CN112717907B - gamma-Al with nano sheet piling hollow spherical structure 2 O 3 Catalyst support material and method for producing the same - Google Patents
gamma-Al with nano sheet piling hollow spherical structure 2 O 3 Catalyst support material and method for producing the same Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 239000002135 nanosheet Substances 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000012876 carrier material Substances 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 20
- 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 abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims description 34
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 20
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 12
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 11
- 238000001914 filtration Methods 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000011068 loading method Methods 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- 239000000843 powder Substances 0.000 description 10
- 229910002706 AlOOH Inorganic materials 0.000 description 8
- -1 aluminum sec-butoxide toluene Chemical compound 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001493 electron microscopy Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- KKWVSPRXEUBOHT-UHFFFAOYSA-N CC1=CC=CC=C1.[AlH3] Chemical compound CC1=CC=CC=C1.[AlH3] KKWVSPRXEUBOHT-UHFFFAOYSA-N 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- 241000045365 Microporus <basidiomycete fungus> Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
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Classifications
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B01J35/51—
-
- B01J35/60—
-
- B01J35/61—
Abstract
The invention discloses a gamma-Al with a nano-sheet stacked hollow spherical structure 2 O 3 Catalyst support materials and methods of making the same. The carrier material is of a hollow spherical structure formed by stacking curled nano sheets, and has macropores and mesopores. The preparation method comprises the following steps: 1. dissolving aluminum sec-butoxide in toluene to obtain a clear solution I;2. taking an organic solvent which is insoluble or slightly soluble in water and has a density similar to that of water, adding water and stirring uniformly to obtain a mixed solution II; 3. quickly dripping the clarified solution I into the mixed solution II before small water drops are gathered together to obtain a mixed solution III, standing, washing with alcohol, filtering, drying and burning to obtain the gamma-Al with the hollow spherical structure of the nano-sheet stacking sphere 2 O 3 Catalyst support material. The carrier material has the advantages of large specific surface area, good mobility of spherical structure, easy loading of active molecules, rich pore canal structure, good catalytic performance, simple and convenient preparation process, mild reaction conditions and high repetition rate, and is suitable for popularization and use.
Description
Technical Field
The invention relates to a gamma-Al 2 O 3 The technical field of catalyst carrier materials, in particular to a gamma-Al with a nano-sheet stacked hollow spherical structure 2 O 3 Catalyst support materials and methods of making the same.
Background
Heretofore, the use of catalysts to obtain clean fuels by hydrogenation of heavy oils has been one of the most mature and effective methods. Catalyst support materials currently put into commercial production are known to include alumina, activated carbon, aluminosilicate, and the like. In heterogeneous catalysis, alumina, especially gamma-Al 2 O 3 Is widely used as catalyst and catalyst carrier or carrier, accounting for more than 70% of the industrial supported catalyst carrier. While when gamma-Al 2 O 3 When the catalyst has mesoporous, macroporous and other pore structures, the specific surface area is increased, the adsorptivity is enhanced, and the catalytic performance is further improved. In addition, the advantages and disadvantages of the alumina catalytic performance are not only determined by the specific surface area and the pore size, but also by the special morphology thereof, and the morphology of the alumina prepared at present only has a sphere, a rod or a sheet shape. The nano-sheet alumina has large specific surface area, has good diffusion effect on reaction molecules, and is beneficial to improving the catalytic performance of the reaction molecules.
Shi (Zongbo Shi, wenqian Jiao, li Chen, peng Wu. Microporus and Mesoporous Materials (2016) 253-261) et Al synthesized a flower-like hierarchical pore gamma-Al 2 O 3 The nano-sheet thickness of the carrier material is only 1-5 nm, the nano-sheet with high specific surface area and large aperture is regular and ordered, and the cracking activity of the carrier material on massive TIPB is obviously superior to that of industrial gamma-Al 2 O 3 . However, the preparation process uses the Bayer stone as a precursor, and a high-temperature phase transformation stage is needed, so that the preparation period is relatively long and the operation is complex.
