CN102826564A - Preparation method for Beta zeolite molecular sieve with hierarchical porous structure - Google Patents
Preparation method for Beta zeolite molecular sieve with hierarchical porous structure Download PDFInfo
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- CN102826564A CN102826564A CN2012102874114A CN201210287411A CN102826564A CN 102826564 A CN102826564 A CN 102826564A CN 2012102874114 A CN2012102874114 A CN 2012102874114A CN 201210287411 A CN201210287411 A CN 201210287411A CN 102826564 A CN102826564 A CN 102826564A
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Abstract
The invention discloses a preparation method for a Beta zeolite molecular sieve with a hierarchical porous structure. Ethyl orthosilicate is used as a silicon source, sodium metaaluminate is used as an aluminum source, hexaammonio cationic quaternary ammonium surfactant is used as a template, and then the hierarchical porous zeolite molecular sieve containing meso pores and Beta zeolite micropores is prepared by using a hydro-thermal synthesis process under an alkaline condition. According to the invention, the hexaammonio cationic quaternary ammonium surfactant is used as a Beta zeolite structure guiding agent and generates micropores, aggregation of hydrophobic long-chain alkyl groups on the surfactant forms the meso pores, so the prepared Beta zeolite molecular sieve has both meso pores and the crystalline micropores. The structure with both the meso pores and the micropores enables defects of a single pore structure to be avoided and mass transfer efficiency to be improved, and the Beta zeolite molecular sieve has a wide application prospect in aspects of macro-molecular catalysis, adsorption, separation, etc.
Description
Technical field
The invention belongs to technical field of inorganic material, relate to a kind of zeolite molecular sieve and preparation method thereof, be specifically related to a kind of preparation method who includes the Beta zeolite molecular sieve of micropore and mesoporous hierarchical porous structure.
Background technology
The Beta zeolite is a kind of have three-dimensional twelve-ring pore passage structure, edge
aDirection with
bDirection has twelve-ring straight hole, edge
cDirection has the micro porous molecular sieve of the twelve-ring pore passage structure of distortion a little.Because pore passage structure, peracidity and good hydrothermal stability that the Beta zeolite is unique, its prospects for commercial application is very outstanding, successfully is applied to the petrochemical industries such as alkylation of isomerizing, catalytic cracking and aromatic hydrocarbons.But because the narrow relatively pore passage structure of micro-pore zeolite molecular sieve causes reaction product in time not spread and causes carbon distribution easily; It is lost activity; Especially when the kinetics size of reactant molecule has surpassed the aperture of micro-pore zeolite molecular sieve; Reactant molecule can only react at the crystal grain outside surface, so there is certain use limitation in micro porous molecular sieve in relating to macromolecular reaction.
The nineties in 20th century; U.S. Mobil company reported first has been synthesized the MCM-41 mesoporous molecular sieve; This material with regular pore canal structure and narrower mesopore pore size distribution has good diffusion, can solve macromolecular reaction thing and product spread difficulty in micro-pore zeolite problem.Yet, mesoporous material be in order on meso-scale in order, the mode of connection between inner each atom of hole wall is similar with amorphous material, causes its hydrothermal stability relatively poor, acidity a little less than.This has greatly influenced the application of these mesoporous materials in the petrochemical complex industrial aspect.
In order to overcome micro-pore zeolite and mesopore molecular sieve limitation separately, the two is had complementary advantages, caused widely for the research of the molecular sieve of hierarchical porous structure in recent years and paid close attention to.This material has combined the duct advantage of mesoporous material and the strongly-acid and the high hydrothermal stability of micro-pore zeolite, can make two kinds of material advantage complementations, coordinative role.People [Karlsson A. St cker M. Schmidt R. Composites of micro-and mesoporous materials:simultaneous syntheses of MFI/MCM-41 like phases by a mixed template approach. Microporous Mesoporous Mater such as Karlsson Arne; 1999; (27): 181-192] utilize two kinds of template of six alkyl trimethyl ammonium bromides and TTAB; Through two step crystallization methods, prepared multistage porous molecular sieve with MFI micropore and MCM-41 meso-hole structure; People [Proke ov á P. ejka M.J. Bein T. Preparation of nanosized micro/mesoporous composites via simultaneous synthesis of Beta/MCM-48 phases. Microporous Mesoporous Mater such as Proke ov á P; 2003; (64): 165-174] crystal seed method is preset in utilization; At first make the beta-molecular sieve seed-solution, crystallization is that XRD detects and to be unbodied seed-solution then, mixes with the fresh solution of synthetic MCM-48 molecular sieve fast after being chilled to room temperature; Through synchronous hydrothermal treatment consists, obtain the composite molecular screen of β/MCM-48 micropore-mesopore hierarchical porous structure.Although these existing techniques in realizing the Gradient distribution and the tart of multistage porous molecular sieve pore structure reasonably combined, the hole wall of the multilevel hole material of preparation is still unbodied in essence, can not fundamentally improve the acidity and the hydrothermal stability of mesoporous material.The soft template method that generally adopts at present prepares molecular sieve, only can synthesize the micro-pore zeolite of mesopore molecular sieve with single amorphous hole wall structure or pure crystallization.
