CN109647541B - Three-dimensional mesoporous aluminosilicate catalyst carrier and preparation method thereof - Google Patents
Three-dimensional mesoporous aluminosilicate catalyst carrier and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 229910000323 aluminium silicate Inorganic materials 0.000 title claims abstract description 38
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000011148 porous material Substances 0.000 claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000002244 precipitate Substances 0.000 claims abstract description 12
- -1 aluminum alkoxide Chemical class 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000002073 nanorod Substances 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 claims description 2
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 22
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000001354 calcination Methods 0.000 abstract description 6
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 22
- 239000012876 carrier material Substances 0.000 description 11
- 238000001000 micrograph Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供了一种三维介孔硅铝酸盐催化剂载体及其制备方法。所述三维介孔硅铝酸盐催化剂载体的制备方法包括：(1)配制乙腈水溶液，其中水和乙腈的体积比为0.1：20至5：20；(2)将有机醇铝与乙腈水溶液混合均匀，反应得到液体I；(3)将硅源和步骤(2)得到的液体I混合均匀，反应得到白色沉淀I；(4)将步骤(3)得到的白色沉淀I抽滤洗涤干燥，得到白色粉末II；(5)将步骤(4)得到的白色粉末II焙烧处理，得到所述三维介孔硅铝酸盐催化剂载体。本发明实现了等级孔三维介孔结构在硅铝酸盐催化剂载体中的构筑，改善了材料的流通扩散性能，有效地防止了反应过程中催化剂堵塞，中毒的现象。
The invention provides a three-dimensional mesoporous aluminosilicate catalyst carrier and a preparation method thereof. The preparation method of the three-dimensional mesoporous aluminosilicate catalyst carrier includes: (1) preparing an acetonitrile aqueous solution, wherein the volume ratio of water and acetonitrile is 0.1:20 to 5:20; (2) mixing organic aluminum alkoxide with the acetonitrile aqueous solution evenly, the reaction obtains liquid I; (3) the silicon source and the liquid I obtained in step (2) are mixed uniformly, and the reaction obtains white precipitate I; (4) the white precipitate I obtained in step (3) is filtered, washed and dried to obtain White powder II; (5) calcining the white powder II obtained in step (4) to obtain the three-dimensional mesoporous aluminosilicate catalyst carrier. The invention realizes the construction of the graded pore three-dimensional mesoporous structure in the aluminosilicate catalyst carrier, improves the flow and diffusion performance of the material, and effectively prevents the phenomenon of catalyst blockage and poisoning in the reaction process.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a three-dimensional mesoporous aluminosilicate catalyst carrier and a preparation method thereof.
Background
The catalyst is the core of petrochemical reactions. In fact, catalyst performance is indistinguishable from the development of catalyst support materials. With the development of petrochemical industry, the components of petroleum raw materials are more and more complex, and the requirement of the industry on petroleum catalytic reaction is higher and higher. With the improvement of national requirement standards, a single conventional carrier cannot meet the requirement of a catalyst with high performance. Therefore, it has become one of the trends of catalyst carrier development that a single carrier is compounded by a chemical physical method to prepare a composite oxide carrier, and the advantages of each component are exerted synergistically.
The silicon-aluminum composite oxide carrier is an industrially important catalyst carrier material, and has the advantages of large specific surface area, large pore volume, high mechanical stability, high thermal stability, surface acidity and the like. Therefore, the catalyst is widely applied to a plurality of petrochemical catalytic reactions, particularly catalytic cracking, hydrocracking and the like.
At present, the method for preparing the silicon-aluminum composite oxide mainly comprises the following steps: sol-gel method, precipitation method, hydrothermal synthesis method, mixing method, and the like. Although researchers at home and abroad have made a great deal of basic research and have obtained a series of achievements according to the methods. However, due to the complexity of the preparation process, the difficulty in adjusting parameters in the synthesis process, and the like, the prepared composite carrier material is often accompanied with a plurality of problems. For example: the silicon-aluminum material prepared by a precipitation method or a sol-gel method often adsorbs a plurality of impurities on the surface or forms coating of the impurities in the synthesis process because of strong surface adsorbability, so that poisoning of active sites and the like are caused.
