CN116282052A - Method for rapidly preparing nano hollow silicon dioxide - Google Patents

Method for rapidly preparing nano hollow silicon dioxide Download PDF

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CN116282052A
CN116282052A CN202310204552.3A CN202310204552A CN116282052A CN 116282052 A CN116282052 A CN 116282052A CN 202310204552 A CN202310204552 A CN 202310204552A CN 116282052 A CN116282052 A CN 116282052A
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feed liquid
acid
nano
hollow silica
calcium carbonate
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陈建峰
王康
王洁欣
孙宝昌
王丹
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
    • C01B33/193—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow
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    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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    • C01P2006/17—Pore diameter distribution
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention discloses a method for rapidly preparing nano hollow silicon dioxide, which comprises the following steps: adding the nano calcium carbonate filter cake and sodium silicate into water according to a certain proportion to prepare a suspension of nano calcium carbonate and sodium silicate, and marking the suspension as feed liquid A; adding organic acid or inorganic acid into water to prepare an acidic solution, and marking the acidic solution as feed liquid B; simultaneously injecting the feed liquid A and the feed liquid B into a super-gravity rotating packed bed reactor through a feed inlet to enable the feed liquid A and the feed liquid B to be fully mixed and reacted, collecting slurry, preserving heat and aging, filtering and washing to obtain CaCO 3 @SiO 2 A composite particle filter cake; and (3) putting the filter cake into an acid solution to dissolve nano calcium carbonate, filtering, washing and drying to obtain the nano hollow silicon dioxide. The invention can rapidly prepare low-cost high-quality nano hollow silicon dioxide material by using the supergravity technology, the particle size is 10-500nm, and the thickness is controllable to 1-20nm; no organic solvent is needed in the preparation process, and the preparation method is suitable for mass production。

Description

Method for rapidly preparing nano hollow silicon dioxide
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a method for rapidly preparing nano hollow silicon dioxide.
Background
Hollow materials have unique hollow structures that allow them to have low density, large specific surface area, special optical properties, and high loading capacity as compared to conventional materials. Therefore, they have been widely used in the fields of optics, electronics, catalysis, and sustained release over the past several decades. Among the inorganic matrices available, silica is highly biocompatible, thermodynamically and mechanically stable, and is readily functionalized. Thus, nano-hollow silica has a greater potential for use than other hollow inorganic materials.
At present, a plurality of methods for preparing the nano hollow silica at home and abroad mainly comprise the following steps: template-assisted synthesis, spray drying, self-assembly techniques, emulsion/interfacial polymerization, and the like. Of these, template-assisted synthesis is most common. Gao Yun of the university of agricultural in China uses polystyrene as a hard template, cetyl Trimethyl Ammonium Bromide (CTAB) as a surfactant as a pore-expanding agent, and tetraethyl orthosilicate (TEOS) as a silicon source to prepare the nano hollow silica. Finally, the grain diameter is about 500nm, the aperture is 2.96nm, the specific surface area is 711.28m 2 /g of nano hollow silica (Gao Yun, university of agricultural university of China, shuoshi treatises, 2018).
Li Zhuzhu (L-X Wen, Z-Z Li, H-K Zou, et al controlled release of avermectin from porous hollow silica nanoparticles [ J ]. Pest Management Science,2005,61,583.) nanometer hollow silica with a diameter of about 70nm, a wall thickness of about 15nm, and a pore diameter of 4nm was prepared using nanometer nano calcium carbonate as a hard template, a surfactant as a soft template, and sodium silicate as a silicon source.
In the preparation method, the polystyrene microsphere and the tetraethoxysilane are expensive, and are difficult to meet the large-scale application requirements. Meanwhile, the preparation method using sodium silicate as a silicon source adopts a dropwise adding mode for feeding, and mainly comprises the steps of long auxiliary time and reaction time of disassembling and assembling equipment and charging and discharging in the intermittent reaction production process, unstable product performance among batches and difficult industrial amplification. Therefore, aiming at the defects of the existing method, a preparation method of the nano hollow silicon dioxide which has the advantages of simple process flow, low energy consumption, short time, low cost and easy mass production is needed.
