CN107954438B - Straight-through mesoporous FAU molecular sieve and preparation method thereof - Google Patents
Straight-through mesoporous FAU molecular sieve and preparation method thereof Download PDFInfo
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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
- 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
- C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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Abstract
The invention relates to a straight-through mesoporous FAU molecular sieve and a preparation method thereof. Mainly solves the problems that micropore-mesopore channels can not be completely communicated when the mesoporous FAU molecular sieve is prepared by the prior art, the mesopore channels are easy to collapse and the like. The invention adopts a secondary treatment method to dip the microemulsion rich in the silicon/aluminum/FAU template agent in the mesoporous molecular sieve, and the FAU molecular sieve is epitaxially grown on the inner surface of the mesoporous molecular sieve through secondary crystallization, thereby generating the mesoporous FAU molecular sieve with a straight-through type. The method perfectly solves the problems mentioned above, and the method can be used for industrial production of various straight-through mesoporous molecular sieves.
Description
Technical Field
The invention relates to a straight-through mesoporous FAU molecular sieve and a preparation method thereof.
Background
The FAU structure molecular sieve belongs to the microporous molecular sieve series, belongs to the octahedra class, and comprises an X type and a Y type with low silica-alumina ratio. The framework of the composite material mainly comprises aluminosilicate and has a secondary structure of double six-membered rings and beta cages, and the beta cages are connected through the double six-membered rings to form a three-dimensional open framework structure. The Y-type with high Si/Al ratio has high selectivity, high hydrothermal stability and proper acidity. In the 60 th of the 20 th century, Linde company was used for catalytic cracking for the first time, and the Linde company shows excellent catalytic cracking performance in the subsequent FCC reaction, so that the Linde catalyst is widely applied to various industrial enterprises. The FAU molecular sieve is prepared by crystallizing for 6h-10d at 100-180 ℃ by using sodium hydroxide or tetrapropylammonium bromide and the like as a structure directing agent. The active center of the microporous molecular sieve is mostly in the pore canal. The longer main pore canal of the molecular sieve can increase the diffusion resistance of molecules in the pore canal, so that the target product molecules can not diffuse out of the pore canal in time and finally generate secondary reaction to generate other molecules. Therefore, it is important to shorten the diffusion path and reduce the diffusion resistance. Mesopores are introduced into one microporous molecular sieve crystal to reduce diffusion resistance and accelerate diffusion: that is, the synthesis of the molecular sieve material with the microporous-mesoporous composite hierarchical pore structure has become a hot point of current research. A common method for synthesizing a hierarchical porous FAU molecular sieve is to add a microporous template agent for promoting the formation of the FAU framework and a mesoporous template for inducing the formation of mesopores in a synthesis system, wherein the mesoporous template comprises carbon black particles, carbon nanotubes, carbon aerogel, polysaccharide compounds and the like serving as hard templates, cationic polymers and organosilane of amphiphilic molecules serving as soft templates and the like; garcia-Martinez et al (j.garcia-Martinez et al, cat. sci & tech, 2012, 2, 987) prepare mesoporous FAU molecular sieves by introducing cetyltrimethylammonium bromide (CTAB) with secondary growth of Y small crystallites; song et al synthesized mesoporous FAU molecular sieves by adding starch during synthesis (Song Li Juan et al, Petroleum technology and applications, 2015,33, 288); he (he Long et al, "college of higher schools of petrochemical industry", 2015,28,31) and the like adopt an alkaline solution etching method to prepare the mesoporous FAU molecular sieve. Although the above method can obtain the mesoporous distribution, the use of the mesoporous template not only increases the cost but also complicates the synthesis step, and is not suitable for industrialization. In addition, although the mesoporous molecular sieves of FAU are prepared by the above methods, mesoporous FAU with directly communicated micropores and mesopores has been researched to find out hot spots and difficulties, and the reported methods have the disadvantages of complicated preparation process, high cost due to the introduction of more expensive surfactants, complicated large-size templates and the like, complicated post-treatment and environmental pollution. Or, the resulting multiwell bore is not in true sense in direct communication. Therefore, the preparation of the mesoporous FAU with direct communication still has great challenges, and the development and industrial application of the straight-through mesoporous FAU molecular sieve are limited by the conventional synthesis method.