Therefore, it has been desired by scientists to prepare a silicon-aluminum carrier material which has a high specific surface area, hierarchical pores, and cross-through pores, has adjustable pore channel property parameters, and simultaneously satisfies a simple preparation method. Vandadan et al successfully synthesized a macroporous amorphous silica-alumina material (publication No. CN104549540A), the synthesized material has uniform distribution of silica and alumina, high content of silica, and large pore volume and specific surface area. Although this material has good cell properties, the process is too complex. On the basis, the silicon-aluminum carrier material with the through large-hole and mesoporous-hole is successfully synthesized in an acetonitrile aqueous solution system by utilizing the phenomenon that metal organic alkoxide is hydrolyzed and condensed under the water-containing condition to generate alcohol molecules, and the alcohol molecules diffuse outwards to form a pore channel. The macropores in the framework can effectively increase the permeability of the catalyst, prevent pore channels from being blocked and prolong the service life of the catalyst. The mesopores can greatly increase the specific surface area of the material, so that the active component can be fully dispersed on the surface of the catalyst carrier, thereby improving the catalytic efficiency. It is worth mentioning that the method is simple, can be synthesized in one step, and is easy for large-scale production.
Disclosure of Invention
An object of the present invention is to provide a three-dimensional mesoporous aluminosilicate catalyst support;
another object of the present invention is to provide a method for preparing the catalyst carrier.
In order to achieve the above object, in one aspect, the present invention provides a method for preparing a three-dimensional mesoporous aluminosilicate catalyst support, wherein the method comprises the following steps:
(1) preparing an acetonitrile water solution, wherein the volume ratio of water to acetonitrile is 0.1: 20 to 5: 20;
(2) uniformly mixing organic aluminum alkoxide and acetonitrile aqueous solution, and reacting to obtain liquid I;
(3) uniformly mixing a silicon source and the liquid I obtained in the step (2), and reacting to obtain a white precipitate I;
(4) filtering, washing and drying the white precipitate I obtained in the step (3) to obtain white powder II;
(5) and (4) roasting the white powder II obtained in the step (4) to obtain the three-dimensional mesoporous aluminosilicate catalyst carrier.
According to some specific embodiments of the present invention, wherein the organic aluminum alkoxide in the step (2) is selected from one or more of aluminum n-butoxide, aluminum sec-butoxide and aluminum tert-butoxide.
According to some embodiments of the invention, the mass ratio of the added aluminum organoalkoxide to the silicon source is 5: 1 to 20: 1.
according to some embodiments of the present invention, the mass ratio of the aluminum organoalkoxide in the step (2) to the acetonitrile aqueous solution in the step (1) is 1: 2 to 1: 20.
the acetonitrile of the present invention is conventional commercially available acetonitrile, and according to some embodiments of the present invention, the acetonitrile is at least 99.5% acetonitrile by mass.
According to some embodiments of the present invention, wherein the silicon source in step (2) is selected from a mixture of one or more of tetramethoxysilane, tetraethoxysilane and silica sol.
According to some embodiments of the present invention, in the step (2), the organic aluminum alkoxide and the acetonitrile aqueous solution are mixed uniformly and reacted to obtain the liquid I.
According to some embodiments of the present invention, in the step (2), the aluminum alkoxide and the aqueous acetonitrile solution are mixed uniformly and reacted at room temperature to 60 ℃ for 5min to 24 h.
According to some embodiments of the present invention, in step (2), the aluminum alkoxide is added dropwise to the acetonitrile aqueous solution and mixed uniformly.
According to some embodiments of the present invention, in the step (2), the aluminum organylalkoxide is added dropwise to the acetonitrile aqueous solution, and then stirred for 30min to 2h to mix uniformly.