Therefore, development of a method for preparing nano-particles with high specific surface area at low cost and high efficiency is neededgamma-Al in rice flake morphology 2 O 3 The carrier material can effectively improve and control the pore channel property of the alumina carrier material.
Disclosure of Invention
The invention aims to provide gamma-Al with a nano-sheet stacked hollow spherical structure 2 O 3 The catalyst carrier has a hollow spherical structure, the spherical structure is formed by stacking nano sheets, and the catalyst carrier has macropores and mesopores, so that the catalytic efficiency and selectivity of the catalyst can be effectively enhanced, the one-step liquid drop method is adopted, the operation is simple and convenient, the reaction condition is mild, and the repetition rate is high, thereby being suitable for popularization and use.
In order to achieve the above purpose, the invention adopts the following technical scheme:
provides gamma-Al with nano-sheet stacked hollow spherical structure 2 O 3 The catalyst carrier material is a hollow spherical structure formed by stacking curled nano sheets and has macropores and mesopores.
According to the scheme, the spherical diameter in the hollow spherical structure is 400-700 nm; the thickness of the nano-sheet is 1-4 nm.
According to the scheme, the size of the macropores is 50-500 nm, and the size of the mesopores is 2-50 nm.
Provides gamma-Al with nano-sheet stacked hollow spherical structure 2 O 3 A method for preparing a catalyst support material comprising the steps of:
1) Dissolving aluminum sec-butoxide in toluene to obtain a clear solution I;
2) Adding water into an organic solvent which is insoluble or slightly soluble in water and has a density similar to that of water, and stirring uniformly to obtain a mixed solution II, wherein the density of the organic solvent is 0.9-1.1 g/cm 3 ；
3) Quickly dripping the clarified solution I obtained in the step 1) into the mixed solution II obtained in the step 2) before the small water drops are gathered together to obtain a mixed solution III;
4) Standing the mixed solution III obtained in the step 3), washing with alcohol, filtering, and drying to obtain a white precipitate precursor;
5) Burning the white precipitate precursor obtained in the step 4)Firing to obtain gamma-Al with nano-sheet stacked hollow spherical structure 2 O 3 Catalyst support material.
In the scheme, the mass concentration of the aluminum sec-butoxide solution is 95%.
In the scheme, the molar ratio of toluene to aluminum sec-butoxide in the step 1) is (0.6-2.3): 1; preferably, the molar ratio of toluene to aluminum sec-butoxide is (1 to 1.7): 1.
In the above scheme, the organic solvent in step 2) is aniline or acetophenone.
In the scheme, the volume ratio of the organic solvent to the water in the step 2) is (17-19) (1-3).
In the scheme, the molar ratio of the aluminum sec-butoxide in the step 1) to the water in the step 2) is 1 (12-15).
In the scheme, the stirring time in the step 2) is 5-10 min.
In the above scheme, the standing temperature of the step 4) is 15-25 ℃.
In the scheme, the standing time in the step 4) is 2-3 h.
In the scheme, the drying temperature in the step 4) is 40-100 ℃ and the drying time is 18-24 h.
In the scheme, the firing temperature in the step 5) is 500-700 ℃ and the firing time is 3-5 h.
In the invention, aluminum sec-butoxide is dispersed and dissolved in toluene, then organic solvent which is insoluble or slightly soluble in water and has the density close to that of water is selected to be mixed with water, water is uniformly dispersed in the organic solvent, then toluene solution of aluminum sec-butoxide is rapidly added before the water in the organic solvent is condensed, aluminum sec-butoxide is contacted with a small amount of water drops to generate hydrolysis to obtain AOOH nano particles, the AOOH nano particles cannot be condensed and spread outwards to generate straight pore channels under the action of surrounding mixed solution, and spontaneously gather together to form solid pellets, after washing the solid pellets with alcohol, crystallization and growth are started in the drying process to form curled nano sheets, the nano sheets are mutually piled to form a hollow spherical structure, and then the gamma-Al nano sheet piled hollow spherical structure is obtained through burning 2 O 3 Catalyst support material. The obtained gamma-Al 2 O 3 The catalyst carrier material is formed by crimpingThe hollow spherical structure formed by stacking the nano sheets has macropores and mesopores, wherein the macropores are cavities and inter-sphere pores in the spherical structure, and the mesopores are formed by stacking the curled nano sheets.