Disclosure of Invention
The invention aims to solve the technical problems of high cost, low crystallinity of the obtained mesoporous FAU molecular sieve and poor straight-through property in the prior art, and provides a novel preparation method of the straight-through mesoporous FAU molecular sieve. The method has the advantages of simple post-treatment process; the preparation cost is low (any mesoporous molecular sieve can be directly communicated); the method is environment-friendly (the microemulsion is completely impregnated, so that zero discharge of waste liquid is realized); the obtained mesoporous FAU has the characteristics of true microporous and mesoporous unbounded communication and the like.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a straight-through mesoporous FAU molecular sieve is characterized in that micropores in the structure are directly communicated with mesopores, and the micropores are in mesoporous pore channels.
In the technical scheme, micropores in the FAU molecular sieve structure are directly communicated with mesopores in the mesoporous molecular sieve structure, and the micropores exist in the mesopore pore canal.
In the technical scheme, the mesoporous molecular sieve is a mesoporous molecular sieve with straight through channels, preferably SBA or MCM series, and more preferably SBA-15 or MCM-41 or MCM-48.
In the technical scheme, the micropores are seamlessly connected with the wall of the mesoporous pore, and the parallel orientation of the pore canal of the micropores and the pore canal of the mesoporous pore is shorter than that of the mesoporous pore canal, so that a directly communicated micro-mesoporous part is formed.
In the technical scheme, the straight-through mesoporous FAU molecular sieve is prepared by dipping microemulsion containing FAU molecular sieve stock solution into a mesoporous molecular sieve, and crystallizing and roasting the microemulsion.
The invention also provides a preparation method of the straight-through mesoporous FAU molecular sieve, which comprises the following steps:
a) mixing a template agent, a surfactant, water, an aluminum source, a silicon source and an organic solvent to prepare FAU molecular sieve microemulsion;
b) dipping the prepared FAU molecular sieve microemulsion into a mesoporous molecular sieve to obtain a precursor A;
c) crystallizing the FAU molecular sieve microemulsion in a mesoporous molecular sieve at 90-260 ℃ under autogenous pressure to obtain a mesoporous FAU molecular sieve;
d) roasting the obtained product for 0.5 to 72 hours at the temperature of 300 to 600 ℃ to obtain the straight-through mesoporous FAU molecular sieve.
In the technical scheme, the FAU molecular sieve microemulsion is a water-in-oil microemulsion.
In the technical scheme, in the FAU molecular sieve microemulsion, a template agent, a surfactant and water are mixed to form a water phase, a silicon source, an aluminum source and an organic solvent are mixed to form an oil phase, and the water phase and the oil phase are mixed to obtain the microemulsion.
In the above technical solution, the silicon source: an aluminum source: the mol ratio of the template agent is 10: 1-10: 1-3; the molar ratio of the organic solvent to the surfactant to the water is 2-20: 1-10: 1.
in the technical scheme, the mass ratio of the FAU molecular sieve microemulsion to the mesoporous molecular sieve is 1: 0.5-5
In the technical scheme, the mesoporous molecular sieve is a mesoporous molecular sieve with straight through channels.
In the technical scheme, the mesoporous molecular sieve is selected from SBA or MCM series; more preferably, the diameter of the pore channel is 2-8 nanometers.
In the technical scheme, the mesoporous molecular sieve is SBA-15 or MCM-41 or MCM-48.
In the technical scheme, the mesoporous molecular sieve can be synthesized by means of conventional technical means in the field, and the size of the pore channel can be adjusted by the size of the surfactant.
In the above technical scheme, the silicon source comprises at least one selected from ethyl orthosilicate, butyl orthosilicate, white carbon black and water glass; the aluminum source comprises at least one selected from aluminum isopropoxide, aluminum nitrate and boehmite; the organic solvent comprises at least one selected from benzene, toluene and alkane with more than 6 carbon atoms, and in a specific embodiment of the invention, the organic solvent is toluene; the surfactant comprises at least one of amphiphilic molecules of C8-C12, amphiphilic polyether and amine compounds of C8-C18, and in a specific embodiment of the invention, the surfactant is tri-n-octylamine; the template agent is Na2O, NaOH or quaternary ammonium salts, preferably sodium hydroxide or tetrapropylammonium bromide.
In the above technical scheme, the crystallization temperature is 100-; the crystallization time is 6-48h, preferably 24 h.