Disclosure of Invention
The invention aims to provide a method for rapidly preparing nano hollow silicon dioxide; the preparation method adopts the supergravity rotary packed bed reactor, greatly strengthens the mass transfer and micromixing process of the reaction, and prepares CaCO with uniform granularity 3 @SiO 2 Composite particles; caCO is then added 3 @SiO 2 The composite particles are placed in an acid solution to dissolve nano calcium carbonate, and the nano hollow silicon dioxide is obtained through filtration, washing and drying.
In order to solve the first technical problem, the invention adopts the following technical scheme:
a method for rapidly preparing nano hollow silica, comprising the following steps:
s1, adding a nano calcium carbonate filter cake and sodium silicate into water according to a certain proportion to prepare a suspension of nano calcium carbonate and sodium silicate, and marking the suspension as feed liquid A;
s2, adding organic acid or inorganic acid into water to prepare an acidic solution, and marking the acidic solution as feed liquid B;
s3, simultaneously injecting the feed liquid A and the feed liquid B into the super-gravity rotating packed bed reactor through the feed inlet to enable the feed liquid A and the feed liquid B to be fully mixed and reacted, collecting slurry, preserving heat and aging, filtering and washing to obtain CaCO 3 @SiO 2 A composite particle filter cake;
s4, caCO is added 3 @SiO 2 And (3) putting the composite particle filter cake into an organic acid or inorganic acid solution to dissolve nano calcium carbonate, filtering, washing and drying to obtain nano hollow silicon dioxide.
Preferably, in step S1, the nano calcium carbonate has a shape of needle, spindle, sphere, cube, petal or flake.
Preferably, in the step S1, the concentration of the nano calcium carbonate in the feed liquid A is 2-40wt%.
Preferably, in step S1, the concentration of sodium silicate in the feed liquid A is 2-40wt%.
Preferably, in step S2, the organic acid or inorganic acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, selenoic acid, phosphoric acid, perchloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, hydrocyanic acid, sulfurous acid, nitrous acid, citric acid, lactic acid, tartaric acid, malic acid, meta-tartaric acid, oxalic acid, and fumaric acid solution.
Preferably, in the step S2, the concentration of the feed liquid B is 0.01mol/L-2mol/L.
Preferably, in the step S3, the temperature of the heat preservation aging is 20-90 ℃; more preferably, the temperature of the thermal insulation ageing is 30-80 ℃;
preferably, in the step S3, the heat preservation aging time is 5-120min.
Preferably, in the step S3, the feeding flow rate of the feed liquid A is 20-2000mL/min, and the feeding flow rate of the feed liquid B is 20-2000mL/min; the feeding flow rate ratio of the feed liquid A to the feed liquid B is 1:3-3:1, and the volume flow ratio of the feed liquid A to the feed liquid B which is introduced into the super-gravity rotary packed bed reactor is 0.3-3.
Preferably, in the step S3, the rotating speed of the rotor of the super-gravity rotating packed bed reactor is 300-3000rpm; more preferably, the rotor speed of the super gravity rotating packed bed reactor is 500-2500rpm.
Preferably, in step S4, the shell thickness of the nano hollow silica is 1-30nm.
Preferably, in step S4, the drying is air drying, the drying temperature is 25-120 ℃, and the drying time is 2-24 hours; more preferably, the drying temperature is 30-110 ℃ and the drying time is 3-14h.
Any range recited in the invention includes any numerical value between the endpoints and any sub-range of any numerical value between the endpoints or any numerical value between the endpoints.
Unless otherwise indicated, all starting materials herein are commercially available, and the equipment used in the present invention may be conventional in the art or may be conventional in the art.
