CN107954448B - mesoporous-SAPO-34 molecular sieve with through pore canals and preparation method thereof - Google Patents
mesoporous-SAPO-34 molecular sieve with through pore canals and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a through-channel mesoporous-SAPO-34 molecular sieve and a preparation method thereof. Mainly solves the problems that micropores and mesoporous channels of the prior art cannot be completely communicated when the mesoporous-SAPO-34 molecular sieve is prepared, the mesoporous channels are easy to collapse and the like. The invention adopts the technical scheme that the microemulsion rich in silicon/aluminum/phosphorus/SAPO-34 template agent/structure directing agent is dipped in the mesoporous molecular sieve by adopting a secondary treatment method, the proper pH value is adjusted, the SAPO-34 molecular sieve is epitaxially grown on the inner surface of the mesoporous molecular sieve by secondary crystallization at a certain temperature, and then the mesoporous SAPO-34 molecular sieve with a straight-through type is generated, and the method can be used for preparing various straight-through mesoporous molecular sieves in industrial production.
Description
Technical Field
The invention relates to a through-channel mesoporous-SAPO-34 molecular sieve and a preparation method thereof.
Background
The SAPO-34 molecular sieve belongs to the microporous molecular sieve series and belongs to chabazite, and the framework of the SAPO-34 molecular sieve mainly comprises silicon-aluminum-phosphorus-oxygen, and has a CHA cage and a three-dimensional cross channel structure which are formed by double six-membered rings, eight-membered rings and four-membered rings. SAPO-34 has high selectivity, high hydrothermal stability, suitable acidity, and excellent catalytic performance in MTO reaction. The SAPO-34 molecular sieve was first developed by United states carbide (UCC) in 1984, and was prepared by crystallization at 100-180 ℃ for 6h-10 days using triethylamine 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 pore SAPO-34 molecular sieve is to add a microporous template agent for promoting formation of an SAPO-34 framework and a mesoporous template for inducing 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 serving as soft templates, organosilane of amphiphilic molecules and the like; van Binsan et al (proceedings of materials science and engineering, 2015, 33, 382) prepared mesoporous SAPO-34 molecular sieves by introducing a silane coupling agent KH 550; yang et al induced synthesis of mesoporous SAPO-34 molecular sieve (s.t.yang et al, j.mater.res.ball.2012, 47,3888) by microwave; askari (Askari et al, j. mater. res. bull,2013,48,1851) et al used the Taguchi method to form SAPO-34 molecular sieves with mesoporous distribution with nano-SAPO-34 crystallites stacked. 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 SAPO-34 are prepared by the various methods, the mesoporous SAPO-34 with directly communicated micropores and mesopores has been researched to find out hot spots and difficulties, and the reported method has the disadvantages of complicated preparation process, extremely high cost due to the introduction of more expensive surfactants, complicated large-size template agents 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 SAPO-34 with direct communication still has great challenges, and the development and industrial application of the straight-through mesoporous SAPO-34 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 and poor straight-through property of the obtained mesoporous SAPO-34 molecular sieve in the prior art, and provides a novel straight-through mesoporous SAPO-34 molecular sieve. The method has the advantages of simple post-treatment process; the preparation cost is low, and any mesoporous molecular sieve can be directly communicated; the method is environment-friendly, and the microemulsion is completely impregnated, so that zero discharge of waste liquid is realized; the obtained mesoporous SAPO-34 achieves the characteristics of true micropore-mesoporous unbounded communication and the like.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a through mesoporous-SAPO-34 molecular sieve is characterized in that a through pore channel along the b-direction is spontaneously constructed in a pore channel of a mesoporous molecular sieve, and the through pore channel along the b-direction is oriented in parallel with the mesoporous pore channel.
In the technical scheme, the mesoporous molecular sieve is selected from at least one of SBA and MCM with pore diameters of 2-10 nanometers, and has a through pore.
In the technical scheme, the mesoporous molecular sieve is selected from SBA and MCM with pore diameters of 2-8 nanometers and has a straight-through pore channel.
In the technical scheme, the mesoporous molecular sieve is SBA-15 or MCM-41 or MCM-48.