Compared with the prior art, the invention has the beneficial effects that:
1. the gamma-Al with the nano-sheet stacking hollow spherical structure provided by the invention 2 O 3 The catalyst carrier material is of a hollow spherical structure formed by stacking curled nano sheets, the existence of the curled nano sheets greatly increases the specific surface area of the material, the spherical structure has good flowing property, can be more fully contacted with reaction fluid, and active molecules can be more easily and uniformly loaded on the surface of the spherical carrier, so that the catalytic performance is improved. In addition, the catalyst carrier material has macropores and mesopores, so that the pore canal attribute of the carrier material is enriched, the flow and diffusion properties of reactant molecules are improved, and the catalytic performance is further improved.
2. The invention adopts a one-step liquid drop method, has simple and convenient operation, mild reaction conditions, easy control and high repetition rate, and is suitable for popularization and use.
Drawings
FIG. 1 shows the precursor AlOOH and the gamma-Al of the nano-sheet stacked hollow spherical structure prepared at a standing temperature of 15℃in example 1 of the present invention 2 O 3 Wide angle diffraction XRD pattern of the catalyst support material.
FIG. 2 shows γ -Al of nano-sheet stacked hollow spherical structure obtained in example 1 of the present invention 2 O 3 SEM electron microscope pictures of catalyst carrier material, pictures a and b are respectively gamma-Al prepared at a standing temperature of 15 ℃ and 25 DEG C 2 O 3 。
FIG. 3 shows the gamma-Al of the nano-sheet stacked hollow spherical structure obtained at a standing temperature of 15℃in example 1 of the present invention 2 O 3 TEM electron microscopy of the catalyst support material, with the magnifications of figures a and b increasing in sequence.
FIG. 4 shows γ -Al of nano-sheet stacked hollow spherical structure obtained in example 2 of the present invention 2 O 3 Nitrogen adsorption curve of the catalyst support material.
FIG. 5 shows the embodiment of the present inventiongamma-Al of nano-sheet stacked hollow spherical structure prepared in example 2 2 O 3 Pore size distribution curve of catalyst support material.
FIG. 6 shows gamma-Al of the nano-sheet stacked hollow spherical structure obtained in example 3 of the present invention 2 O 3 SEM electron microscope pictures of catalyst carrier material, pictures a, b and c are respectively gamma-Al prepared at oven temperature of 40 ℃, 80 ℃ and 100 DEG C 2 O 3 。
FIG. 7 shows the production of gamma-Al in comparative example 1 of the present invention 2 O 3 SEM electron microscopy of the catalyst support material.
FIG. 8 shows the production of gamma-Al in comparative example 2 of the present invention 2 O 3 SEM electron microscopy of the catalyst support material.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and examples, but the content of the present invention is not limited to the following examples only.
In the following examples, the reagents described are all commercially available chemical reagents unless specifically indicated.