Compared with the prior art, the invention has the following beneficial effects：
1) In the prior art, the preparation of the nano hollow silicon dioxide mainly adopts a polystyrene organic template method, and has the advantages of larger particle size, high price and difficult industrial amplification; the auxiliary time and the reaction time for disassembling and assembling equipment and charging and discharging in the intermittent reaction production process are long, and the product performance among batches is unstable. The invention utilizes the supergravity technology to realize the rapid production of the nano hollow silica, and determines the influence of various control conditions on the product performance, thereby preparing the high-quality nano hollow silica material suitable for industrial application;
2) The nano hollow silicon dioxide prepared by the invention is spherical, and the particle size is 80-100nm;
3) The nano hollow silicon dioxide prepared by the invention is spherical, and the thickness is controllable to be 1-20nm;
4) The invention has simple technical process, no need of any organic solvent in the preparation process, low price and easy obtainment of raw materials, high production efficiency and suitability for mass production.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings
FIG. 1 is a transmission electron microscope image of inorganic template nano calcium carbonate used for preparing nano hollow silica in example 1;
FIG. 2 is a transmission electron microscope image of the nano hollow silica in example 1;
FIG. 3 is an adsorption/desorption isothermal curve of the nano hollow silica in example 1;
FIG. 4 is a transmission electron microscope image of the nano hollow silica in example 1;
FIG. 5 is a transmission electron microscope image of the nano hollow silica in example 2;
FIG. 6 is a transmission electron microscope image of the nano hollow silica in example 3;
FIG. 7 is a transmission electron microscope image of the nano hollow silica in example 4;
FIG. 8 is a transmission electron microscope image of the nano hollow silica in example 5;
FIG. 9 is a transmission electron microscope image of the nano hollow silica in example 6;
FIG. 10 is a transmission electron microscope image of the nano hollow silica of comparative example 1;
FIG. 11 is a transmission electron microscope image of the nano hollow silica of comparative example 2;
FIG. 12 is a transmission electron microscope image of the nano hollow silica of comparative example 3;
FIG. 13 is a transmission electron microscope image of the nano hollow silica of comparative example 4;
FIG. 14 is a transmission electron microscope image of the nano hollow silica of comparative example 5;
FIG. 15 is a transmission electron microscope image of the nano hollow silica of comparative example 6;
FIG. 16 is a transmission electron microscope image of the nano hollow silica of comparative example 7;
FIG. 17 is a transmission electron microscope image of the nano hollow silica of comparative example 8;
FIG. 18 is a transmission electron microscope image of the nano hollow silica of comparative example 9;
FIG. 19 is an adsorption/desorption isothermal curve of nano hollow silica in comparative example 9;
FIG. 20 is a transmission electron microscope image of the nano hollow silica of comparative example 10;
fig. 21 is a schematic flow chart of the technical scheme of the present invention.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
As one aspect of the present invention, the present invention is a method for rapidly preparing nano hollow silica, comprising the steps of:
s1, adding a nano calcium carbonate filter cake and sodium silicate into water according to a certain proportion to prepare a suspension of nano calcium carbonate and sodium silicate, and marking the suspension as feed liquid A;
s2, adding organic acid or inorganic acid into water to prepare an acidic solution, and marking the acidic solution as feed liquid B;
s3, simultaneously injecting the feed liquid A and the feed liquid B into the super-gravity rotary packed bed reactor through the feed inlet to charge the feed liquid A and the feed liquid BMixing, reacting, collecting slurry, maintaining the temperature, aging, filtering and washing to obtain CaCO 3 @SiO 2 A composite particle filter cake;
s4, caCO is added 3 @SiO 2 And (3) putting the composite particle filter cake into an organic acid or inorganic acid solution to dissolve nano calcium carbonate, filtering, washing and drying to obtain nano hollow silicon dioxide.
In certain embodiments, in step S1, the nano-calcium carbonate has a shape of needle, spindle, sphere, cube, petal, or flake.
In certain embodiments, in step S1, the concentration of nano calcium carbonate in feed liquid A is 2-40wt%, including but not limited to 2-35wt%, 2-30wt%, 2-25wt%, 2-20wt%, 2-15wt%, 2-10wt%, 5-40wt%, 5-35wt%, 5-30wt%, 5-25wt%, 5-20wt%, 5-15wt%, 5-10wt%, 10-40wt%, 10-35wt%, 10-30wt%, 10-25wt%, 10-20wt%, 10-15wt%, 15-40wt%, 15-35wt%, 15-30wt%, 15-25wt%, 15-20wt%, 20-40wt%, 20-35wt%, 20-30wt%, 20-25wt%, 25-40wt%, 25-35wt%, 25-30wt%, 30-40wt%, 30-35wt%, or 35-40wt%.
