WO2024183307A1 - 一种快速制备纳米空心二氧化硅的方法 - Google Patents

一种快速制备纳米空心二氧化硅的方法 Download PDF

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WO2024183307A1
WO2024183307A1 PCT/CN2023/128180 CN2023128180W WO2024183307A1 WO 2024183307 A1 WO2024183307 A1 WO 2024183307A1 CN 2023128180 W CN2023128180 W CN 2023128180W WO 2024183307 A1 WO2024183307 A1 WO 2024183307A1
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acid
feed liquid
hollow silica
nano hollow
feed
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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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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the technical field of material preparation, and in particular relates to a method for rapidly preparing nano hollow silica.
  • hollow materials Compared with conventional materials, hollow materials have a unique hollow structure that gives them low density, large specific surface area, special optical properties and high loading capacity. Therefore, they have been widely used in optics, electronics, catalysis and controlled release in the past few decades.
  • silica Among the available inorganic matrices, silica has high biocompatibility, thermodynamic and mechanical stability, and is easy to functionalize. Therefore, nano hollow silica has greater utilization potential than other hollow inorganic materials.
  • template-assisted synthesis is the most common.
  • Gao Yunhao of Huazhong Agricultural University used polystyrene as a hard template, surfactant hexadecyltrimethylammonium bromide (CTAB) as a pore expander, and tetraethyl orthosilicate (TEOS) as a silicon source to prepare nano hollow silica.
  • CTAB surfactant hexadecyltrimethylammonium bromide
  • TEOS tetraethyl orthosilicate
  • nano hollow silica with a particle size of about 500nm, a pore size of 2.96nm, and a specific surface area of 711.28m2 /g was obtained (Gao Yunhao, Master's thesis of Huazhong Agricultural University, 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. used nano-calcium carbonate as a hard template, surfactant as a soft template, and sodium silicate as a silicon source to prepare nano-hollow silica with a diameter of about 70 nm, a wall thickness of about 15 nm, and a pore size of 4 nm.
  • polystyrene microspheres and tetraethyl orthosilicate are expensive and difficult to meet the needs of large-scale applications.
  • the preparation method using sodium silicate as the silicon source is to add materials by dripping, and the auxiliary time and reaction time of disassembling equipment and loading and discharging materials in the intermittent reaction production process are long, and the product performance between batches is unstable, making industrial amplification difficult. Therefore, in view of the shortcomings of the existing methods, a preparation method of nano hollow silica with simple process flow, low energy consumption, short time, low cost and easy mass production is needed.
  • the technical problem to be solved by the present invention is to provide a method for rapidly preparing nano hollow silica; the preparation method adopts a high gravity rotating packed bed reactor to greatly enhance the mass transfer and micro-mixing process of the reaction, and prepares CaCO 3 @SiO 2 composite particles with uniform particle size; the CaCO 3 @SiO 2 composite particles are then placed in an acidic solution to dissolve nano calcium carbonate, and the nano hollow silica is obtained by filtering, washing and drying.
  • the present invention adopts the following technical solution:
  • a method for rapidly preparing nano hollow silica comprises the following steps:
  • the shape of the nano calcium carbonate is needle-shaped, spindle-shaped, spherical, cubic, petal-shaped or flake-shaped.
  • the concentration of nano calcium carbonate in the slurry A is 2-40wt%.
  • the concentration of sodium silicate in the slurry A is 2-40wt%.
  • the organic acid or inorganic acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, selenic 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, metatartaric acid, oxalic acid, and fumaric acid solution.
  • the concentration of the feed solution B is 0.01 mol/L-2 mol/L.
  • the temperature of the heat preservation and aging is 20-90°C; more preferably, the temperature of the heat preservation and aging is 30-80°C;
  • the heat preservation and aging time is 5-120 minutes.
  • the feed flow rate of the feed liquid A is 20-2000 mL/min
  • the feed flow rate of the feed liquid B is 20-2000 mL/min
  • the feed flow rate ratio of the feed liquid A to the feed liquid B is 1:3-3:1
  • the feed liquid A and the feed liquid B are passed through
  • the volume flow ratio into the supergravity rotating packed bed reactor is 0.3-3.
