CN111217382B - A kind of nanowire spherical alumina with large aspect ratio and preparation method thereof - Google Patents
A kind of nanowire spherical alumina with large aspect ratio and preparation method thereof Download PDFInfo
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Abstract
本发明公开了一种大长径比的纳米线型球形氧化铝及其制备方法。以异丙醇铝为原料，通过水解制备勃姆石溶胶，然后进行水热反应，得到一种大长径比的纳米线型勃姆石溶胶前驱体。其直径2‑5nm，长度100‑2000nm，长径比为20‑1000。将前驱体滴入上层油相下层氨相的油氨柱中形成球状凝胶粒子，经过老化、干燥、焙烧得到球形氧化铝。该氧化铝由上述规格的纳米线团聚而成，具有高的比表面积，规整的介孔结构以及较高的机械强度，球形颗粒尺寸大小可控，可作为催化剂的载体。成型过程简便易行，成本低廉，可大批量生产。
The invention discloses a nanowire-shaped spherical alumina with a large aspect ratio and a preparation method thereof. Using aluminum isopropoxide as a raw material, a boehmite sol is prepared by hydrolysis, and then a hydrothermal reaction is performed to obtain a nanowire boehmite sol precursor with a large aspect ratio. Its diameter is 2‑5nm, its length is 100‑2000nm, and its aspect ratio is 20‑1000. The precursor is dropped into the oil-ammonia column of the upper-layer oil phase and the lower-layer ammonia phase to form spherical gel particles, which are then aged, dried and calcined to obtain spherical alumina. The alumina is formed by agglomeration of the above-mentioned nanowires, has high specific surface area, regular mesoporous structure and high mechanical strength, and the size of spherical particles is controllable, and can be used as a catalyst carrier. The molding process is simple and easy, the cost is low, and it can be mass-produced.
Description
Technical Field
The invention relates to the technical field of preparation processes of spherical alumina, in particular to a preparation method of nanowire-type spherical alumina.
Background
Alumina has characteristics of large specific surface area, special pore structure, good adsorbability, certain acidity and the like, and is widely applied to various fields of catalysts, catalyst carriers, adsorption, ceramics and the like. The alumina one-dimensional nano material also has the characteristics of high elastic modulus, high dielectric constant, low magnetic permeability, high thermal conductivity, unique optical performance and the like, and can be used for catalysts and catalyst carriers, ceramic materials and composite material reinforcements. Therefore, the preparation of alumina nano-materials, especially alumina one-dimensional nano-materials, becomes a hot research point in the material science community. However, when the vapor phase method is used for preparing the alumina one-dimensional nanomaterial, the preparation needs to be carried out under the conditions of high temperature, vacuum or protective atmosphere and catalyst, the preparation conditions are very strict, and special equipment is usually required, so the application of the alumina one-dimensional nanomaterial is limited. At present, reports about the formation of alumina one-dimensional nano materials are not seen, which greatly limits the application of the alumina one-dimensional nano materials in the field of catalysis, such as the application of the alumina one-dimensional nano materials as carriers.
Boehmite, the english Boehmite, means alumina monohydrate, the molecular formula AlOOH, is a series of evolutions from disordered to ordered, weakly crystalline to crystalline with uncertain composition and incomplete crystallization, and the typical structure is a very thin corrugated sheet. It is mainly used as raw material for preparing gamma-Al 2O3 and alpha-Al 2O3 and binder for difficult-to-mold catalyst or catalyst carrier. In recent years, many patents have adopted pseudo-boehmite powder (SB powder) produced by Condea, Germany as a raw material to prepare spherical alumina. However, in the molding process, more organic substances need to be added, which not only complicates the process and causes pollution, but also increases the cost of the SB powder.
Disclosure of Invention
The invention aims to provide the nanowire-type spherical alumina with the large length-diameter ratio and the preparation method thereof. The preparation method is simple and easy to implement, has low cost and can be used for mass production.
The invention takes aluminum isopropoxide as a raw material, prepares boehmite sol through hydrolysis, and then carries out hydrothermal reaction to obtain the nanowire-type boehmite sol precursor with large length-diameter ratio. Dripping the precursor into an oil-ammonia column of an upper oil phase and a lower ammonia phase to form spherical gel particles, and aging, drying and roasting to obtain spherical alumina. The alumina is formed by the agglomeration of nano-wires with the specification, and due to the special one-dimensional shape and appearance characteristics, the specific surface area of the spherical alumina is 200-300 square meters per gram, and the pore volume is 0.3-0.6cm3The volume ratio of pores with the diameter of 3-6nm is more than 80%, and the mechanical strength is more than 160N per particle.