In certain embodiments, in step S1, the concentration of sodium silicate in feed liquid A is 2-40wt%, including but not limited to 2-35wt%, 2-30wt%, 2-25wt%, 2-20wt%, 2-15wt%, 2-10wt%, 5-40wt%, 5-35wt%, 5-30wt%, 5-25wt%, 5-20wt%, 5-15wt%, 5-10wt%, 10-40wt%, 10-35wt%, 10-30wt%, 10-25wt%, 10-20wt%, 10-15wt%, 15-40wt%, 15-35wt%, 15-30wt%, 15-25wt%, 15-20wt%, 20-40wt%, 20-35wt%, 20-30wt%, 20-25wt%, 25-40wt%, 25-35wt%, 25-30wt%, 30-40wt%, 30-35wt%, 35-40wt%.
In certain embodiments, in step S2, the organic or inorganic acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, selenoic acid, phosphoric acid, perchloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, hydrocyanic acid, sulfurous acid, nitrous acid, citric acid, lactic acid, tartaric acid, malic acid, meta-tartaric acid, oxalic acid, fumaric acid solution.
In certain embodiments, in step S2, the concentration of feed liquid B is 0.01mol/L to 2mol/L.
In certain embodiments, in step S3, the temperature of the heat-preserving aging is 20-90 ℃, including, but not limited to, 20-80 ℃, 20-70 ℃, 20-60 ℃, 20-50 ℃, 20-40 ℃, 20-30 ℃, 30-90 ℃, 30-80 ℃, 30-70 ℃, 30-60 ℃, 30-50 ℃, 30-40 ℃, 20-30 ℃, 40-90 ℃, 40-80 ℃, 40-70 ℃, 40-60 ℃, 40-50 ℃, 50-90 ℃, 50-80 ℃, 50-70 ℃, 50-60 ℃, 60-90 ℃, 60-80 ℃, 60-70 ℃, 70-90 ℃, 70-80 ℃, 80-90 ℃.
In certain embodiments, in step S3, the hold aging time is from 5 to 120 minutes, including but not limited to 5-110, 5-100, 5-90, 5-80, 5-70, 5-60, 5-50, 5-40, 5-30, 5-20, 5-10, 10-120, 10-110, 10-100, 10-90, 10-80, 10-70, 10-60, 10-50, 10-40, 10-30, 10-20, 20-120, 20-110, 20-100, 20-90, 20-80, 20-70, 20-60, 20-50, 20-40, 20-30, 30-120 30-110min, 30-100min, 30-90min, 30-80min, 30-70min, 30-60min, 30-50min, 30-40min, 40-120min, 40-110min, 40-100min, 40-90min, 40-80min, 40-70min, 40-60min, 40-50min, 50-120min, 50-110min, 50-100min, 50-90min, 50-80min, 50-70min, 50-60min, 60-120min, 60-110min, 60-100min, 60-90min, 60-80min, 60-70min, 70-120min, 70-110min, 70-100min, 70-90min, 70-80min.
In certain embodiments, in step S3, the feed liquid A feed flow rate is 20-2000mL/min, and the feed liquid B feed flow rate is 20-2000mL/min; the feeding flow rate ratio of the feed liquid A to the feed liquid B is 1:3-3:1, and the volume flow ratio of the feed liquid A to the feed liquid B which is introduced into the super-gravity rotary packed bed reactor is 0.3-3.
In certain embodiments, in step S3, the rotor speed of the super gravity rotating packed bed reactor is 300-3000rpm, including but not limited to 300-2500rpm, 300-2000rpm, 300-1500rpm, 300-1000rpm, 300-500rpm, 500-2500rpm, 500-2000rpm, 500-1500rpm, 500-1000rpm, 1000-2500rpm, 1000-2000rpm, 1000-1500rpm.
In certain embodiments, in step S4, the shell thickness of the nano-hollow silica is 1-30nm.
In certain embodiments, in step S4, the drying is air drying at 25-120 ℃ for 2-24 hours; more preferably, the drying temperature is 30-110 ℃ and the drying time is 3-14h.