  • the rotor speed of the high gravity rotating packed bed reactor is 300-3000 rpm; more preferably, the rotor speed of the high gravity rotating packed bed reactor is 500-2500 rpm.
  • the shell thickness of the nano hollow silica is 1-30 nm.
  • the drying is forced air drying
  • the drying temperature is 25-120° C.
  • the drying time is 2-24 h; more preferably, the drying temperature is 30-110° C., and the drying time is 3-14 h.
  • Any range described in the present invention includes the end value and any numerical value between the end values and any sub-range formed by the end value or any numerical value between the end values.
  • the preparation of nano hollow silica in the prior art is mainly based on the polystyrene organic template method, which has a large particle size, is expensive, and is difficult to scale up industrially; and the auxiliary time and reaction time for disassembling equipment and loading and unloading materials in the intermittent reaction production process are long, and the product performance is unstable between batches.
  • the present invention uses ultra-gravity technology to achieve rapid production of nano hollow silica, and determines the effects of various control conditions on product performance, thereby preparing high-quality nano hollow silica materials suitable for industrial applications;
  • the nano hollow silica prepared by the present invention is spherical and has a particle size of 80-100 nm;
  • the nano hollow silica prepared by the present invention is spherical and has a controllable thickness of 1-20 nm;
  • the process of the present invention is simple, no organic solvent is required in the preparation process, and the raw materials are cheap and easily available, the production efficiency is high, and it is suitable for mass production.
  • FIG1 is a transmission electron microscope image of the inorganic template nano calcium carbonate used in preparing nano hollow silica in Example 1;
  • FIG2 is a transmission electron microscope image of nano hollow silica in Example 1;
  • FIG3 is an adsorption-desorption isotherm of nano hollow silica in Example 1;
  • FIG4 is a transmission electron microscope image of nano hollow silica in Example 1.
  • FIG5 is a transmission electron microscope image of nano hollow silica in Example 2.
  • FIG6 is a transmission electron microscope image of nano hollow silica in Example 3.
  • FIG7 is a transmission electron microscope image of nano hollow silica in Example 4.
  • FIG8 is a transmission electron microscope image of nano hollow silica in Example 5.
  • FIG9 is a transmission electron microscope image of nano hollow silica in Example 6.
  • FIG10 is a transmission electron microscope image of nano hollow silica in Comparative Example 1;
  • FIG11 is a transmission electron microscope image of nano hollow silica in Comparative Example 2.
  • FIG12 is a transmission electron microscopy image of nano hollow silica in Comparative Example 3.
  • FIG13 is a transmission electron microscopy image of nano hollow silica in Comparative Example 4.
  • FIG14 is a transmission electron microscopy image of nano hollow silica in Comparative Example 5.
  • FIG15 is a transmission electron microscope image of nano hollow silica in Comparative Example 6;
  • FIG16 is a transmission electron microscopy image of nano hollow silica in Comparative Example 7.
  • FIG17 is a transmission electron microscope image of nano hollow silica in Comparative Example 8.
  • FIG18 is a transmission electron microscope image of nano hollow silica in Comparative Example 9;
  • FIG19 is an adsorption-desorption isotherm of nano hollow silica in Comparative Example 9;
  • FIG20 is a transmission electron microscope image of nano hollow silica in Comparative Example 10.
  • FIG. 21 is a schematic diagram of the flow chart of the technical solution of the present invention.
  • a method for rapidly preparing nano hollow silica comprises the following steps:
  • feed liquid A and feed liquid B are simultaneously injected into the high gravity rotating packed bed reactor through the feed inlet, so that feed liquid A Fully mix with liquid B for reaction, collect the slurry and keep it warm for aging, filter and wash to obtain a CaCO 3 @SiO 2 composite particle filter cake;
  • the shape of the nano-calcium carbonate is needle-shaped, spindle-shaped, spherical, cubic, petal-shaped or flake-shaped.