According to some embodiments of the present invention, in step (3), a silicon source is added to the liquid I obtained in step (2) under stirring, and a white precipitate I is obtained.
According to some embodiments of the present invention, step (3) is to add the silicon source dropwise to the liquid I obtained in step (2).
According to some embodiments of the invention, step (3) is carried out at room temperature to 60 ℃ for 5min to 24 h.
According to some embodiments of the present invention, in the step (3), a silicon source is added into the liquid I obtained in the step (2) under stirring, and stirred for 30min to 2h after dropping to mix uniformly, and then reacted to obtain a white precipitate I.
The reaction in the above steps of the present invention may be a reaction under stirring or a reaction under standing, and according to some embodiments of the present invention, the reaction in the above steps may be a reaction under standing.
According to some embodiments of the present invention, wherein the calcination temperature in step (5) is 300-800 ℃.
According to some embodiments of the invention, the calcination time in step (5) is 1 to 5 hours.
According to some embodiments of the invention, wherein the drying temperature of step (4) is 30 to 100 ℃.
On the other hand, the invention also provides the three-dimensional mesoporous aluminosilicate catalyst carrier prepared by the preparation method.
According to some embodiments of the present invention, the diameter of the mesoporous channel in the three-dimensional mesoporous aluminosilicate catalyst support is 50 to 100 nm.
According to some specific embodiments of the present invention, the mesoporous channels of the three-dimensional mesoporous aluminosilicate catalyst carrier are formed by stacking aluminosilicate nanorods, the pore walls are formed by assembling mesoporous aluminosilicate nanorods, and have a filamentous shape, and the pores are communicated with each other.
According to the three-dimensional mesoporous aluminosilicate catalyst carrier, mesoporous channels are formed by stacking aluminosilicate nanorods, the diameter of the mesoporous channels is about 50-100 nm, the pore walls are formed by assembling the mesoporous aluminosilicate nanorods and are in filiform shapes, and the pores are communicated with one another to form a good-grade pore three-dimensional mesoporous structure.
In summary, the invention provides a three-dimensional mesoporous aluminosilicate catalyst carrier and a preparation method thereof. The catalyst carrier of the invention has the following advantages:
1) the construction of a porous structure in an aluminosilicate carrier is realized, the circulation diffusion performance of the material is improved, and the phenomena of catalyst blockage and poisoning in the reaction process are effectively prevented.
2) The pore channels of the synthesized porous material are uniformly distributed, so that the specific surface area of the material is greatly increased, active substances can be uniformly and effectively dispersed in a carrier material, and the catalytic performance is improved.
3) The experimental synthesis condition is mild, the operation process is simple, the repetition is convenient, and the large-scale synthesis can be realized.
4) In the porous aluminosilicate carrier material synthesized by the method, the pore channel structure in the framework can effectively increase the permeability of a target catalyst, prevent dust and inorganic salt from blocking pore channels, prolong the service life, and greatly increase the specific surface area of the material, so that the porous aluminosilicate carrier material can be used as a carrier material to provide a larger specific surface area for the target catalyst, active components are fully dispersed on the carrier material, and the catalytic performance of the target catalyst is further improved.
Drawings
FIG. 1 is an X-ray diffraction chart of a three-dimensional mesoporous aluminosilicate material produced in example 1 of the present invention; with the abscissa being the 2Theta value (2Theta) and the ordinate being the Intensity (Intensity).
Fig. 2 is a scanning electron microscope image of the three-dimensional mesoporous aluminosilicate material prepared in example 1 of the present invention.
FIG. 3 shows N of the three-dimensional mesoporous aluminosilicate material prepared in example 1 of the present invention2Adsorption and desorption curves; wherein the abscissa is Relative Pressure (Relative Pressure), the ordinate is Volume Adsorbed (Volume Adsorbed), the curve represented by the square is amount of adsorption (Quantity Adsorbed), and the curve represented by the circular block is amount of desorption (Quantity desorbed).