Summary of the invention
The objective of the invention is to provides a kind of preparation method of Beta zeolite molecular sieve of hierarchical porous structure to above-mentioned existing in prior technology problem and defective, and this Beta zeolite molecular sieve includes micropore and mesoporous, has the β zeolite micropore hole wall structure of crystallization.
The present invention is a template with the cationic quaternary surfactant of six ammoniums with special construction; Adopt traditional hydrothermal synthesis method; Electronegative silico-aluminate interacts in ammonium functional group through positively charged in the tensio-active agent and the gel, has played the effect of structure directing, has formed the multistage porous molecular sieve with β zeolite pore wall construction; The hole wall degree of order of mesopore molecular sieve be can improve, and then its hydrothermal stability and strongly-acid improved.
In order to achieve the above object, the present invention has adopted following technical scheme.
A kind of preparation method of Beta zeolite molecular sieve of hierarchical porous structure may further comprise the steps:
(1) sodium hydroxide, sodium metaaluminate, six ammonium quaternary surfactants and water stirring are obtained settled solution;
(2) under 50～60 ℃, dropping tetraethoxy and alcoholic acid mixing solutions obtain silica-alumina gel in the settled solution that step (1) obtains while stirring;
(3) after the silica-alumina gel that step (2) is obtained remains on 50～60 ℃ of continuation stirring 6～12h, still aging;
(4) with product crystallization under air-proof condition of step (3), the solid after crystallization finishes is calcined in air after suction filtration, washing and drying again, obtains the Beta zeolite molecular sieve of hierarchical porous structure.
The mol ratio of said each material is: tetraethoxy: sodium metaaluminate: sodium hydroxide: six ammonium quaternary surfactants: ethanol: water=1: (0.04～0.08): (0.35～0.41): (0.04～0.08): 4: (70～72).
In the step (3), said still aging temperature is 30～40 ℃, and the time is 16～20h.
In the step (4), the temperature of said crystallization is 140～150 ℃, and the time is 110～130h.
In the step (4), said incinerating temperature is 500～550 ℃, and the time is 5～8h.
The mol ratio of said each material is preferably: tetraethoxy: sodium metaaluminate: sodium hydroxide: six ammonium quaternary surfactants: ethanol: water=1:0.05:0.38:0.05:4:71.06.
Si/Al=16 of the Beta zeolite molecular sieve of said hierarchical porous structure.