  • the concentration of nano calcium carbonate in the slurry 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%.
  • the concentration of sodium silicate in the slurry 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%, 10-3 0wt%, 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%.
  • the organic acid or inorganic acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, selenic 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, metatartaric acid, oxalic acid, and fumaric acid solution.
  • the concentration of the slurry B is 0.01 mol/L-2 mol/L.
  • the temperature of the thermal insulation aging is 20-90°C, including but not limited to 20-80°C, 20-70°C, 20-60°C, 20-50°C, 20-40°C, 20-30°C, 30-90°C, 30-80°C, 30-70°C, 30-60°C, 30-50°C, 30-40°C, 20-30°C, 40-90°C, 40-80°C, 40-70°C, 40-60°C, 40-50°C, 50-90°C, 50-80°C, 50-70°C, 50-60°C, 60-90°C, 60-80°C, 60-70°C, 70-90°C, 70-80°C, 80-90°C.
  • the heat preservation and aging time is 5-120 minutes, including but not limited to 5-110 minutes, 5-100min,5-90min,5-80min,5-70min,5-60min,5-50min,5-40min,5-30min,5-20min,5-10min,10-120min,10-110min,10-100min,10-90min,10-80min,10-70min,10-60min,10-50min,1 0-40min, 10-30min, 10-20min, 20-120min, 20-110min, 20-100min, 20-90min, 20-80min, 20-70min, 20-60min, 20-50min, 20-40min, 20-30min, 30-120min, 30-110min, 30-100m in, 30-90min, 30-80min, 30-70min, 30-80min, 30-70min, 30-80min, 30-70min, 30-80min, 30-70min, 30-80min, 30-70min, 30-60min, 30-50min, 30-40min, 40-120min, 40-110min, 40-100min, 40-90min, 40-80min,
  • step S3 the feed flow rate of the feed liquid A is 20-2000 mL/min, and the feed flow rate of the feed liquid B is 20-2000 mL/min; the feed 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 passing into the high gravity rotating packed bed reactor is 0.3-3.
  • the rotor speed of the ultragravity 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, and 1000-1500rpm.
  • the shell thickness of the nano hollow silica is 1-30 nm.
  • the drying is forced air drying
  • the drying temperature is 25-120°C
  • the drying time is 2-24h; more preferably, the drying temperature is 30-110°C, and the drying time is 3-14h.
  • a method for rapidly preparing nano hollow silica according to the present invention comprises the following steps:
  • Na2SiO3 ⁇ 9H2O is added to a suspension with a solid content of CaCO3 of 6wt % and dissolved, and stirred evenly, which is recorded as feed liquid A; hydrochloric acid is added to water to prepare a dilute hydrochloric acid solution, which is recorded as feed liquid B; feed liquid A and feed liquid B are simultaneously injected into a high-gravity rotating packed bed reactor through a feed inlet, with a flow ratio of 1:1 and a rotation speed of 1500rpm, so that feed liquid A and feed liquid B are fully mixed and reacted, the slurry is collected and aged at 60°C for 20min, filtered and washed to obtain a CaCO3 @ SiO2 composite particle filter cake; the CaCO3 @ SiO2 composite particle filter cake is placed in an acidic solution to dissolve nano calcium carbonate, filtered, washed and dried to obtain nano hollow silica.
  • FIG1 is a transmission electron microscope image of the inorganic template nano calcium carbonate used to prepare nano hollow silica in this embodiment
  • FIG2 is a transmission electron microscope image obtained in Example 1, showing an obvious and complete hollow structure, with a specific surface area as high as 662.6 m 2 /g;
  • FIG3 is an adsorption-desorption isotherm of nano hollow silica in Example 1;
  • FIG. 4 is a pore size distribution curve of nano hollow silica in Example 1.
  • a method for rapidly preparing nano hollow silica comprises the following steps:
  • a method for rapidly preparing nano hollow silica comprises the following steps:
  • a method for rapidly preparing nano hollow silica comprises the following steps:
  • Na2SiO3 ⁇ 9H2O was added to a suspension containing 6wt% CaCO3 at a SiO2 / CaCO3 ratio of 20% (mass ratio) and dissolved, and stirred evenly, which was recorded as feed liquid A.