In the technical scheme, a more preferable technical scheme is that the mesoporous molecular sieves are SBA-15 and MCM-48, wherein the mass ratio of the SBA-15 to the MCM-48 is 1-2: 1
The invention also provides a preparation method of the straight-through mesoporous SAPO-34 molecular sieve, which comprises the following steps:
a) synthesizing a mesoporous molecular sieve, wherein the size of a pore channel is adjusted by a surfactant;
b) mixing a template agent, a surfactant, water, an aluminum source, a silicon source and an organic solvent to prepare SAPO-34 molecular sieve microemulsion;
c) dipping the prepared SAPO-34 molecular sieve microemulsion into the mesoporous molecular sieve in the step a) to obtain a precursor A;
d) slowly crystallizing the SAPO-34 microemulsion in the mesoporous molecular sieve at a temperature of 95-255 ℃ and under a certain pressure to obtain the mesoporous-SAPO-34 molecular sieve;
e) roasting the obtained product for 1-70 hours at the temperature of 310-590 ℃ to obtain the straight-through mesoporous-SAPO-34 molecular sieve.
In the technical scheme, the surfactant is selected from amphiphilic polyether and amine compounds of C8-C18.
In the above technical solution, the organic solvent is at least one selected from benzene, toluene, and an alkane having 6 or more carbon atoms.
The silicon source comprises at least one of tetraethoxysilane, tetrabutyl orthosilicate, white carbon black and water glass;
the aluminum source comprises at least one selected from aluminum isopropoxide, aluminum nitrate and boehmite.
The silicon source is as follows: an aluminum source: the molar ratio of the template agent is 10 (1-8) to (1-4); the molar ratio of the organic solvent, the surfactant and the water is (2-18): 1-9): 1.
The mass ratio of the SAPO-34 molecular sieve microemulsion to the mesoporous molecular sieve is 1: 0.5-5.
In the above technical solution, it is more preferable that the organic solvent and the surfactant are selected from trimethylbenzene and n-octylamine.
In the technical scheme, the SAPO-34 molecular sieve microemulsion is a water-in-oil microemulsion.
In the technical scheme, in the SAPO-34 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 technical scheme, the crystallization temperature is 95-210 ℃, and the reaction time is 6-40 h.
By adopting the technical scheme of the invention, as the method of epitaxial growth on the inner wall of the mesoporous molecular sieve is used, during crystallization, a part of mesoporous pore wall is used as a silicon source to enter a microporous structure, so that seamless connection between the microporous pore wall and the mesoporous pore wall is realized; in the crystallization process, SAPO-34 slowly grows on the inner wall of the round mesoporous in the a-, c-direction in an LBL mode, and finally a straight pore channel in the b-direction is spontaneously constructed in the mesoporous pore channel, and the straight pore channel and the mesoporous pore channel in the direction are oriented in parallel and are shorter than the mesoporous pore channel, so that a directly communicated micropore-mesoporous part is formed. The N, O-containing template agent and the guiding agent are removed by roasting, and a very uniform meso-microporous communicated structure is generated. Because the whole process adopts a complete infiltration method, the microemulsion of the SAPO-34 has no redundant part which needs to be discharged, 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 a straight-through mesoporous SAPO-34 molecular sieve prepared at 150 ℃ in example 1. In the figure, dense micropore channels with apparent 0.4nm and relatively loose mesopore channels with apparent 2.1nm are arranged in parallel, and the non-boundary communication between the micropore and the mesopore part is clearly revealed, which is shown in detail in figure 1. FIG. 1 is a high resolution electron micrograph of a straight through mesoporous SAPO-34 molecular sieve. FIG. 1-1 is a microporous-mesoporous through-channel structure of an SAPO-34 molecular sieve; fig. 1-2 are fourier transform diagrams corresponding to the red boxes in fig. 1, which are identical to XRD results, and indicate that the microporous-mesoporous channels are arranged in parallel.
FIG. 2 is a small angle and wide angle X-ray diffraction pattern of the straight-through mesoporous SAPO-34 molecular sieve prepared under the condition of 150 ℃ in example 1. 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 SAPO-34.