FIG. 4 is a pore size distribution curve of the three-dimensional mesoporous aluminosilicate material prepared in example 1 of the present invention; where the abscissa is aperture (Port Diameter) and the ordinate is dV/dlog (D) Pore Volume.
Fig. 5 is a transmission electron microscope image of the three-dimensional mesoporous aluminosilicate material prepared in example 1 of the present invention.
Detailed Description
The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is not intended to limit the scope of the present disclosure.
Example 1
Taking 20ml of acetonitrile solution with the mass fraction of 99.5%, adding 1ml of deionized water, and uniformly mixing for later use. Uniformly dripping 2g of secondary butanol aluminum solution (97 wt%) into acetonitrile aqueous solution to immediately generate white precipitate, uniformly stirring with a glass rod for 30min, standing at 25 ℃ for 1h, dripping 0.1g of tetramethoxysilane with the mass fraction of 98% at a uniform speed, uniformly stirring with a glass rod for 30min, standing at 25 ℃ for 1h, carrying out suction filtration on the product, drying the product obtained by suction filtration in a 60 ℃ oven, standing for 12h to obtain white powder, and calcining the powder in a muffle furnace at 550 ℃ for 4h to obtain the product, namely the three-dimensional mesoporous aluminosilicate catalyst carrier material.
FIG. 1 is an X-ray diffraction pattern of the product made in this example, the sample exhibiting an amorphous phase of silicon and aluminum. Fig. 2 is a scanning electron microscope image of the product prepared in this embodiment, which shows that the material exhibits a pore structure of three-dimensional mesopores, and the mesopores are formed by stacking aluminosilicate nanorods. Fig. 3 is a nitrogen adsorption and desorption isotherm graph of the product prepared in this example, and the presence of a hysteresis loop can prove that a large number of mesopores exist in the material. FIG. 4 is a graph showing the pore size distribution of the product of this example, and the material prepared therefromHas uniform mesopores, and the average pore diameter is 7.47 nm. The total specific surface area of the sample was 407.04g/cm3The total pore volume is 0.68g/cm3. FIG. 5 is a transmission electron micrograph of a sample showing that the sample has a three-dimensional mesoporous structure.
Example 2
Taking 20ml of acetonitrile solution with the mass fraction of 99.5%, adding 3ml of deionized water, and uniformly mixing for later use. Uniformly dripping 2g of secondary butanol aluminum solution (97 wt%) into acetonitrile aqueous solution to immediately generate white precipitate, uniformly stirring the mixture by using a glass rod for 2 hours, standing the mixture at 40 ℃ for 12 hours, uniformly dripping 0.2g of tetramethoxysilane with the mass fraction of 98%, uniformly stirring the mixture by using the glass rod for 2 hours, standing the mixture at 40 ℃ for 12 hours, performing suction filtration on the product, drying the product obtained by suction filtration in a 60 ℃ oven, standing the product for 12 hours to obtain white powder, and calcining the powder in a muffle furnace at 550 ℃ for 4 hours to obtain the product, namely the three-dimensional mesoporous aluminosilicate catalyst carrier material. The structural properties of the material obtained in this example were the same as in example 1. The X-ray diffraction pattern, the scanning electron microscope image and the transmission electron microscope image of the product are basically the same as those of the product in the example 1, and the N2 adsorption and desorption curve and the pore size distribution curve of the product are also similar to those of the product in the example 1. The prepared material has uniform mesopores, and the average pore diameter is 5.29 nm. The total specific surface area of the sample was 423.65g/cm3The total pore volume is 0.71g/cm3. The transmission electron micrograph of the sample is similar to that of FIG. 5, and shows that the sample has a three-dimensional mesoporous structure.