Example 1
gamma-Al with nano sheet piling hollow spherical structure 2 O 3 The preparation method of the catalyst carrier material comprises the following steps:
1) 1ml of toluene is added into aluminum sec-butoxide (2 g,97wt percent, relative density ρ=0.97), and the mixture is stirred uniformly to obtain aluminum sec-butoxide toluene solution;
2) Adding 2ml of deionized water into aniline (18 ml,99.5wt% and relative density ρ=1.02), stirring until the deionized water is uniformly dispersed in the aniline to obtain a mixed solution, then quickly dripping the aluminum sec-butoxide toluene solution in the step 1) into the mixed solution before water molecules are condensed, immediately generating white precipitate, and standing for 3 hours at 15 ℃ or 25 ℃ to obtain white precipitate I;
3) Washing the white precipitate I obtained in the step 2) by ethanol, then washing by deionized water, and continuing washing by deionized water until the white precipitate I does not react any more to obtain a white precipitate II;
4) The white precipitate II is filtered by suction,the product obtained by suction filtration is put into a 60 ℃ oven, kept stand for 24 hours and fully dried to obtain white powder (AlOOH precursor), the white powder is put into a muffle furnace and burnt for 4 hours at a high temperature of 550 ℃ to obtain the gamma-Al with nano-sheet stacked hollow spherical structure 2 O 3 Catalyst support material.
FIG. 1 shows the precursor AlOOH and the burnt gamma-Al obtained at a standing temperature of 15℃in this example 2 O 3 Wide angle diffraction XRD pattern of the catalyst support material. Before firing, characteristic peaks of AlOOH are shown, and gamma-Al is shown after firing 2 O 3 The characteristic peaks of (2) are both free of other impurity peaks, which indicates that the synthesis is pure phase.
FIG. 2 shows the gamma-Al obtained in the example of the present invention 2 O 3 SEM electron microscope image of catalyst carrier material, wherein image a and image b are respectively gamma-Al prepared at standing temperature 15 ℃ and 25 DEG C 2 O 3 . The resulting gamma-Al can be seen in the figure 2 O 3 The catalyst carrier material is nano-sheet stacked sphere, the diameter of the sphere is 400-700 nm, the size of the macropores is 50-500 nm, the size of the mesopores is 2-50 nm, and the thickness of the nano-sheet is about 1-4 nm; the reaction temperature is 15 ℃ and 25 ℃ and can prepare nano-sheet stacked spherical gamma-Al 2 O 3 。
FIG. 3 shows the result of the gamma-Al obtained at a resting temperature of 15℃in the examples of the present invention 2 O 3 TEM electron microscope pictures of the catalyst carrier material under different magnifications, and the magnifications of the pictures a and b are sequentially increased; from the figure, it can be seen that macropores are mainly composed of spherical internal cavities and inter-spherical voids, and mesopores are mainly formed by stacking curled nano-sheets.
Example 2
gamma-Al with nano sheet piling hollow spherical structure 2 O 3 The preparation method of the catalyst carrier material comprises the following steps:
1) 1ml of toluene is added into aluminum sec-butoxide (2 g,97wt percent, relative density ρ=0.97), and the mixture is stirred uniformly to obtain aluminum sec-butoxide toluene solution;
2) Adding 2ml of deionized water into acetophenone (18 ml,99.5wt% and relative density ρ=1.03), stirring until the deionized water is uniformly dispersed in the acetophenone to obtain a mixed solution, then quickly dripping the aluminum sec-butoxide toluene solution in the step 1) into the mixed solution before water molecules are condensed, immediately generating white precipitate, and standing for 3 hours at 20 ℃ to obtain white precipitate I;
3) Washing the white precipitate I obtained in the step 2) by ethanol, then washing by deionized water, and continuing washing by deionized water until the white precipitate I does not react any more to obtain a white precipitate II;
4) Filtering the white precipitate II, placing the product obtained by filtering into a 60 ℃ oven, standing for 24 hours, fully drying to obtain white powder (AlOOH precursor), placing the white powder into a muffle furnace, and burning at 550 ℃ for 4 hours to obtain the gamma-Al with nano-sheet stacked hollow spherical structure 2 O 3 Catalyst support material.