FIG. 3 is a schematic diagram of a through-channel mesopore of a molecular sieve.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
The preparation of the straight-through mesoporous SAPO-34 molecular sieve comprises the following steps: firstly, preparing SAPO-34 water-in-oil microemulsion, taking an aqueous solution prepared from Triethylamine (TEA), phosphoric acid 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 a clear microemulsion I. Si in microemulsion I: al: the molar ratio of TEA was 1: 1: 3; the molar ratio of toluene to tri-n-octylamine to water is 2: 1: 1; under the normal temperature condition, the microemulsion I and the baked SBA-15 molecular sieve with the pore canal diameter of 4-8 nanometers are mixed according to the mass ratio of 0.5: 1 impregnation gives precursor II. Aging at 60 ℃ for 1 hour, then loading the precursor II into a stainless steel reaction kettle, and crystallizing at 180 ℃ for 48 hours to obtain the template-containing mesoporous SAPO-34 molecular sieve. After the product is taken out, the product is roasted for 6 hours at the temperature of 550 ℃ to obtain the mesoporous-SAPO-34 molecular sieve with the through pore channel, wherein the pore ratio of the mesoporous molecular sieve to the SAPO-34 molecular sieve is 1.3. The data are detailed in table 1.
[ example 2 ]
The preparation of the straight-through mesoporous SAPO-34 molecular sieve comprises the following steps: firstly, preparing SAPO-34 water-in-oil microemulsion, taking an aqueous solution prepared from Triethylamine (TEA), phosphoric acid 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 a clear microemulsion I. Si in microemulsion I: al: the molar ratio of TEA was 1: 1: 3; the molar ratio of toluene to tri-n-octylamine to water is 2: 1: 1; under the normal temperature condition, the microemulsion I and the roasted hexagonal MCM-41 with the molecular sieve pore diameter of 2-6 nanometers are mixed according to the mass ratio of 0.5: 1 impregnation gives precursor II. Aging at 60 ℃ for 1 hour, then loading the precursor II into a stainless steel reaction kettle, and crystallizing at 180 ℃ for 48 hours to obtain the template-containing mesoporous SAPO-34 molecular sieve. And (3) taking out the product, and roasting for 6 hours at 550 ℃ to obtain the straight-through mesoporous SAPO-34 molecular sieve. Wherein the pore ratio of the mesoporous molecular sieve to the SAPO-34 molecular sieve is 1.25. The data are detailed in table 1.
[ example 3 ]
The preparation of the straight-through mesoporous SAPO-34 molecular sieve comprises the following steps: firstly, preparing SAPO-34 water-in-oil microemulsion, taking an aqueous solution prepared from Triethylamine (TEA), phosphoric acid 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 a clear microemulsion I. Si in microemulsion I: al: the molar ratio of TEA was 1: 1: 3; the molar ratio of toluene to tri-n-octylamine to water is 2: 1: 1; under the condition of normal temperature, the microemulsion I and the calcined mesoporous molecular sieve are mixed according to the mass ratio of 0.5: 1 to obtain a precursor II, wherein the mesoporous molecular sieve is a cubic MCM-48 molecular sieve with the pore canal diameter of 2-4 nanometers. Aging at 60 ℃ for 1 hour, then loading the precursor II into a stainless steel reaction kettle, and crystallizing at 180 ℃ for 48 hours to obtain the template-containing mesoporous SAPO-34 molecular sieve. And (3) taking out the product, and roasting for 6 hours at 550 ℃ to obtain the straight-through mesoporous SAPO-34 molecular sieve. The pore ratio of the mesoporous molecular sieve to the SAPO-34 molecular sieve is 1.1. The data are detailed in table 1.