Said six ammonium quaternary surfactants are according to document [Na K. Jo C. Kim J. Cho K. Jung J. Seo Y. Messinger R.J. Chmelka B.F. Ryoo. R. Directing Zeolite Structures into Hierarchically Nanoporous Architectures. Science; 2011; (333): 328-332 method] is synthetic, and concrete steps are following:
(1) with the 1-bromine n-Hexadecane of 0.01mol and the N of 0.1mol, N, N'; N'-tetramethyl--1,6-hexanediamine are dissolved in toluene and the acetonitrile volume ratio is in the 50ml mixing solutions of 1:1, refluxes while stirring 10 hours in 65 ℃; Cool to room temperature; Volatilization removes and desolvates, and the deposition that obtains is through washing, filtration, vacuum-drying, and the solid that obtains is designated as [C
16H
33– N
+(CH
3)
2– C
6H
12– N (CH
3)
2] [Br
-];
(2) with [C of 0.0025mol
16H
33– N
+(CH
3)
2– C
6H
12– N (CH
3)
2] [Br
-] and the α of 0.025mol, α '-dichloro-p-xylene is dissolved in the acetonitrile solvent of 50ml, refluxed while stirring 50 hours in 65 ℃, and cool to room temperature, volatilization removes and desolvates, and the deposition that obtains is through washing, filtration, vacuum-drying, and the solid that obtains is designated as [C
16H
33– N
+(CH
3)
2– C
6H
12– N
+(CH
3)
2-CH
2– (
p-C
6H
4) – CH
2-Cl] [Br
-] [Cl
-];
(3) with [C of 0.005mol
16H
33– N
+(CH
3)
2– C
6H
12– N
+(CH
3)
2-CH
2– (
p-C
6H
4) – CH
2-Cl] [Br
-] [Cl
-] and the N of 0.0025mol, N, N', N'-tetramethyl--1; The 6-hexanediamine is dissolved in the chloroform solvent of 30ml, refluxes cool to room temperature while stirring 24 hours in 61 ℃; Volatilization removes and desolvates, and the deposition that obtains promptly obtains six ammonium quaternary surfactants through washing, filtration, vacuum-drying.
The present invention compared with prior art has the following advantages and beneficial effect:
(1) the present invention utilizes the cationic quaternary surfactant of six ammoniums to be template; In the tensio-active agent in the ammonium functional group of positively charged and the gel electronegative silico-aluminate interact; Played the effect of structure directing, formed multistage porous molecular sieve with β zeolite pore wall construction;
(2) as raw material, it is inexpensive to be easy to get with tetraethoxy, sodium metaaluminate and sodium hydroxide in the present invention, adopts hydrothermal synthesis method, has simplified synthesis step, and technology is simple, and cost is low;
(3) the Beta zeolite molecular sieve of the present invention's preparation includes micropore and mesoporous; β zeolite micropore hole wall structure with crystallization; This molecular sieve with multiple pore structure and overlaying function can be avoided the defective of single pore structure; Improve the hole wall degree of order of mesopore molecular sieve, and then improve its hydrothermal stability and strongly-acid, having broad application prospects aspect macromole absorption and the catalysis.
Description of drawings
Fig. 1 is the X-ray diffraction map of Beta zeolite molecular sieve (a) and common Beta zeolite (b) of the hierarchical porous structure of the embodiment of the invention 3 preparation.
Fig. 2 is the stereoscan photograph of Beta zeolite molecular sieve of the hierarchical porous structure of the embodiment of the invention 3 preparation.
Fig. 3 is the transmission electron microscope photo of Beta zeolite molecular sieve material of the hierarchical porous structure of the embodiment of the invention 3 preparation.
Fig. 4 is Beta zeolite molecular sieve and the nitrogen adsorption-desorption isotherm of common Beta zeolite of the hierarchical porous structure of the embodiment of the invention 3 preparation.
Fig. 5 is the Beta zeolite molecular sieve pore size distribution curve of the hierarchical porous structure of embodiment 3 preparations that obtain according to the BJH Model Calculation.
Embodiment
Below in conjunction with specific embodiment the present invention is further described, but the scope that the present invention requires to protect is not limited thereto.
Embodiment 1
(1) with 0.2428g sodium hydroxide, 0.0745g sodium metaaluminate (44.7wt% Na
2O, 52wt% Al
2O
3), 1.1842g six ammonium quaternary surfactants and 21mL water stirs and obtains settled solution;
(2) under 50 ℃ of magnetic agitation, dropping 3.6mL tetraethoxy (98%, J ￡ K) and 3.8mL alcoholic acid mixing solutions obtain silica-alumina gel in the settled solution that step (1) obtains;
(3) after the silica-alumina gel that step (2) is obtained remains on 50 ℃ of continuation stirring 6h, again at 30 ℃ of following still aging 16h;
(4) with the product of step (3) pack into the sealing stainless steel cauldron in; In 145 ℃ of following crystallization 120h; Solid after crystallization finishes is calcined 5h again and is removed organic formwork agent after suction filtration, washing and drying under 550 ℃ in air, obtain the Beta zeolite molecular sieve of hierarchical porous structure.