The invention adopts a microemulsion dipping method, so that the aqueous solution containing the template agent can completely enter the hydrophobic mesoporous pore canal, and the micropore crystallization can be completely carried out in the mesoporous pore canal. Specifically, by using a method of epitaxial growth on the inner wall of the mesoporous molecular sieve, during crystallization, a part of the mesoporous pore wall is used as a silicon source to enter a microporous structure, so that the microporous/mesoporous pore wall is connected seamlessly; in the crystallization process, FAU slowly grows on the inner wall of a round mesopore in an LBL mode, and finally a straight pore channel along the direction of the mesopore pore channel is spontaneously constructed in the mesopore pore channel, and the straight pore channel and the mesopore pore channel in the direction are oriented in parallel and are shorter than the mesopore pore channel, so that a directly communicated micro-mesopore part and a mesopore part are formed. The N, O-containing templating agent was removed by firing, i.e., a very uniform meso/microporous interconnected structure was produced. Because the whole process adopts a complete infiltration method, the FAU microemulsion has no redundant part needing sewage discharge, the reaction cost is greatly reduced, and the method is environment-friendly. And a better technical effect is achieved.
Figures and description
Fig. 1 is a high-resolution transmission electron microscope image of the straight-through mesoporous FAU molecular sieve prepared under the condition of 110 ℃ in the first example. In the figure, compact micropore pore channels with the apparent size of 0.8nm and relatively loose mesopore pore channels with the apparent size of 2nm are arranged in parallel and covered, and the unbounded communication of micropores and mesopore parts is clearly revealed.
FIG. 2 is a small-angle X-ray diffraction pattern of the straight-through mesoporous FAU molecular sieve prepared at 110 ℃ in example I. XRD reveals that the mesoporous part of the material is ordered, and the main diffraction peak of the microporous part is consistent with the main characteristic peak of the standard spectrogram of FAU.
FIG. 3 is a wide-angle X-ray diffraction pattern of the straight-through mesoporous FAU molecular sieve prepared at 110 ℃ in example I. XRD reveals that the mesoporous part of the material is ordered, and the main diffraction peak of the microporous part is consistent with the main characteristic peak of the standard spectrogram of FAU.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
The preparation of the straight-through mesoporous FAU molecular sieve comprises the following steps: firstly, preparing FAU water-in-oil microemulsion, taking an aqueous solution prepared from sodium hydroxide and tri-n-octylamine as a microemulsion water phase, taking a toluene solution of Tetraethoxysilane (TEOS) and aluminum isopropoxide as an oil phase, and mixing the water phase and the oil phase to obtain clear microemulsion I. Si in microemulsion I: al: the molar ratio of NaOH or TPABr is 10: 1: 10; the molar ratio of toluene to tri-n-octylamine to water is 2: 1: 1; under the condition of normal temperature, mixing the microemulsion I and the roasted SBA-15 according to the mass ratio of 0.3: 1 impregnation gives precursor II. Aging at 60 ℃ for 6 hours, then loading the precursor II into a stainless steel reaction kettle, and crystallizing at 110 ℃ for 24 hours to obtain the mesoporous FAU molecular sieve containing the template agent. And (3) taking out the product, and roasting for 6 hours at 550 ℃ to obtain the straight-through mesoporous FAU molecular sieve.
The mesoporous SBA-15 can be synthesized by means of the conventional technical means in the field.
[ examples 2 to 3 ]
According to the method of example 1, the mesoporous and microporous distributions of the straight-through mesoporous FAU molecular sieve can be adjusted by changing the type of the mesoporous molecular sieve, so as to obtain straight-through mesoporous FAU molecular sieves with different mesoporous/microporous pore ratios.
The mesoporous MCM series may be synthesized by means conventional in the art.
[ example 4 ]
The procedure of example 1 was followed except that the surfactant was changed.
[ example 5 ]
The procedure of example 1 was followed except that the templating agent was changed to tetrapropylammonium bromide.
[ example 6 ]
The procedure of example 1 was followed except that the molar ratio of organic solvent to water was changed.
[ COMPARATIVE EXAMPLES 1 to 2 ]
According to the method of example 1, only by changing the water-oil balance of the microemulsion, the mesoporous FAU molecular sieve can be obtained, but the pore channels are not communicated.
The results of the specific examples and the results of the comparative examples are shown in the following table.