The invention provides a preparation method of nanowire-type spherical alumina with a large length-diameter ratio, which comprises the following specific steps:
(1) adding aluminum isopropoxide into deionized water, heating to hydrolyze, evaporating to remove isopropanol, replenishing water to 0.5-1 times of original volume, adding acetic acid, and continuously stirring to obtain boehmite sol;
(2) putting the boehmite sol into a hydrothermal kettle for reaction, and cooling to obtain a nanowire-type boehmite sol precursor;
(3) carrying out decompression rotary evaporation on the boehmite sol precursor to remove water to reach the required concentration;
(4) and (4) dripping the precursor obtained in the step (3) into an oil ammonia column of an upper oil phase and a lower ammonia phase to form spherical gel particles, and aging, drying and roasting to obtain spherical alumina.
The spherical alumina is characterized in that: the diameter of the spherical alumina is 1-5 mm.
In the step (1), the mass fraction of the aqueous solution of aluminum isopropoxide is 10-20%, and the final mass fraction of acetic acid in water is 1-2%. The temperature of hydrolysis, evaporation and continuous stirring is 80-120 ℃, and the continuous stirring time is 0.5-2 hours.
The hydrothermal reaction time in the step (2) is 6-10 hours, and the hydrothermal reaction temperature is 150-180 ℃.
In the step (3), the rotary evaporation temperature is 40-60 ℃, and the required concentration is 16-35%.
The upper oil phase substance in the step (4) can be one or a mixture of more of hexane, heptane, octane, nonane, decane, undecane, dodecane, toluene, gasoline, kerosene and petroleum ether, and the height is 20-50 cm; the lower layer ammonia phase substance can be ammonia water with a mass fraction of 3-8% and a height of 90-150 cm; and no surfactant is added between the oil phase and the ammonia phase or a surfactant can be added, the surfactant can be one of sodium dodecyl benzene sulfonate, tetrabutyl ammonium bromide, hexadecyl trimethyl ammonium bromide or octyl phenyl polyoxyethylene ether, and the amount of the surfactant added is up to the level of the liquid level between the oil phase and the ammonia phase.
The aging time in the step (4) is 8-16 hours, the drying temperature is 60 ℃, the drying time is 10-20 hours, the roasting time is 4-6 hours, and the roasting temperature is 400-600 ℃.
Compared with the prior art, the invention has the advantages that: aluminum isopropoxide is used as a raw material, and boehmite is prepared by a hydrolysis method, wherein the raw material is lower in price compared with SB powder used in the prior art; the boehmite sol is reacted in a hydrothermal kettle by adopting a liquid phase method to prepare a precursor with a one-dimensional nano linear structure, and the method has the characteristics of easy realization of reaction conditions, good controllability of product size, structure and components and capability of large-scale preparation; the diameter of the precursor nanowire used in the invention is 2-5nm, the length is 100-2000nm, the length-diameter ratio is 20-1000, and the length-diameter ratio is very large; the precursor is formed by an oil ammonia column method, and the prepared spherical alumina is formed by the agglomeration of the nanowires with the specifications, has large specific surface area, regular mesoporous structure and higher mechanical strength, because of the special nanowire linear structure, the nanowire has good ductility due to the large length-diameter ratio, and has high mechanical strength after agglomeration; in the forming process, the boehmite sol does not need to be aged, dried and roasted, but the gel is directly dripped into the oil ammonia column for forming, so that the preparation process has simple steps and low cost, and can be produced in large batch. The alumina prepared by the invention can be used as a catalyst and/or a catalyst carrier, or used for preparing a raw material of a ceramic material and/or a composite material reinforcement.
Drawings
FIG. 1 is a microscopic view of a nanowire-type boehmite sol precursor prepared in example 1 under a transmission electron microscope;
FIG. 2 is a microscopic image of spherical alumina prepared in preparation example 1 under a projection electron microscope;
FIG. 3 is a schematic representation of spherical alumina prepared in examples 1, 2 and 3.
Detailed Description
Example 1
(1) 66g of aluminium isopropoxide are taken and added to 600ml of deionized water and stirred until complete hydrolysis, and the solution is then evaporated at 95 ℃. Deionized water was added to 600g, and 6.2g of acetic acid was added and stirred at 95 ℃ for 0.5 h.
(2) Transferring the obtained reaction mixture into a reaction kettle, sealing, carrying out hydrothermal reaction for 6h at 150 ℃, and cooling to room temperature after the reaction is finished to obtain sol.
(3) And (3) carrying out rotary evaporation on the sol at 50 ℃ to prepare boehmite sol with the mass fraction of 16.9% for later use. The microstructure of the sol was observed by transmission electron microscopy, and the results are shown in FIG. 1. As can be seen, the boehmite sol has a one-dimensional nano-linear microstructure with the diameter of 2-5nm, the length of 100-2000nm and the length-diameter ratio of 20-1000.