Example 1
Referring to fig. 21, a method for rapidly preparing nano hollow silica according to the present invention includes the steps of:
according to SiO 2 /CaCO 3 At a ratio of 20% by mass to CaCO 3 Na was added to the suspension having a solids content of 6wt% 2 SiO 3 ·9H 2 O is dissolved and stirred uniformly and is marked as feed liquid A; adding hydrochloric acid into water to prepare a dilute hydrochloric acid solution, and marking the dilute hydrochloric acid solution as feed liquid B; simultaneously injecting the feed liquid A and the feed liquid B into the super-gravity rotary packed bed reactor through a feed inlet, wherein the flow ratio is 1:1, rotating at 1500rpm, fully mixing the feed liquid A and the feed liquid B for reaction, collecting slurry, maintaining the temperature at 60 ℃ for ageing for 20min, filtering and washing to obtain CaCO 3 @SiO 2 A composite particle filter cake; caCO is put into 3 @SiO 2 And (3) putting the composite particle filter cake into an acid solution to dissolve nano calcium carbonate, filtering, washing and drying to obtain the nano hollow silica.
FIG. 1 is a transmission electron microscope image of inorganic template nano calcium carbonate used for preparing nano hollow silica in the present example;
FIG. 2 is a transmission electron microscope image obtained in example 1, with an obvious and complete hollow structure and a specific surface area of up to 662.6m 2 /g；
FIG. 3 is an adsorption/desorption isothermal curve of the nano hollow silica in example 1;
FIG. 4 is a graph showing pore size distribution of nano-hollow silica in example 1.
Example 2
A method for rapidly preparing nano hollow silica, comprising the following steps:
according to SiO 2 /CaCO 3 At a ratio of 20% by mass to CaCO 3 Na was added to the suspension having a solids content of 6wt% 2 SiO 3 ·9H 2 O is dissolved and stirred uniformly and is marked as feed liquid A; according to HCl/Na 2 SiO 3 ·9H 2 Preparing a dilute HCl solution with the O ratio of 1.6/1 (molar ratio) to prepare a dilute hydrochloric acid solution, and marking the dilute hydrochloric acid solution as feed liquid B; simultaneously injecting the feed liquid A and the feed liquid B into the super-gravity rotary packed bed reactor through a feed inlet, wherein the flow ratio is 1:1, rotating at 300rpm, fully mixing the feed liquid A and the feed liquid B for reaction, collecting slurry, maintaining the temperature at 40 ℃ for aging for 40min, filtering and washing to obtain CaCO 3 @SiO 2 A composite particle filter cake; caCO is put into 3 @SiO 2 And (3) putting the composite particle filter cake into an acid solution to dissolve nano calcium carbonate, filtering, washing and drying to obtain the nano hollow silica. Fig. 5 is a transmission electron microscope image obtained in this example 2.
Example 3
A method for rapidly preparing nano hollow silica, comprising the following steps:
according to SiO 2 /CaCO 3 At a ratio of 20% by mass to CaCO 3 Na was added to the suspension having a solids content of 6wt% 2 SiO 3 ·9H 2 O is dissolved and stirred uniformly and is marked as feed liquid A; according to HCl/Na 2 SiO 3 ·9H 2 Preparing a dilute HCl solution with the O ratio of 1.6/1 (molar ratio) to prepare a dilute hydrochloric acid solution, and marking the dilute hydrochloric acid solution as feed liquid B; simultaneously injecting the feed liquid A and the feed liquid B into the super-gravity rotary packed bed reactor through a feed inlet, wherein the flow ratio is 1:1, rotating at 300rpm, fully mixing the feed liquid A and the feed liquid B for reaction, collecting slurry, maintaining the temperature at 25 ℃ for ageing for 120min, filtering and washing to obtain CaCO 3 @SiO 2 A composite particle filter cake; caCO is put into 3 @SiO 2 And (3) putting the composite particle filter cake into an acid solution to dissolve nano calcium carbonate, filtering, washing and drying to obtain the nano hollow silica. Fig. 6 is a transmission electron microscope image obtained in example 3.
