CN107954432B - Preparation method of oriented AFI molecular sieve membrane - Google Patents
Preparation method of oriented AFI molecular sieve membrane Download PDFInfo
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- CN107954432B CN107954432B CN201610898393.1A CN201610898393A CN107954432B CN 107954432 B CN107954432 B CN 107954432B CN 201610898393 A CN201610898393 A CN 201610898393A CN 107954432 B CN107954432 B CN 107954432B
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- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
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Abstract
The invention relates to a preparation method of an oriented AFI molecular sieve membrane. Mainly solves the problems that the prior oriented molecular sieve membrane is difficult to effectively control the oriented growth in the preparation technology and cannot be prepared in a large scale. The invention prepares the aluminum-containing, phosphorus-containing species and amine compound into a mixed solution, and prepares a reverse microemulsion (water-in-oil type) on the basis, and adds a high molecular polymer into the microemulsion; the technical scheme of carrying out hydrothermal crystallization treatment and roasting the product for 6-48 hours at 500-800 ℃ to obtain the highly oriented AFI molecular sieve membrane well solves the problem and can be used for industrial production of preparing the highly oriented AFI molecular sieve membrane.
Description
Technical Field
The invention relates to a preparation method of a highly oriented AFI molecular sieve membrane
Background
The molecular sieve membrane as a microporous polycrystalline inorganic membrane has a regular pore channel structure, good chemical stability, mechanical strength, thermal stability and catalytic performance (Xuren, Powen Qin, in Jihong). Chemistry of molecular sieves and porous materials, Beijing: scientific publishing house, 2004], has potential application value in the fields of membrane separation technology and membrane catalytic reaction, etc., and has become a hotspot of research and development in academia and industry [ engineering, chaulmoogra, wanhui Lin. < chemical evolution >,2004, 16, 61-67 ]. Microporous molecular sieve membranes such as MFI-type, LTA-type, FAU-type, CHA-type, MOR-type, and AFI-type, which are currently mainly studied, are known in terms of the crystal structure types of molecular sieves [ Caro J, Noack M. < micropor.mesopor.mat. >,2008,115, 215-. Because the microporous molecular sieve has a unique nano-pore structure, the effective pore diameter can be adjusted in a range of several nanometers, and the microporous molecular sieve is very suitable for adsorbing and catalyzing a plurality of important industrial raw materials [ Lai Z P, Tsapatsis M, Nicolich J R. < adv.Funct.Mater. >,2004,14,716-729 ]; and the molecular sieve has good thermal stability, acid resistance, hydrothermal stability and excellent catalytic performance.
AFI is a member of the APO-n family of molecular sieves of aluminophosphate molecular sieves whose framework is made of AlO4And PO4Two tetrahedrons. Because the electric quantity of the two tetrahedrons is equal, the framework of the molecular sieve has no ion exchange property but has the pore canal characteristic, and the molecular sieve is an effective electrocatalystSupport and confinement materials [ Fuerte A, Corma A, Iglesias M.<J Mol Catal A:Chem>,2006,246,109-117]. The molecular sieve membrane is synthesized by a plurality of methods, including an in-situ hydrothermal method, a secondary growth method, a gas phase transfer method, a microwave synthesis method and new synthesis technologies, such as an electrophoresis method, a plasma-assisted synthesis method and the like. Different preparation methods have a large influence on the performance of the membrane. In the preparation research of the molecular sieve membrane, the orientation control of crystals is a hot topic, and the large-scale preparation of the molecular sieve membrane with high orientation degree has the problems of extremely harsh preparation conditions, complex post-treatment and the like. The preparation of highly oriented AFI molecular sieve membranes presents significant challenges, and conventional synthetic methods limit the development and industrial application of oriented AFI molecular sieve membranes.
Disclosure of Invention
The invention aims to solve the technical problems of difficult effective control of oriented growth, harsh preparation conditions and complex post-treatment in the prior art, and provides a novel preparation method of a highly oriented AFI molecular sieve membrane. The method has the advantages of good film forming orientation and simple and controllable preparation process; low requirement on preparation conditions and the like.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method of making an oriented AFI molecular sieve membrane comprising the steps of:
1) mixing an aluminum source, a phosphorus source, a template agent, water, a surfactant and an organic solvent to prepare a water-in-oil type microemulsion;
2) adding a high molecular monomer into the microemulsion;
3) coating on a carrier, and carrying out hydrothermal crystallization treatment;
4) and roasting to obtain the highly oriented AFI molecular sieve membrane.