  • a dilute HCl solution was prepared at a HCl / Na2SiO3 ⁇ 9H2O ratio of 1.6/1 (molar ratio) to prepare a dilute hydrochloric acid solution, which was recorded as feed liquid B.
  • Feed liquid A and feed liquid B were simultaneously injected into the feed port .
  • a method for rapidly preparing nano hollow silica comprises the following steps:
  • Example 1 was repeated, except that the flow ratio of liquid A to liquid B was 2:1.
  • the experimental results were as follows: As can be seen from the TEM electron microscope (see FIG. 10 ), the obtained nano hollow silica still had a large number of hollow structures, but a small number of solid particles.
  • Example 1 was repeated: the only difference was that the flow ratio of liquid A to liquid B was 4:1, and the experimental results were as follows: It can be seen from the TEM electron microscope (see Figure 11) that the obtained nano hollow silica still has a large number of hollow structures, but the solid particles are increased compared with Comparative Example 1.
  • Example 1 was repeated, except that the flow ratio of liquid A to liquid B was 20:1.
  • the experimental results were as follows: TEM electron microscopy showed (see FIG. 12 ) that the obtained nano hollow silica had a hollow structure and a large number of solid particles.
  • Example 1 was repeated, except that the solid content of CaCO 3 in liquid A was 45 wt %.
  • the experimental results were as follows: TEM electron microscopy showed (see FIG. 13 ) that the obtained nano hollow silica had a hollow structure, but a small amount of solid particles.
  • Example 1 was repeated, except that the solid content of CaCO 3 in liquid A was 50 wt %.
  • the experimental results were as follows: It can be seen from the TEM electron microscope (see FIG. 14 ) that the obtained nano hollow silica has a hollow structure and a large number of solid particles.
  • Example 1 was repeated except that the feed solution B was prepared at a molar ratio of HCl/Na 2 SiO 3 ⁇ 9H 2 O of 2/1.