Example 3
Taking 20ml of acetonitrile solution with the mass fraction of 99.5%, adding 5ml of deionized water, and uniformly mixing for later use. Uniformly dripping 2g of aluminum tert-butoxide (97 wt%) into acetonitrile aqueous solution to immediately generate white precipitate, uniformly stirring with a glass rod for 4h, standing at 60 ℃ for 24h, dripping 0.4g of tetramethoxysilane with the mass fraction of 98% at a uniform speed, uniformly stirring with a glass rod for 4h, standing at 60 ℃ for 24h, suction-filtering the product, drying the product obtained by suction-filtering in a 60 ℃ oven, standing for 12h to obtain white powder, calcining the powder in a muffle furnace at 550 ℃ for 4h to obtain the product, namely the three-dimensional mesoporous aluminosilicate catalyst carrier materialAnd (5) feeding. The structural properties of the material obtained in this example were the same as in example 1. The X-ray diffraction pattern, the scanning electron microscope image and the transmission electron microscope image of the product are basically the same as those of the product in the example 1, and the N2 adsorption and desorption curve and the pore size distribution curve of the product are also similar to those of the product in the example 1. The prepared material has uniform mesopores, and the average pore diameter is 6.12 nm. The total specific surface area of the sample was 396.24g/cm3The total pore volume is 0.59g/cm3. The transmission electron micrograph of the sample is similar to that of FIG. 5, and shows that the sample has a three-dimensional mesoporous structure.
Claims (10)
1. A preparation method of a three-dimensional mesoporous aluminosilicate catalyst carrier comprises the following steps:
(1) preparing an acetonitrile water solution, wherein the volume ratio of water to acetonitrile is 0.1: 20 to 5: 20;
(2) uniformly mixing organic aluminum alkoxide and acetonitrile aqueous solution, and reacting at room temperature to 60 ℃ for 5min to 24h to obtain liquid I; the mass ratio of the organic aluminum alkoxide to the acetonitrile aqueous solution in the step (1) is 1: 2 to 1: 20;
(3) adding a silicon source into the liquid I obtained in the step (2) under the stirring condition, uniformly mixing, and reacting at room temperature to 60 ℃ for 5min to 24h to obtain a white precipitate I; the mass ratio of the added organic aluminum alkoxide to the silicon source is 5: 1 to 20: 1;
(4) filtering, washing and drying the white precipitate I obtained in the step (3) to obtain white powder II;
(5) and (4) roasting the white powder II obtained in the step (4) at the temperature of 300-800 ℃ for 1-5h to obtain the three-dimensional mesoporous aluminosilicate catalyst carrier.
2. The production process according to claim 1, wherein the organic aluminum alkoxide in the step (2) is selected from a mixture of one or more of aluminum n-butoxide, aluminum sec-butoxide and aluminum tert-butoxide.
3. The method according to claim 1, wherein the silicon source in step (2) is selected from a mixture of one or more of tetramethoxysilane, tetraethoxysilane and silica sol.
4. The method according to claim 1, wherein the step (2) is to drop the aluminum organylalkoxide into the aqueous acetonitrile solution and mix it uniformly.
5. The preparation method according to claim 4, wherein the step (2) is to drop the aluminum organylalkoxide into the aqueous acetonitrile solution, and then stir for 30min to 2h to mix uniformly.
6. The method according to claim 1, wherein the silicon source is added dropwise to the liquid I obtained in the step (2) in the step (3).
7. The preparation method according to claim 6, wherein the step (3) comprises adding a silicon source into the liquid I obtained in the step (2) under stirring, stirring for 30min to 2h after dripping to mix uniformly, and then reacting to obtain a white precipitate I.
8. The production method according to claim 1, wherein the drying temperature in the step (4) is 30 to 100 ℃.
9. The three-dimensional mesoporous aluminosilicate catalyst carrier prepared by the preparation method of any one of claims 1 to 8, wherein the diameter of mesoporous channels in the three-dimensional mesoporous aluminosilicate catalyst carrier is 50 to 100 nm.
10. The preparation method of claim 9, wherein the mesoporous channels of the three-dimensional mesoporous aluminosilicate catalyst carrier are formed by stacking aluminosilicate nanorods, the pore walls are formed by assembling mesoporous aluminosilicate nanorods and are in filiform shapes, and the pores are communicated with one another.
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