(4) In an oleylamine column with the length of 1.5m and the diameter of 40mm, 8% of ammonia water is firstly added to be a water phase till the distance from a column port is about 15cm, then n-dodecane is added to be an oil phase till the liquid level is about 2-3cm away from the column port, and finally a surfactant (1gTX-100, 33g of absolute ethyl alcohol and 66g of ultrapure water) is added till the liquid level of an oleylamine phase is crossed and jointed. Pouring the boehmite sol into a ball dropping device positioned above an oil amine column, wherein the distance between a needle hole at the bottom of the ball dropping device and the oil surface is 3cm, dropping the boehmite sol into the oil amine column at a dropping speed of 2 s/drop, wherein sol particles form balls in the oil phase, enter an ammonia water phase and are gelled into a solid. Aging the gel particles in ammonia water for 15h, taking out, drying in the shade at room temperature for 24h, drying at 60 ℃ for 12h, and roasting at 550 ℃ for 4h to obtain Al with smooth surface2O3And (4) a small ball. The microstructure of the alumina was observed using a transmission electron microscope, as shown in fig. 2. It can be seen from the figure that the formed alumina pellets are formed by the aggregation of the nanowires with the above specifications. The diameter of the pellet is about 2mm, the appearance is shown in fig. 3, and as can be seen from fig. 3, the outer surface of the pellet is smooth and spherical, the particle size is uniform, and the physical properties are shown in table 1.
Example 2
Al obtained by the method of example 12O3The beads were manufactured with a diameter of about 2.5mm except that the boehmite sol concentration in step (3) was 25.8%, and the appearance thereof is shown in FIG. 3. As can be seen from FIG. 3, the beads had smooth outer surfaces, were spherical, had uniform particle sizes, and had the physical properties shown in Table 1.
Example 3
Al obtained by the method of example 12O3The beads were manufactured with a diameter of about 3mm except that the boehmite sol concentration in step (3) was 30.35%, and the appearance of the beads is shown in fig. 3. as can be seen from fig. 3, the beads had smooth outer surfaces, were spherical, had uniform particle sizes, and had the physical properties shown in table 1.
Example 4
The boehmite sol prepared according to example 1 was prepared except that the hydrothermal conditions in step (2) were 160 ℃ for 6 hours.
Example 5
The boehmite sol prepared according to example 1 was prepared except that the hydrothermal conditions in step (2) were 160 ℃ for 10 hours.
Example 6
The boehmite sol prepared according to example 1 was prepared except that the hydrothermal conditions in step (2) were 180 ℃ for 6 hours.
Example 7
Pellets of alumina prepared as in example 1 except that 120g of aluminum isopropoxide in step (1) was added to 600ml of deionized water and stirred until complete hydrolysis, and then the solution was evaporated from the isopropanol at 95 ℃. Deionized water was added to 600g and 12g acetic acid was added.
Example 8
Alumina pellets were prepared as in example 1 except that in step (1) the solution was evaporated at 120 ℃ to give isopropanol, and after addition of 6.2g of acetic acid, stirring was continued for a further 2 h.
Example 9
Alumina pellets were obtained by following the procedure of example 1 except that in the step (4), the pellets were aged in aqueous ammonia for 8 hours, then dried at 60 ℃ for 20 hours and calcined at 400 ℃ for 6 hours.
Example 10
Alumina pellets were obtained by following the procedure of example 1 except that in the step (4), the pellets were aged in aqueous ammonia for 16 hours, then dried at 60 ℃ for 10 hours and calcined at 600 ℃ for 4 hours.
Comparative example
Comparative tests were carried out on the spherical aluminas obtained in examples 1 to 3 with the spherical alumina of Sasol (type Spheresl.8/210) purchased on the market, the results of which are shown in Table 1.
Wherein the specific surface area, the pore volume and the most probable pore diameter are all measured by an Autosorb-1MP type full-automatic specific surface and pore analyzer of Quantachrome company. Mechanical Strength the crush strength was measured using a DL III-500 type Strength tester.
As can be seen from Table 1, the mechanical strength of the spherical alumina prepared by the present invention is 5-7 times that of the commercially available Sasol, and the specific surface area is increased by 10%.