Example 4
A method for rapidly preparing nano hollow silica, comprising the following steps:
according to SiO 2 /CaCO 3 At a ratio of 20% by mass to CaCO 3 Na was added to the suspension having a solids content of 6wt% 2 SiO 3 ·9H 2 O is dissolved and stirred uniformly and is marked as feed liquid A; according to HCl/Na 2 SiO 3 ·9H 2 Preparing a dilute HCl solution with the O ratio of 1.6/1 (molar ratio) to prepare a dilute hydrochloric acid solution, and marking the dilute hydrochloric acid solution as feed liquid B; simultaneously injecting the feed liquid A and the feed liquid B into the super-gravity rotary packed bed reactor through a feed inlet, wherein the flow ratio is 1:1, rotating at 1000rpm, fully mixing the feed liquid A and the feed liquid B for reaction, collecting slurry, maintaining the temperature at 60 ℃ for ageing for 120min, filtering and washing to obtain CaCO 3 @SiO 2 A composite particle filter cake; caCO is put into 3 @SiO 2 And (3) putting the composite particle filter cake into an acid solution to dissolve nano calcium carbonate, filtering, washing and drying to obtain the nano hollow silica. Fig. 7 is a transmission electron microscope image obtained in this example 4.
Example 5
A method for rapidly preparing nano hollow silica, comprising the following steps:
according to SiO 2 /CaCO 3 At a ratio of 20% by mass to CaCO 3 Na was added to the suspension having a solids content of 6wt% 2 SiO 3 ·9H 2 O is dissolved and stirred uniformly and is marked as feed liquid A; according to HCl/Na 2 SiO 3 ·9H 2 Preparing a dilute HCl solution with the O ratio of 1.6/1 (molar ratio) to prepare a dilute hydrochloric acid solution, and marking the dilute hydrochloric acid solution as feed liquid B; simultaneously injecting the feed liquid A and the feed liquid B into the super-gravity rotary packed bed reactor through a feed inlet, wherein the flow ratio is 1:1, rotating at 2000rpm, fully mixing the feed liquid A and the feed liquid B for reaction, collecting slurry, maintaining the temperature at 60 ℃ for ageing for 20min, filtering and washing to obtain CaCO 3 @SiO 2 A composite particle filter cake; caCO is put into 3 @SiO 2 And (3) putting the composite particle filter cake into an acid solution to dissolve nano calcium carbonate, filtering, washing and drying to obtain the nano hollow silica. Fig. 8 is a transmission electron microscope image obtained in this example 5.
Example 6
A method for rapidly preparing nano hollow silica, comprising the following steps:
according to SiO 2 /CaCO 3 At a ratio of 20% by mass to CaCO 3 Na was added to the suspension having a solids content of 4.5wt% 2 SiO 3 ·9H 2 O is dissolved and stirred uniformly and is marked as feed liquid A; according to HCl/Na 2 SiO 3 ·9H 2 Preparing a dilute HCl solution with the O ratio of 1.6/1 (molar ratio) to prepare a dilute hydrochloric acid solution, and marking the dilute hydrochloric acid solution as feed liquid B; simultaneously injecting the feed liquid A and the feed liquid B into the super-gravity rotary packed bed reactor through a feed inlet, wherein the flow ratio is 1:1, rotating at 300rpm, fully mixing the feed liquid A and the feed liquid B for reaction, collecting slurry, maintaining the temperature at 60 ℃ for ageing for 20min, filtering and washing to obtain CaCO 3 @SiO 2 A composite particle filter cake; caCO is put into 3 @SiO 2 And (3) putting the composite particle filter cake into an acid solution to dissolve nano calcium carbonate, filtering, washing and drying to obtain the nano hollow silica. Fig. 9 is a transmission electron microscope image obtained in this example 1.
Comparative example 1
Example 1 was repeated: the difference is that the flow ratio of the feed liquid A to the feed liquid B is 2:1, the experimental results are as follows: it can be seen from TEM electron microscopy that the obtained nano-hollow silica still has a large amount of hollow structure, but a small amount of solid particles.
Comparative example 2
Example 1 was repeated: the difference is that the flow ratio of the feed liquid A to the feed liquid B is 4:1, the experimental results are as follows: it can be seen from TEM electron microscopy that the obtained nano hollow silica still has a large number of hollow structures, but the solid particles are increased compared to comparative example 1.