Embodiment 2
(1) with 0.3623g sodium hydroxide, 0.1112g sodium metaaluminate (44.7wt% Na
2O, 52wt% Al
2O
3), 1.7675g six ammonium quaternary surfactants and 32mL water stirs and obtains settled solution;
(2) under 60 ℃ of magnetic agitation, Dropwise 5 .4mL tetraethoxy in the settled solution that step (1) obtains (98%, J ￡ K) and 5.6mL alcoholic acid mixing solutions obtain silica-alumina gel;
(3) after the silica-alumina gel that step (2) is obtained remains on 60 ℃ of continuation stirring 10h, again at 35 ℃ of following still aging 18h;
(4) with the product of step (3) pack into the sealing stainless steel cauldron in; In 140 ℃ of following crystallization 110h; Solid after crystallization finishes is calcined 8h again and is removed organic formwork agent after suction filtration, washing and drying under 500 ℃ in air, obtain the Beta zeolite molecular sieve of hierarchical porous structure.
Embodiment 3
(1) with 0.4536g sodium hydroxide, 0.1395g sodium metaaluminate (44.7wt% Na
2O, 52wt% Al
2O
3), 2.2094g six ammonium quaternary surfactants and 39.4mL water stirs and obtains settled solution;
(2) under 55 ℃ of magnetic agitation, dropping 6.8mL tetraethoxy (98%, J ￡ K) and 7mL alcoholic acid mixing solutions obtain silica-alumina gel in the settled solution that step (1) obtains;
(3) after the silica-alumina gel that step (2) is obtained remains on 55 ℃ of continuation stirring 12h, again at 40 ℃ of following still aging 20h;
(4) with the product of step (3) pack into the sealing stainless steel cauldron in; In 150 ℃ of following crystallization 130h; Solid after crystallization finishes is calcined 6h again and is removed organic formwork agent after suction filtration, washing and drying under 550 ℃ in air, obtain the Beta zeolite molecular sieve of hierarchical porous structure.
Beta zeolite molecular sieve to the hierarchical porous structure of embodiment 3 preparation is analyzed.
Adopt D8 Advance type X-ray diffractometer (Bruker company, Germany) that sample is characterized.The result is as shown in Figure 1, and sample is explained to have the β zeolite facies in the product at 7.6 ° and the 22.4 ° characteristic diffraction peaks that present the β zeolite.
Adopt ZEISS Ultra 55 type field emission scanning electron microscopes (Carl Zeiss company, Germany) that the surface topography of sample is characterized.The result is as shown in Figure 2, and sample has presented the surface topography of relative homogeneous crystallization, does not observe the β zeolite mixture of out of phase unbodied aluminosilicate material and pure crystalline state.
Adopt JEM-2100HR type transmission electron microscope (JEOL of electronics corporation, Japan) that product is characterized.The result is as shown in Figure 3, and sample has presented β zeolite lattice fringe on mesoporous wall, explains that Beta zeolite molecular sieve of the present invention has the β zeolite pore wall construction of crystalline state.
Adopt ASAP 2010 type N
2Adsorption analysis appearance (Merck & Co., Inc, the U.S.) is analyzed the pore structure of product.The result is shown in 4, and the Beta zeolite molecular sieve of hierarchical porous structure of the present invention has shown IV type adsorption isothermal line.0.0＜
P/P 0 ＜0.1 low
P/P 0 The district, adsorptive capacity with
P/P 0 Increase and sharply increase, this is because N
2Filling in the micropore district; 0.5＜
P/P 0 The desorption hysteresis loop appears in＜0.8 district, explains to exist mesoporously in the product, belongs to N
2Capillary condensation phenomenon in mesoporous; Greater than
P/P 0 =0.9 zone, adsorptive capacity rises again, and this is N
2Absorption in the macropore that between particle, forms.
The pore size distribution curve of Fig. 5 for obtaining according to desorption BJH Model Calculation explains that there is narrower mesoporous pore size distribution in Beta zeolite molecular sieve of the present invention, and its mean pore size is 4.3nm.
Above result shows that the Beta zeolite molecular sieve of the hierarchical porous structure of the present invention's preparation has the irregular mesopore orbit of three-dimensional communication and the β zeolite micropore hole wall structure of crystallization.