Claims (8)
1. A nanowire-type spherical alumina with a large length-diameter ratio is characterized in that: the alumina is prepared from a nanowire-type boehmite sol precursor with a large length-diameter ratio, wherein the diameter of the precursor nanowire is 2-5nm, the length of the precursor nanowire is 100-2000nm, and the length-diameter ratio of the precursor nanowire is 20-1000; the spherical alumina is formed by the agglomeration of the nanowires with the specification, the specific surface area is 200-300 square meters per gram, the pore volume is 0.3-0.6cm in weight/gram, the diameter of the pore is more than 90 percent when the diameter of the pore is 3-6nm, and the diameter of the spherical alumina is 1-5 mm;
the method comprises the following steps:
(1) adding aluminum isopropoxide into deionized water, heating to hydrolyze, evaporating to remove isopropanol, replenishing water to 0.5-1 times of original volume, adding acetic acid, and continuously stirring to obtain boehmite sol; in the step (1), the temperature of hydrolysis, evaporation and continuous stirring is 80-120 ℃, and the continuous stirring time is 0.5-2 hours; in the step (1), the mass fraction of the aqueous solution of aluminum isopropoxide is 10-20%, and the final mass fraction of acetic acid in water is 1-2%;
(2) putting the boehmite sol into a hydrothermal kettle for reaction, and cooling to obtain a nanowire-type boehmite sol precursor;
(3) carrying out decompression rotary evaporation on the boehmite sol precursor to remove water to reach the required concentration;
(4) and (4) dripping the precursor obtained in the step (3) into an oil ammonia column of an upper oil phase and a lower ammonia phase to form spherical gel particles, and aging, drying and roasting to obtain spherical alumina.
2. The spherical alumina according to claim 1, wherein: the mechanical strength is more than 160N/particle.
3. A method for preparing the nano linear spherical alumina with large length-diameter ratio according to claim 1 or 2, which comprises the following steps:
(1) adding aluminum isopropoxide into deionized water, heating to hydrolyze, evaporating to remove isopropanol, replenishing water to 0.5-1 times of original volume, adding acetic acid, and continuously stirring to obtain boehmite sol; in the step (1), the temperature of hydrolysis, evaporation and continuous stirring is 80-120 ℃, and the continuous stirring time is 0.5-2 hours; in the step (1), the mass fraction of the aqueous solution of aluminum isopropoxide is 10-20%, and the final mass fraction of acetic acid in water is 1-2%;
(2) putting the boehmite sol into a hydrothermal kettle for reaction, and cooling to obtain a nanowire-type boehmite sol precursor;
(3) carrying out decompression rotary evaporation on the boehmite sol precursor to remove water to reach the required concentration;
(4) and (4) dripping the precursor obtained in the step (3) into an oil ammonia column of an upper oil phase and a lower ammonia phase to form spherical gel particles, and aging, drying and roasting to obtain spherical alumina.
4. The method for preparing spherical alumina according to claim 3, wherein: the hydrothermal reaction time in the step (2) is 6-10 hours, and the hydrothermal reaction temperature is 150-180 ℃.
5. The method for preparing spherical alumina according to claim 3, wherein: in the step (3), the rotary evaporation temperature is 40-60 ℃, and the required concentration is 16-35%.
6. The method for preparing spherical alumina according to claim 3, wherein: in the step (4), the upper oil phase substance is one or a mixture of more of hexane, heptane, octane, nonane, decane, undecane, dodecane, toluene, gasoline, kerosene and petroleum ether, and the height is 20-50 cm; the lower layer ammonia phase substance is ammonia water with the mass fraction of 3-8% and the height of 90-150 cm; and no surfactant is added or added between the oil phase and the ammonia phase, the surfactant is one of sodium dodecyl benzene sulfonate, tetrabutyl ammonium bromide, hexadecyl trimethyl ammonium bromide or octyl phenyl polyoxyethylene ether, and the amount of the added surfactant is equal to the level of the liquid level between the oil phase and the ammonia phase.
7. The method for preparing spherical alumina according to claim 3, wherein: the aging time in the step (4) is 8-16 hours, the drying temperature is 60 ℃, the drying time is 10-20 hours, the roasting time is 4-6 hours, and the roasting temperature is 400-600 ℃.
8. Use of the nanowire-shaped spherical alumina with a large length to diameter ratio as claimed in claim 1 or 2 as a catalyst or catalyst support, or as a raw material for making ceramic materials or as a composite reinforcement.
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| US9994715B2 (en) * | 2016-02-16 | 2018-06-12 | Sila Nanotechnologies Inc. | Formation and modifications of ceramic nanowires and their use in functional materials |
| US12053521B2 (en) * | 2019-05-17 | 2024-08-06 | Sila Nanotechnologies, Inc. | Nanofiber compositions for a vaccine adjuvant, porous scaffold or porous membrane |
| CN114853457B (en) * | 2022-06-02 | 2023-03-10 | 航天特种材料及工艺技术研究所 | A kind of alumina-carbon composite nanofiber airgel material and preparation method thereof |
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