In the technical scheme, the aluminum source, the phosphorus source, the template agent, water, the surfactant and the organic solvent are in a molar ratio of 1: 1-5: 100-500; preferably 1:2:2:400:400: 800.
In the technical scheme, the mass ratio of the high-molecular monomer to the microemulsion is 1: 1-20; preferably 1: 10; more preferably 1: 5.
In the above technical scheme, the polymer monomer is a non-volatile olefin polymerization monomer; styrene is preferred.
In the technical scheme, in the water-in-oil microemulsion, an aluminum source, a phosphorus source and a template agent are in a water phase. Preferably, an aluminum source, a phosphorus source, an amine compound and water are prepared into a mixed solution, and then the mixed solution is mixed with a template agent, a surfactant and an organic solvent to prepare the water-in-oil microemulsion.
In the technical scheme, the aluminum source is a water-soluble aluminum-containing compound; preferably, the aluminum source comprises at least one selected from the group consisting of aluminum chloride, aluminum sulfate, sodium metaaluminate, and aluminum isopropoxide.
In the technical scheme, the phosphorus source is a water-soluble phosphorus-containing compound; preferably, the source of phosphorus is a water soluble phosphate or phosphoric acid; more preferably, the water-soluble phosphate is sodium dihydrogen phosphate.
In the technical scheme, the template agent is a water-soluble amine compound; preferably, an organic amine; more preferably, triethylamine or methylamine.
In the technical scheme, the surface activity comprises at least one of amine compounds, sulfonate and quaternary ammonium compounds selected from C8-C18; preferably, the amine compound of C8-C18 is tri-n-octylamine, the sulfonate is sodium dodecyl sulfate, and the quaternary ammonium compound is cetyl trimethyl ammonium bromide.
In the above technical solution, the organic solvent in the microemulsion comprises at least one selected from toluene and C4-C8 alkane.
In the technical scheme, the crystallization temperature is 100-280 ℃; preferably, the crystallization temperature is 180 ℃.
In the technical scheme, the roasting temperature is 500-800 ℃, and the roasting time is 6-48 h; preferably, the firing temperature is 550 ℃.
In the above technical solution, the carrier is any carrier that can be used for preparing a molecular sieve membrane, for example, aluminum oxide, and the coating manner is a conventional method that can be used for preparing a molecular sieve membrane.
The invention also provides the AFI molecular sieve membrane prepared by the method.
Here, the mixed aqueous solution of aluminum source-phosphorus source-template agent is both the growth source of the AFI molecular sieve and the aqueous phase of the microemulsion. The growth of the AFI molecular sieve crystal is limited by a microemulsion system of water phase-surfactant (sodium dodecyl sulfate) -oil phase (organic solvent), a high-molecular polymerization monomer is polymerized into a network structure in the oil phase in the hydrothermal crystallization process, and the growth of the AFI crystal in the direction is retarded by adsorption on different crystal faces. The crystal growth orientation of the AFI molecular sieve membrane can be effectively controlled by adjusting the content of the polymerized monomer in the microemulsion. Namely, under the condition of low polymer content, the AFI molecular sieve grows into a lamellar structure; under the condition of medium polymer content, the AFI molecular sieve and an aluminum phosphate dense phase form a mixed crystal blocky structure; in the case of high polymer content, the AFI molecular sieve has a vertically grown structure; at too high a polymer content, the AFI molecular sieve has a secondary growth hierarchical structure. By using the method, AFI molecular sieves with different surface orientations can be successfully prepared by simply modulating the content of the polymer monomer in the whole process. The solvent can be repeatedly used, the reaction cost is reduced, and a better technical effect is achieved.
Figures and description
FIG. 1 is a Scanning Electron Microscope (SEM) picture of the prepared high-orientation AFI molecular sieve membrane in example 1.
Fig. 2 is an XRD spectrum of the prepared high-orientation AFI molecular sieve membrane of example 1.
FIG. 3 is a Scanning Electron Microscope (SEM) picture of the prepared highly oriented AFI molecular sieve membrane in comparative example 1.
FIG. 4 is a Scanning Electron Microscope (SEM) picture of the prepared highly oriented AFI molecular sieve membrane in comparative example 5.