  • the experimental results are as follows: TEM electron microscopy (see FIG. 15 ) shows that the obtained nano hollow silica has a hollow structure, but solid particles appear.
  • Example 1 was repeated except that the feed solution B was prepared at a molar ratio of HCl/Na 2 SiO 3 ⁇ 9H 2 O of 2.4/1.
  • the experimental results are as follows: It can be seen from the TEM (see FIG. 16 ) that there is basically no hollow structure.
  • Example 1 was repeated, except that the aging temperature was 15° C. and the aging time was 2 min.
  • the experimental results were as follows: It can be seen from the TEM electron microscope (see FIG. 17 ) that the hollow structure of the obtained nanomaterial is incomplete.

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Abstract

一种快速制备纳米空心二氧化硅的方法，包括如下步骤：将纳米碳酸钙滤饼和硅酸钠按一定比例加入水中，配制成纳米碳酸钙和硅酸钠的悬浮液，记为料液A；将有机酸或无机酸加入到水中，配置成酸性溶液，记为料液B；将料液A和料液B通过进料口同时注入到超重力旋转填充床反应器中，使料液A和料液B充分混合反应，收集浆料并保温陈化，过滤、洗涤得到CaCO 3@SiO 2复合粒子滤饼；将滤饼置于酸溶液中溶解纳米碳酸钙，过滤、洗涤、干燥得到纳米空心二氧化硅。利用超重力技术，可快速制备出低成本优质纳米空心二氧化硅材料，粒径在10-500nm，厚度可控为1-20nm；制备过程中无需任何有机溶剂，适合大批量生产。

Description

一种快速制备纳米空心二氧化硅的方法 技术领域
本发明属于材料制备技术领域，尤其是涉及一种快速制备纳米空心二氧化硅的方法。
背景技术
空心材料与常规材料相比，独特的空心结构使它们具有低密度、大比表面积、特殊的光学性质和高负载能力。因此，它们在过去的几十年中被广泛应用于光学、电子学、催化和缓控释等领域。在可用的无机基质中，二氧化硅具有高度的生物相容性、热力学和机械稳定性，且易于功能化。因此，纳米空心二氧化硅与其他中空无机材料相比具有更大的利用潜力。
目前，国内外制备纳米空心二氧化硅的方法有很多，主要包括：模板辅助合成、喷雾干燥法、自组装技术、乳液/界面聚合法等。其中模板辅助合成是最为常见的。华中农业大学的高云昊以聚苯乙烯为硬模板，表面活性剂为十六烷基三甲基溴化铵(CTAB)作为扩孔剂，正硅酸乙酯(TEOS)为硅源来制备纳米空心二氧化硅。最后得到了粒径大约为500nm，孔径为2.96nm，比表面积为711.28m2/g的纳米空心二氧化硅(高云昊，华中农业大学硕士学位论文，2018)。
李珠柱(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.)利用纳米纳米碳酸钙为硬模板，表面活性剂为软模板，以硅酸钠为硅源，制备了直径约为70nm，壁厚约为15nm，孔径4nm的纳米空心二氧化硅。
在上述制备方法中，聚苯乙烯微球、正硅酸乙酯价格昂贵，难以满足大规模应用需求。与此同时，以硅酸钠为硅源的制备方法，都是采用滴加的方式加料，且主要是间歇反应生产过程中拆装设备及装料出料的辅助时间和反应时间较长，且各批次间产品性能不稳定，工业放大困难。因此，针对现有方法的不足，需要一种工艺流程简单、能耗低、时间短、成本低且易大批量生产的纳米空心二氧化硅的制备方法。
发明内容
本发明要解决的技术问题是提供一种快速制备纳米空心二氧化硅的方法；该制备方法通过采用超重力旋转填充床反应器，极大地强化了反应的传质和微观混合过程，制备出粒度均一的CaCO3@SiO2复合粒子；再将CaCO3@SiO2复合粒子置于酸性溶液中溶解纳米碳酸钙，过滤、洗涤、干燥得到纳米空心二氧化硅。