FIG. 4 shows the production of gamma-Al in the examples of the present invention 2 O 3 The nitrogen adsorption curve of the catalyst support material, wherein the presence of a hysteresis ring indicates that a large number of mesopores are present in the material. FIG. 5 shows the production of gamma-Al in the examples of the present invention 2 O 3 The pore diameter distribution diagram of the catalyst carrier material is that the prepared material has uniform mesopores, and the average pore diameter is between 6.41 nm. The total specific surface area of the sample was 258m 2 Per gram, a total pore volume of 0.57cm 3 /g。
Example 3
gamma-Al with nano sheet piling hollow spherical structure 2 O 3 The preparation method of the catalyst carrier material comprises the following steps:
1) 1ml of toluene is added into aluminum sec-butoxide (2 g,97wt percent, relative density ρ=0.97), and the mixture is stirred uniformly to obtain aluminum sec-butoxide toluene solution;
2) Adding 2ml of deionized water into aniline (18 ml,99.5wt% and relative density ρ=1.02), stirring until the deionized water is uniformly dispersed in the aniline to obtain a mixed solution, then quickly dripping the aluminum sec-butoxide toluene solution in the step 1) into the mixed solution before water molecules are condensed, immediately generating white precipitate, and standing for 3 hours at 20 ℃ to obtain white precipitate I;
3) Washing the white precipitate I obtained in the step 2) by ethanol, then washing by deionized water, and continuing washing by deionized water until the white precipitate I does not react any more to obtain a white precipitate II;
4) Filtering the white precipitate II, drying the product obtained by filtering in an oven at 40 ℃ and 80 ℃ and 100 ℃ for 24 hours to obtain white powder (AlOOH precursor), and burning the white powder in a muffle furnace at 550 ℃ for 4 hours to obtain the gamma-Al with nano-sheet stacked hollow spherical structure 2 O 3 Catalyst support material.
FIG. 6 shows the production of gamma-Al in the examples of the present invention 2 O 3 SEM electron microscope pictures of catalyst carrier material, pictures a, b and c are respectively gamma-Al prepared at oven temperature of 40 ℃, 80 ℃ and 100 DEG C 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the From the figure, the drying temperature of the oven is 40-100 ℃ and the oven is in a nano flaky stacked spherical structure, and the sizes of the spherical structures tend to be consistent along with the increase of the drying temperature.
Comparative example 1
Gamma-Al 2 O 3 A catalyst support material, the method of preparation comprising the steps of:
1) Adding 2ml of deionized water into aniline (18 ml,99.5wt% and relative density ρ=1.02), stirring until the deionized water is uniformly dispersed in the aniline, preparing a mixed solution, then rapidly dropwise adding aluminum sec-butoxide (2 g,97wt% and relative density ρ=0.97) into the mixed solution before water molecules are condensed, immediately generating white precipitate, and standing for 3h at 20 ℃ to obtain white precipitate I;
2) Washing the white precipitate I obtained in the step 1) by ethanol, then washing by deionized water, and continuing washing by deionized water until the white precipitate I does not react any more to obtain a white precipitate II;
3) Filtering the white precipitate II, placing the product obtained by filtering into a 60 ℃ oven, standing for 24 hours, fully drying to obtain white powder (AlOOH precursor), placing the white powder into a muffle furnace, and burning at 550 ℃ for 4 hours to obtain gamma-Al 2 O 3 Catalyst support material.
FIG. 7 shows the production of gamma-Al in this comparative example 2 O 3 SEM (scanning electron microscope) image of catalyst carrier material, and the product morphology can be seen as straight holesThe channel structure is not generated by the nano-sheet stacked spherical structure.