Comparative example 3
Example 1 was repeated: the difference is that the flow ratio of the feed liquid A to the feed liquid B is 20:1, the experimental results are as follows: the hollow structure of the obtained nano hollow silica was observed by a TEM electron microscope (see fig. 12), and a large number of solid particles appeared.
Comparative example 4
Example 1 was repeated: the difference is that CaCO in the feed liquid A 3 The solid content was 45wt%, and the experimental results were as follows: the hollow structure of the obtained nano hollow silica was found to exist by TEM electron microscopy (see fig. 13), but a few solid particles were present.
Comparative example 5
Example 1 was repeated: the difference is that CaCO in the feed liquid A 3 The solid content was 50wt%, and the experimental results were as follows: the hollow structure of the obtained nano hollow silica was observed by a TEM electron microscope (see fig. 14), and a large number of solid particles appeared.
Comparative example 6
Example 1 was repeated: the difference is only that the ratio HCl/Na is 2 SiO 3 ·9H 2 The O ratio was 2/1 (molar ratio) to prepare feed liquid B, and the experimental results were as follows: the hollow structure of the obtained nano hollow silica was found to exist by TEM electron microscopy (see fig. 15), but solid particles were present.
Comparative example 7
Example 1 was repeated: the difference is only that the ratio HCl/Na is 2 SiO 3 ·9H 2 The O ratio was 2.4/1 (molar ratio) to prepare feed liquid B, and the experimental results were as follows: it can be seen by TEM electron microscopy (see fig. 16) that there is essentially no hollow structure.
Comparative example 8
Example 1 was repeated: the difference is that the aging temperature is 15 ℃ and the aging time is 2min, and the experimental result is as follows: the hollow structure of the obtained nanomaterial is not complete as can be seen by TEM electron microscopy (see fig. 17).
Comparative example 9
In order to study the effect of the supergravity technology on the morphology of the nano hollow silica, the experiment was performed in a conventional Stirred Tank Reactor (STR), the reaction conditions were the same as those of the supergravity rotating packed bed reactor in example 1, and the experimental results were as follows: it can be seen from TEM electron microscopy that the hollow structure of the obtained nanomaterial is largely broken, and the yield, specific surface area are low compared to the supergravity technique. FIG. 19 is an adsorption/desorption isothermal curve of nano hollow silica in comparative example 9.
Comparative example 10
In order to study the influence of the supergravity technology on the morphology of the nano hollow silica, experiments were carried out in a conventional Stirred Tank Reactor (STR), and the reaction conditions were the same as those of the supergravity reactor in example 1, except that dropwise addition of feed was adopted for 30min, and the experimental results were as follows: it can be seen from TEM electron microscopy (see fig. 20) that the obtained nanomaterial has small solid particles, and the time required for STR is greatly prolonged compared to the supergravity technique.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. Not all embodiments are exhaustive. All obvious changes or modifications which come within the spirit of the invention are desired to be protected.

Claims (10)

1. A method for rapidly preparing nano hollow silica, which is characterized by comprising the following steps:
s1, adding a nano calcium carbonate filter cake and sodium silicate into water according to a certain proportion to prepare a suspension of nano calcium carbonate and sodium silicate, and marking the suspension as feed liquid A;
s2, adding organic acid or inorganic acid into water to prepare an acidic solution, and marking the acidic solution as feed liquid B;
s3, simultaneously injecting the feed liquid A and the feed liquid B into the super-gravity rotating packed bed reactor through the feed inlet to enable the feed liquid A and the feed liquid B to be fully mixed and reacted, collecting slurry, preserving heat and aging, filtering and washing to obtain CaCO 3 @SiO 2 A composite particle filter cake;
s4, caCO is added 3 @SiO 2 And (3) putting the composite particle filter cake into an organic acid or inorganic acid solution to dissolve nano calcium carbonate, filtering, washing and drying to obtain nano hollow silicon dioxide.
2. The method for rapidly preparing nano-hollow silica according to claim 1, wherein: in the step S1, the nano calcium carbonate is in a needle shape, a spindle shape, a sphere shape, a cube shape, a petal shape or a sheet shape.
