicate mesoporous molecular sieves |
| CN102963905A (en) * | 2012-11-13 | 2013-03-13 | 中国科学院青岛生物能源与过程研究所 | Method for synthetizing Al-SBA-15 containing plug type silicon/aluminum structure in pore channel |
| CN104857986A (en) * | 2015-04-20 | 2015-08-26 | 南京工业大学 | Preparation method of iron-containing MCM-41 molecular sieve membrane used for catalyzing phenol hydroxylation |
| CN106283187A (en) * | 2015-05-29 | 2017-01-04 | 武汉理工大学 | A kind of ordered big hole-mesoporous multi-stage porous Si-Al molecular sieve ZSM-5 monocrystalline with opal structural and synthetic method thereof |
| CN106283187B (en) * | 2015-05-29 | 2019-04-26 | 武汉理工大学 | A kind of mesoporous multi-stage porous Si-Al molecular sieve ZSM-5 monocrystalline of ordered big hole-with opal structural and its synthetic method |
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