Comparative example 2
Gamma-Al 2 O 3 A catalyst support material, the method of preparation comprising the steps of:
1) 1ml of toluene is added into aluminum sec-butoxide (2 g,97wt percent, relative density ρ=0.97), and the mixture is stirred uniformly to obtain aluminum sec-butoxide toluene solution;
2) Adding 2ml of deionized water into aniline (18 ml,99.5wt% and relative density ρ=1.02), stirring until the deionized water is uniformly dispersed in the aniline to obtain a mixed solution, then quickly dripping the sec-butyl alcohol aluminum toluene solution in the step 1) into the mixed solution before water molecules are condensed, immediately generating white precipitate, and standing for 3 hours at 40 ℃ to obtain white precipitate I;
3) Washing the white precipitate obtained in the step 2) by ethanol, then washing by deionized water, and continuing washing by deionized water until the white precipitate I is reacted vigorously and the white precipitate II is not reacted any more;
4) Filtering the white precipitate II, placing the product obtained by filtering into a 60 ℃ oven, standing for 24 hours, fully drying to obtain white powder I (AlOOH precursor), placing the white powder into a muffle furnace, and burning at 550 ℃ for 4 hours to obtain gamma-Al 2 O 3 Catalyst support material.
FIG. 8 shows the production of gamma-Al in this comparative example 2 O 3 SEM electron microscopy of the catalyst support material shows that the morphology of the product is mostly compact at 40 ℃ and a small amount of nano-sheet structures exist on the bulk, and nano-sheet stacking sphere structures are not prepared.
The foregoing has shown and described the basic principles and advantages of the present invention. Other variations and modifications of the above description will be apparent to those of ordinary skill in the art, and it is not necessary or exhaustive of all embodiments, and thus all obvious variations or modifications that come within the scope of the invention are desired to be protected.
Claims (8)
1. Nanometer sheet piling hollow spherical knotStructured gamma-Al 2 O 3 A method for preparing a catalyst support material, comprising the steps of:
1) Dissolving aluminum sec-butoxide in toluene to obtain a clear solution I;
2) Adding water into an organic solvent which is insoluble or slightly soluble in water and has a density similar to that of water, and stirring uniformly to obtain a mixed solution II, wherein the density of the organic solvent is 0.9-1.1 g/cm 3 ；
3) Quickly dripping the clarified solution I obtained in the step 1) into the mixed solution II obtained in the step 2) before the small water drops are gathered together to obtain a mixed solution III;
4) Standing the mixed solution III obtained in the step 3) at 15-25 ℃, washing with alcohol washing water, performing suction filtration, and drying to obtain a white precipitate precursor;
5) Firing the white precipitate precursor obtained in the step 4) to obtain gamma-Al with nano-sheet stacked hollow spherical structure 2 O 3 A catalyst support material; wherein said gamma-Al 2 O 3 The catalyst carrier material is a hollow spherical structure formed by stacking curled nano sheets, and has macropores and mesopores.
2. The method according to claim 1, wherein the organic solvent in the step 2) is aniline or acetophenone; and in the step 4), the drying temperature is 40-100 ℃, and the drying time is 18-24 hours.
3. The preparation method according to claim 1, wherein the molar ratio of toluene to aluminum sec-butoxide in the step 1) is (0.6-2.3): 1; in the step 2), the volume ratio of the organic solvent to the water is (17-19): 1-3.
4. The method according to claim 3, wherein the molar ratio of toluene to aluminum sec-butoxide is 1 to 1.7.
5. The preparation method according to claim 1, wherein the molar ratio of the aluminum sec-butoxide in the step 1) to the water in the step 2) is 1 (12-15).
6. The preparation method according to claim 1, wherein the stirring time in the step 2) is 5-10 min; the standing time in the step 4) is 2-3 hours; the firing temperature in the step 5) is 500-700 ℃, and the firing time is 3-5 h.
7. The preparation method according to claim 1, wherein the spherical diameter in the hollow spherical structure is 400-700 nm; the thickness of the nano sheet is 1-4 nm.
8. The method of claim 1, wherein the γ -Al 2 O 3 In the catalyst carrier material, the size of macropores is 50-500 nm, and the size of mesopores is 2-50 nm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911029571.7A CN112717907B (en) | 2019-10-28 | 2019-10-28 | gamma-Al with nano sheet piling hollow spherical structure 2 O 3 Catalyst support material and method for producing the same |
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