为解决上述第一个技术问题，本发明采用如下的技术方案：
一种快速制备纳米空心二氧化硅的方法，包括如下步骤：
S1、将纳米碳酸钙滤饼和硅酸钠按一定比例加入水中，配制成纳米碳酸钙和硅酸钠的悬浮液，记为料液A；
S2、将有机酸或无机酸加入到水中，配置成酸性溶液，记为料液B；
S3、将料液A和料液B通过进料口同时注入到超重力旋转填充床反应器中，使料液A和料液B充分混合反应，收集浆料并保温陈化，过滤、洗涤得到CaCO3@SiO2复合粒子滤饼；
S4、将CaCO3@SiO2复合粒子滤饼置于有机酸或无机酸溶液中溶解纳米碳酸钙，过滤、洗涤、干燥得到纳米空心二氧化硅。
优选地，步骤S1中，所述纳米碳酸钙的形状为针状、纺锤状、球形、立方形、花瓣形或片状。
优选地，步骤S1中，所述料液A中的纳米碳酸钙浓度为2-40wt％。
优选地，步骤S1中，所述料液A中硅酸钠的浓度为2-40wt％。
优选地，步骤S2中，所述有机酸或无机酸为盐酸、硫酸、硝酸、醋酸、硒酸、磷酸、高氯酸、氢氟酸、氢溴酸、氢碘酸、氢氰酸、亚硫酸、亚硝酸、柠檬酸、乳酸、酒石酸、苹果酸、偏酒石酸、乙二酸、富马酸溶液的一种或多种。
优选地，步骤S2中，所述料液B的浓度为0.01mol/L-2mol/L。
优选地，步骤S3中，所述保温陈化的温度为20-90℃；更优选地，所述保温陈化的温度为30-80℃；
优选地，步骤S3中，所述保温陈化时间为5-120min。
优选地，步骤S3中，所述料液A进料流率为20-2000mL/min，料液B进料流率为20-2000mL/min；所述料液A与料液B进料流率比为1:3-3:1，且所述料液A与料液B通 入超重力旋转填充床反应器的体积流量比为0.3-3。
优选地，步骤S3中，所述超重力旋转填充床反应器的转子转速为300-3000rpm；更优选地，所述超重力旋转填充床反应器的转子转速为500-2500rpm。
优选地，步骤S4中，所述纳米空心二氧化硅的壳层厚度为1-30nm。
优选地，步骤S4中，所述干燥为鼓风干燥，干燥温度为25-120℃，干燥时间为2-24h；更优选地，干燥温度为30-110℃，干燥时间为3-14h。
本发明所记载的任何范围包括端值以及端值之间的任何数值以及端值或者端值之间的任意数值所构成的任意子范围。
如无特殊说明，本发明中的各原料均可通过市售购买获得，本发明中所用的设备可采用所属领域中的常规设备或参照所属领域的现有技术进行。
与现有技术相比较，本发明具有如下有益效果：
1)现有技术中关于纳米空心二氧化硅的制备主要是聚苯乙烯有机模板法，粒径较大，价格昂贵，工业放大困难；且主要是间歇反应生产过程中拆装设备及装料出料的辅助时间和反应时间较长，且各批次间产品性能不稳定。本发明利用超重力技术来实现快速化生产纳米空心二氧化硅，并确定各种控制条件对产品性能的影响，从而制备出适合工业应用的优质纳米空心二氧化硅材料；
2)本发明制备的纳米空心二氧化硅成球形，粒径在80-100nm；
3)本发明制备的纳米空心二氧化硅成球形，厚度可控为1-20nm；
4)本发明工艺过程简单，制备过程中无需任何有机溶剂，且原料价格低廉易得，生产效率高，适合大批量生产。
附图说明
下面结合附图对本发明的具体实施方式作进一步详细的说明
图1为实施例1中制备纳米空心二氧化硅所用无机模板纳米碳酸钙的透射电镜图；
图2为实施例1中纳米空心二氧化硅透射电镜图；
图3为实施例1中纳米空心二氧化硅吸附脱附等温曲线；
图4为实施例1中纳米空心二氧化硅透射电镜图；
图5为实施例2中纳米空心二氧化硅透射电镜图；
图6为实施例3中纳米空心二氧化硅透射电镜图；
图7为实施例4中纳米空心二氧化硅透射电镜图；
图8为实施例5中纳米空心二氧化硅透射电镜图；
图9为实施例6中纳米空心二氧化硅透射电镜图；
图10为对比例1中纳米空心二氧化硅透射电镜图；
图11为对比例2中纳米空心二氧化硅透射电镜图；
图12为对比例3中纳米空心二氧化硅透射电镜图；
图13为对比例4中纳米空心二氧化硅透射电镜图；
图14为对比例5中纳米空心二氧化硅透射电镜图；
图15为对比例6中纳米空心二氧化硅透射电镜图；
图16为对比例7中纳米空心二氧化硅透射电镜图；
图17为对比例8中纳米空心二氧化硅透射电镜图；
图18为对比例9中纳米空心二氧化硅透射电镜图；
图19为对比例9中纳米空心二氧化硅吸附脱附等温曲线；
图20为对比例10中纳米空心二氧化硅透射电镜图；
图21为本发明技术方案的流程示意图。
具体实施方式
为了更清楚地说明本发明，下面结合优选实施例对本发明做进一步的说明。本领域技术人员应当理解，下面所具体描述的内容是说明性的而非限制性的，不应以此限制本发明的保护范围。