[ COMPARATIVE EXAMPLES 1 to 2 ]
According to the method of example 1, only by changing the water-oil balance of the microemulsion, the mesoporous SAPO-34 molecular sieve can be obtained, but the pore channels are not communicated. See Table 2 for details
TABLE 1
| Examples | 1 | 2 | 3 |
| Synthesis temperature (℃) | 180 | 180 | 180 |
| Reaction time (h) | 48 | 48 | 48 |
| Firing temperature (℃) | 550 | 550 | 550 |
| Mesoporous molecular sieve type | SBA-15 | MCM-41 | MCM-48 |
| Specific surface area (m)2/g) | 370 | 330 | 300 |
| Whether to go straight through | Is that | Is that | Is that |
| Meso/micro (pore ratio) | 1.3 | 1.25 | 1.1 |
TABLE 2
| Comparative example | 1 | 2 |
| Synthesis temperature (℃) | 180 | 180 |
| Reaction time (h) | 48 | 48 |
| Firing temperature (℃) | 550 | 550 |
| Microemulsion type | Continuous water and oil | Oil-in-water |
| Presence or absence of mesopores and SAPO-34 | Is that | Is that |
| Whether or not to communicate | Is not | Is not |
Claims (8)
1. A preparation method of a through-channel mesoporous-SAPO-34 molecular sieve is characterized by comprising the following steps:
a) synthesizing a mesoporous molecular sieve, wherein the size of a pore channel is adjusted by a surfactant;
b) mixing a template agent, a surfactant, water, an aluminum source, a silicon source and an organic solvent to prepare SAPO-34 molecular sieve microemulsion;
c) dipping the microemulsion of the SAPO-34 molecular sieve prepared in the step b) into the mesoporous molecular sieve prepared in the step a) to obtain a precursor A;
d) slowly crystallizing the SAPO-34 microemulsion in the mesoporous molecular sieve at the temperature of 95-255 ℃ to obtain a mesoporous-SAPO-34 molecular sieve;
e) roasting the obtained product for 1 to 70 hours at the temperature of between 310 and 590 ℃ to obtain a through type mesoporous-SAPO-34 molecular sieve;
wherein the silicon source: an aluminum source: the mol ratio of the template agent is 10: (1-8): (1-4); the molar ratio of the organic solvent to the surfactant to the water is (2-18): (1-9): 1; the SAPO-34 molecular sieve microemulsion and the mesoporous molecular sieve are mixed according to the mass ratio of 1:0.5 to 5; the surfactant is at least one selected from amphiphilic polyether and amine compounds of C8-C18; the mesoporous molecular sieve is at least one of SBA and MCM.
2. The preparation method of the through hole channel mesoporous-SAPO-34 molecular sieve according to claim 1, wherein the crystallization temperature is 95-210 ℃ and the crystallization time is 6-40 h.
3. The method for preparing the through-channel mesoporous-SAPO-34 molecular sieve of claim 1, wherein the organic solvent is at least one selected from benzene, toluene and alkanes having 6 or more carbon atoms.
4. The method for preparing the through-channel mesoporous-SAPO-34 molecular sieve according to claim 1, wherein the silicon source is at least one selected from the group consisting of ethyl orthosilicate, butyl orthosilicate, white carbon black and water glass; the aluminum source is selected from at least one of aluminum isopropoxide, aluminum nitrate and boehmite.
5. A through-channel mesoporous-SAPO-34 molecular sieve prepared according to any of claims 1 to 4, wherein the SAPO-34 molecular sieve spontaneously forms through channels in the b-direction within the mesoporous molecular sieve channels, and the through channels in the b-direction are oriented parallel to the mesoporous channels.
6. The mesoporous-SAPO-34 molecular sieve with straight-through pores according to claim 5, wherein the mesoporous molecular sieve is selected from at least one of SBA and MCM with pore diameters of 2-10 nm and has straight-through pores.
7. The mesoporous-SAPO-34 molecular sieve with straight-through pores according to claim 5, wherein the mesoporous molecular sieve is selected from at least one of SBA and MCM with pore diameters of 2-8 nm and has straight-through pores.
8. The through-channel mesoporous-SAPO-34 molecular sieve of claim 5, wherein the ratio of the pores of the mesoporous molecular sieve to the pores of the SAPO-34 molecular sieve is 1.0 to 2.5.
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| CN101121533A (en) * | 2006-08-08 | 2008-02-13 | 中国科学院大连化学物理研究所 | SAPO-34 molecular sieve with micropore and mesopore structure and synthetic method thereof |
| EP2085360A1 (en) * | 2007-12-27 | 2009-08-05 | Chevron USA, Inc. | Synthesis of a crystalline silicoaluminophosphate |
| CN103100399A (en) * | 2011-11-11 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method of mesoporous-microporous composite molecular sieve |
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| CN101121533A (en) * | 2006-08-08 | 2008-02-13 | 中国科学院大连化学物理研究所 | SAPO-34 molecular sieve with micropore and mesopore structure and synthetic method thereof |
| EP2085360A1 (en) * | 2007-12-27 | 2009-08-05 | Chevron USA, Inc. | Synthesis of a crystalline silicoaluminophosphate |
| CN103100399A (en) * | 2011-11-11 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method of mesoporous-microporous composite molecular sieve |
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| ZSM-5/SAPO-34复合分子筛的制备与甲醇芳构化性能研究;刘占宇等;《应用化工》;20141130;第43卷(第11期);第1977页摘要、第1978页"1 实验部分"和第1979页"2.3 SEM表征" * |
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