Examples 1 to 6
| Examples | 1 | 2 | 3 | 4 | 5 | 6 |
| Synthesis temperature (. degree.C.) | 110 | 110 | 110 | 110 | 110 | 110 |
| Reaction time (h) | 24 | 24 | 24 | 24 | 24 | 24 |
| Calcination temperature (. degree.C.) | 550 | 550 | 550 | 550 | 550 | 550 |
| Mesoporous molecular sieve type | SBA-15 | MCM-41 | MCM-48 | SBA-15 | SBA-15 | SBA-15 |
| Specific surface area (m)2/g) | 310 | 310 | 300 | 290 | 330 | 280 |
| Whether to go straight through | Is that | Is that | Is that | Is that | Is that | Is that |
| Meso/micro (pore ratio) | 1.0 | 0.7 | 0.6 | 0.9 | 1.1 | 0.6 |
| Surface active agent | Tri-n-octylamine | Tri-n-octylamine | Tri-n-octylamine | Octyl phenol | Tri-n-octylamine | Tri-n-octylamine |
| Template agent | Sodium hydroxide | Sodium hydroxide | Sodium hydroxide | Sodium hydroxide | Tetrapropylammonium bromide | Sodium hydroxide |
| Organic solvent/water | 2:1 | 2:1 | 2:1 | 2:1 | 2:1 | 4:1 |
Comparative examples 1 to 2
| Comparative example | 1 | 2 |
| Synthesis temperature (. degree.C.) | 110 | 110 |
| Reaction time (h) | 24 | 24 |
| Calcination temperature (. degree.C.) | 550 | 550 |
| Microemulsion type | Continuous water and oil | Oil-in-water |
| Presence or absence of mesopores and FAU | Is that | Is that |
| Whether or not to communicate | Is not | Is not |
Claims (6)
1. A preparation method of a straight-through mesoporous FAU molecular sieve comprises the following steps:
a) mixing a template agent, a surfactant, water, an aluminum source, a silicon source and an organic solvent to prepare FAU molecular sieve microemulsion;
b) dipping the prepared FAU molecular sieve microemulsion into a mesoporous molecular sieve to obtain a precursor A;
c) crystallizing the FAU molecular sieve microemulsion in a mesoporous molecular sieve at 90-260 ℃ under autogenous pressure to obtain a mesoporous FAU molecular sieve;
d) roasting the obtained product for 0.5 to 72 hours at the temperature of 300 to 600 ℃ to obtain a through type mesoporous FAU molecular sieve;
wherein the silicon source: an aluminum source: the mol ratio of the template agent is 10: 1-10: 1-3; the molar ratio of the organic solvent to the surfactant to the water is 2-20: 1-10: 1; the FAU molecular sieve microemulsion and the mesoporous molecular sieve are mixed according to the mass ratio of 1:0.5 to 5; the mesoporous molecular sieve is selected from SBA or MCM series; the crystallization temperature is 100-180 ℃, and the crystallization time is 6-48 h; the surfactant is selected from two of C8-C12At least one of affinity molecules, amphiphilic polyether and amine compounds of C8-C18; the template agent is Na2O, NaOH or quaternary ammonium salts.
2. The method of preparing a straight-through mesoporous FAU molecular sieve according to claim 1, wherein the FAU molecular sieve microemulsion is a water-in-oil microemulsion.
3. The method for preparing a straight-through mesoporous FAU molecular sieve as claimed in claim 1 or 2, wherein in the FAU molecular sieve microemulsion, the templating agent, the surfactant and the water are mixed into an aqueous phase, the silicon source, the aluminum source and the organic solvent are mixed into an oil phase, and the aqueous phase and the oil phase are mixed to obtain the microemulsion.
4. The method of preparing a straight-through mesoporous FAU molecular sieve of claim 1, wherein the mesoporous molecular sieve is a mesoporous molecular sieve having straight-through channels.
5. The method of claim 1, wherein the silicon source is at least one selected from the group consisting of ethyl orthosilicate, butyl orthosilicate, silica white, and water glass; the aluminum source is selected from at least one of aluminum isopropoxide, aluminum nitrate and boehmite; the organic solvent is at least one selected from benzene, toluene and alkane with more than 6 carbon atoms.
6. The through mesoporous FAU molecular sieve prepared by the method of any of claims 1-5, wherein the micropores of the structure are directly connected with the mesopores, and the micropores are in the mesopore channels.
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