Detailed Description
[ example 1 ]
The preparation of the highly oriented AFI molecular sieve membrane comprises the following steps: 1) preparing aluminum isopropoxide, phosphoric acid and triethylamine into a mixed solution, wherein the molar ratio is 0.8 aluminum isopropoxide: 1.0 phosphoric acid: 0.6 Triethylamine: 50 parts of water; 2) on the basis, a reverse microemulsion (water-in-oil type) is prepared, and the mass ratio of toluene to water is 7.0: 2.0 sodium dodecyl sulfate: 1.0 aqueous solution; 3) adding high molecular monomer into the microemulsion, wherein the mass ratio of the microemulsion to the microemulsion is 5.0: 1.0 styrene monomer; 4) coating on an alumina carrier, and carrying out hydrothermal crystallization treatment at 180 ℃ for 24 hours; 5) and centrifugally separating the obtained product, and roasting for 6 hours at 550 ℃ to obtain the highly oriented AFI molecular sieve membrane.
[ examples 2 to 6 ]
According to the preparation conditions and steps of example 1, the water-oil ratio of the microemulsion, the types of organic solvents, the reaction temperature and the reaction time are changed, and highly oriented AFI molecular sieve membranes with different length-diameter ratios can be obtained, and the specific results are listed in a table.
[ COMPARATIVE EXAMPLES 1 to 5 ]
AFI molecular sieve membranes of different surface orientations and morphologies were obtained by varying the amount of styrene monomer added according to the procedure of example 1.
As shown in the SEM photographs of fig. 1, 3, 4, in fig. 1, the addition of a suitable medium content of styrene imparts a high degree of orientation to the AFI zeolite membrane, with the crystals growing almost entirely in a vertical substrate; in fig. 3, the addition of a small amount of styrene makes the AFI molecular sieve present a lamellar structure; in FIG. 4, the addition of excess styrene resulted in secondary growth of AFI molecular sieve crystals in the radial form. Fig. 2 XRD diffraction spectrum of highly oriented AFI molecular sieve membrane, the high intensity of the 002 diffraction peak is a good explanation of the high orientation of AFI molecular sieve membrane.
The results of the specific examples and comparative examples are summarized in the following table.
Claims (10)
1. A method of making an oriented AFI molecular sieve membrane comprising the steps of:
1) mixing an aluminum source, a phosphorus source, a template agent, water, a surfactant and an organic solvent to prepare a water-in-oil type microemulsion; in the water-in-oil microemulsion, an aluminum source, a phosphorus source and a template agent are in a water phase;
2) adding a high molecular monomer into the microemulsion; the high molecular monomer is a non-volatile olefin polymerization monomer;
3) coating on a carrier, and carrying out hydrothermal crystallization treatment;
4) roasting to obtain a highly oriented AFI molecular sieve membrane;
the mass ratio of the high-molecular monomer to the microemulsion is 1: 1-20.
2. The method of preparing an oriented AFI molecular sieve membrane of claim 1 wherein the aluminum source, the phosphorous source, the templating agent, water, the surfactant, the organic solvent are present in a molar ratio of 1: 1-5: 100-500.
3. The method of making an oriented AFI molecular sieve membrane of claim 1 wherein the non-volatile olefin polymerizing monomer is styrene.
4. The method of preparing an oriented AFI molecular sieve membrane of claim 1 wherein the aluminum source is a water soluble aluminum containing compound; the phosphorus source is a phosphorus-containing compound soluble in water; the template agent is a water-soluble amine compound.
5. The method of preparing an oriented AFI molecular sieve membrane according to claim 1 wherein the aluminum source comprises at least one member selected from the group consisting of aluminum chloride, aluminum sulfate, sodium metaaluminate, and aluminum isopropoxide; the phosphorus source is water-soluble phosphate or phosphoric acid; the template agent is organic amine; the surface activity comprises at least one of amine compounds, sulfonate and quaternary ammonium compounds selected from C8-C18.
6. The method of making an oriented AFI molecular sieve membrane of claim 5 wherein the organic amine is triethylamine or methylamine; the amine compound of C8-C18 is tri-n-octylamine, the sulfonate is sodium dodecyl sulfate, and the quaternary ammonium compound is cetyl trimethyl ammonium bromide.
7. The method of preparing an oriented AFI molecular sieve membrane according to claim 1 wherein the organic solvent in the microemulsion comprises at least one selected from the group consisting of toluene, C4-C8 alkanes.
8. The method of preparing an oriented AFI molecular sieve membrane of claim 1 wherein the crystallization temperature is 100 to 280 ℃.
9. The method for preparing an oriented AFI molecular sieve membrane according to claim 1, wherein the baking temperature is 500-800 ℃ and the baking time is 6-48 h.
10. An AFI molecular sieve membrane prepared according to the process of any of claims 1 to 9.
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