3. The method for rapidly preparing nano-hollow silica according to claim 1, wherein: in the step S1, the concentration of the nano calcium carbonate in the feed liquid A is 2-40wt%; the concentration of sodium silicate in the feed liquid A is 2-40wt%.
4. The method for rapidly preparing nano-hollow silica according to claim 1, wherein: in step S2, the organic acid or inorganic acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, selenous acid, phosphoric acid, perchloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, hydrocyanic acid, sulfurous acid, nitrous acid, citric acid, lactic acid, tartaric acid, malic acid, meta-tartaric acid, oxalic acid, and fumaric acid solution.
5. The method for rapidly preparing nano-hollow silica according to claim 1, wherein: in the step S2, the concentration of the feed liquid B is 0.01mol/L-2mol/L.
6. The method for rapidly preparing nano-hollow silica according to claim 1, wherein: in the step S3, the temperature of heat preservation and aging is 20-90 ℃; more preferably, the temperature of the insulated aging is 30-80 ℃.
7. The method for rapidly preparing nano-hollow silica according to claim 1, wherein: in the step S3, the heat preservation aging time is 5-120min.
8. The method for rapidly preparing nano-hollow silica according to claim 1, wherein: in the step S3, the feeding flow rate of the feed liquid A is 20-2000mL/min, and the feeding flow rate of the feed liquid B is 20-2000mL/min; the feeding flow rate ratio of the feed liquid A to the feed liquid B is 1:3-3:1, and the volume flow ratio of the feed liquid A to the feed liquid B which is introduced into the super-gravity rotary packed bed reactor is 0.3-3.
9. The method for rapidly preparing nano-hollow silica according to claim 1, wherein: in the step S3, the rotating speed of the rotor of the super-gravity rotating packed bed reactor is 300-3000rpm; more preferably, the rotor speed of the super gravity rotating packed bed reactor is 500-2500rpm.
10. The method for rapidly preparing nano-hollow silica according to claim 1, wherein: in the step S4, the shell thickness of the nano hollow silicon dioxide is 1-30nm;
preferably, in step S4, the drying is air drying, the drying temperature is 25-120 ℃, and the drying time is 2-24 hours; more preferably, the drying temperature is 30-110 ℃ and the drying time is 3-14h.
CN202310204552.3A 2023-03-03 2023-03-03 Method for rapidly preparing nano hollow silicon dioxide Pending CN116282052A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002070409A1 (en) * 2001-03-07 2002-09-12 Anshan University Of Science And Technology Process for producing nanometer grade powders
CN1445311A (en) * 2002-03-20 2003-10-01 新加坡纳米材料科技有限公司 calcium carbonate/silicon dioxide-water(1/n) nano-compound particle and hollow silicon dioxide-water(1/n) nano-material and its preparation method
CN1781997A (en) * 2004-12-02 2006-06-07 北京化工大学 Novel SiO2 carrier material and use in polyolefin catalyst and its preparing method
CN1803938A (en) * 2005-01-10 2006-07-19 北京化工大学 TiO2/CaCO3 nano composite particle, hollow TiO2 nano material and method for preparing the same
CN109205630A (en) * 2017-07-06 2019-01-15 北京化工大学 A kind of preparation method of monodisperse nano silicon dioxide transparent dispersion

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002070409A1 (en) * 2001-03-07 2002-09-12 Anshan University Of Science And Technology Process for producing nanometer grade powders
CN1445311A (en) * 2002-03-20 2003-10-01 新加坡纳米材料科技有限公司 calcium carbonate/silicon dioxide-water(1/n) nano-compound particle and hollow silicon dioxide-water(1/n) nano-material and its preparation method
CN1781997A (en) * 2004-12-02 2006-06-07 北京化工大学 Novel SiO2 carrier material and use in polyolefin catalyst and its preparing method
CN1803938A (en) * 2005-01-10 2006-07-19 北京化工大学 TiO2/CaCO3 nano composite particle, hollow TiO2 nano material and method for preparing the same
CN109205630A (en) * 2017-07-06 2019-01-15 北京化工大学 A kind of preparation method of monodisperse nano silicon dioxide transparent dispersion

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