Claims (6)
1. the preparation method of the Beta zeolite molecular sieve of a hierarchical porous structure is characterized in that, may further comprise the steps:
(1) sodium hydroxide, sodium metaaluminate, six ammonium quaternary surfactants and water stirring are obtained settled solution;
(2) under 50～60 ℃, dropping tetraethoxy and alcoholic acid mixing solutions obtain silica-alumina gel in the settled solution that step (1) obtains while stirring;
(3) after the silica-alumina gel that step (2) is obtained remains on 50～60 ℃ of continuation stirring 6～12h, still aging;
(4) with product crystallization under air-proof condition of step (3), the solid after crystallization finishes is calcined in air after suction filtration, washing and drying again, obtains the Beta zeolite molecular sieve of hierarchical porous structure.
2. preparation method according to claim 1; It is characterized in that the mol ratio of said each material is: tetraethoxy: sodium metaaluminate: sodium hydroxide: six ammonium quaternary surfactants: ethanol: water=1: (0.04～0.08): (0.35～0.41): (0.04～0.08): 4: (70～72).
3. preparation method according to claim 2 is characterized in that, in the step (3), said still aging temperature is 30～40 ℃, and the time is 16～20h.
4. preparation method according to claim 2 is characterized in that, in the step (4), the temperature of said crystallization is 140～150 ℃, and the time is 110～130h.
5. preparation method according to claim 2 is characterized in that, in the step (4), said incinerating temperature is 500～550 ℃, and the time is 5～8h.
6. according to the described preparation method of one of claim 1 ~ 5, it is characterized in that Si/Al=16 of the Beta zeolite molecular sieve of said hierarchical porous structure.
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| CN103193247A (en) * | 2013-03-09 | 2013-07-10 | 淮南师范学院 | Method for directly preparing composite porous zeolite molecular sieve ball |
| CN103449466A (en) * | 2013-08-23 | 2013-12-18 | 华南理工大学 | Preparation method of MFI micro-mesoporous lamellar molecular sieve with different interlayer spacings |
| WO2015024379A1 (en) * | 2013-08-20 | 2015-02-26 | 中国科学院大连化学物理研究所 | Method for preparing beta molecular sieve having mesoporous/microporous combined channel |
| CN104402020A (en) * | 2014-08-07 | 2015-03-11 | 华南理工大学 | Micro-mesoporous beta molecular sieve and preparation method and application thereof |
| CN105435838A (en) * | 2015-11-05 | 2016-03-30 | 太原理工大学 | T-L composite molecular sieve and preparation method thereof |
| CN106672992A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Beta zeolite and preparation method thereof |
| CN108455629A (en) * | 2018-04-19 | 2018-08-28 | 华南理工大学 | The method that one step of trident rigidity quaternary ammonium salt. template is oriented to synthesis multi-stage porous Beta molecular sieves |
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| CN109534358A (en) * | 2018-12-12 | 2019-03-29 | 华南理工大学 | A kind of hollow multi-stage porous Beta molecular sieve and its preparation method and application |
| CN110621401A (en) * | 2017-05-17 | 2019-12-27 | 沙特阿拉伯石油公司 | Zeolites, their production and their use for upgrading heavy oils |
| CN115893443A (en) * | 2022-11-09 | 2023-04-04 | 成都中科凯特科技有限公司 | Preparation method and application of multistage Kong molecular sieve |
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| WO2015024382A1 (en) | 2013-08-20 | 2015-02-26 | 中国科学院大连化学物理研究所 | Beta molecular sieve having multi-level channel structure, and preparation method thereof |
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| CN103449466A (en) * | 2013-08-23 | 2013-12-18 | 华南理工大学 | Preparation method of MFI micro-mesoporous lamellar molecular sieve with different interlayer spacings |
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| CN105435838A (en) * | 2015-11-05 | 2016-03-30 | 太原理工大学 | T-L composite molecular sieve and preparation method thereof |
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| CN106672992B (en) * | 2015-11-11 | 2018-07-03 | 中国石油化工股份有限公司 | A kind of Beta zeolites and preparation method thereof |
| CN106672992A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Beta zeolite and preparation method thereof |
| CN110621401A (en) * | 2017-05-17 | 2019-12-27 | 沙特阿拉伯石油公司 | Zeolites, their production and their use for upgrading heavy oils |
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| CN109534358A (en) * | 2018-12-12 | 2019-03-29 | 华南理工大学 | A kind of hollow multi-stage porous Beta molecular sieve and its preparation method and application |
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Application publication date: 20121219 |