作为本发明的一个方面，本发明一种快速制备纳米空心二氧化硅的方法，包括如下步骤：
S1、将纳米碳酸钙滤饼和硅酸钠按一定比例加入水中，配制成纳米碳酸钙和硅酸钠的悬浮液，记为料液A；
S2、将有机酸或无机酸加入到水中，配置成酸性溶液，记为料液B；
S3、将料液A和料液B通过进料口同时注入到超重力旋转填充床反应器中，使料液A 和料液B充分混合反应，收集浆料并保温陈化，过滤、洗涤得到CaCO3@SiO2复合粒子滤饼；
S4、将CaCO3@SiO2复合粒子滤饼置于有机酸或无机酸溶液中溶解纳米碳酸钙，过滤、洗涤、干燥得到纳米空心二氧化硅。
在某些实施例中，步骤S1中，所述纳米碳酸钙的形状为针状、纺锤状、球形、立方形、花瓣形或片状。
在某些实施例中，步骤S1中，所述料液A中的纳米碳酸钙浓度为2-40wt％，包括但不限于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％或35-40wt％。
在某些实施例中，步骤S1中，所述料液A中硅酸钠的浓度为2-40wt％，包括但不限于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％。
在某些实施例中，步骤S2中，所述有机酸或无机酸为盐酸、硫酸、硝酸、醋酸、硒酸、磷酸、高氯酸、氢氟酸、氢溴酸、氢碘酸、氢氰酸、亚硫酸、亚硝酸、柠檬酸、乳酸、酒石酸、苹果酸、偏酒石酸、乙二酸、富马酸溶液的一种或多种。
在某些实施例中，步骤S2中，所述料液B的浓度为0.01mol/L-2mol/L。
在某些实施例中，步骤S3中，所述保温陈化的温度为20-90℃，包括但不限于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℃。
在某些实施例中，步骤S3中，所述保温陈化时间为5-120min，包括但不限于5-110min、 5-100min、5-90min、5-80min、5-70min、5-60min、5-50min、5-40min、5-30min、5-20min、5-10min、10-120min、10-110min、10-100min、10-90min、10-80min、10-70min、10-60min、10-50min、10-40min、10-30min、10-20min、20-120min、20-110min、20-100min、20-90min、20-80min、20-70min、20-60min、20-50min、20-40min、20-30min、30-120min、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。
在某些实施例中，步骤S3中，所述料液A进料流率为20-2000mL/min，料液B进料流率为20-2000mL/min；所述料液A与料液B进料流率比为1:3-3:1，且所述料液A与料液B通入超重力旋转填充床反应器的体积流量比为0.3-3。
在某些实施例中，步骤S3中，所述超重力旋转填充床反应器的转子转速为300-3000rpm，包括但不限于300-2500rpm、300-2000rpm、300-1500rpm、300-1000rpm、300-500rpm、500-2500rpm、500-2000rpm、500-1500rpm、500-1000rpm、1000-2500rpm、1000-2000rpm、1000-1500rpm。
在某些实施例中，步骤S4中，所述纳米空心二氧化硅的壳层厚度为1-30nm。
在某些实施例中，步骤S4中，所述干燥为鼓风干燥，干燥温度为25-120℃，干燥时间为2-24h；更优选地，干燥温度为30-110℃，干燥时间为3-14h。
实施例1
参见图21所示，本发明一种快速制备纳米空心二氧化硅的方法，包括如下步骤：
按SiO2/CaCO3的比例为20％(质量比)往CaCO3固含量为6wt％的悬浮液加入Na2SiO3·9H2O并溶解，搅拌均匀，记为料液A；将盐酸加入到水中，配置成稀盐酸溶液，记为料液B；将料液A和料液B通过进料口同时注入到超重力旋转填充床反应器中，流量比为1：1，转速为1500rpm，使料液A和料液B充分混合反应，收集浆料并60℃保温陈化20min，过滤、洗涤得到CaCO3@SiO2复合粒子滤饼；将CaCO3@SiO2复合粒子滤饼置于酸性溶液中溶解纳米碳酸钙，过滤、洗涤、干燥得到纳米空心二氧化硅。
图1为本实施例中制备纳米空心二氧化硅所用无机模板纳米碳酸钙的透射电镜图；
图2为本实施例1所获得的透射电镜图，空心结构明显、完整，比表面积高达662.6m2/g；
图3为实施例1中纳米空心二氧化硅吸附脱附等温曲线；
图4为实施例1中纳米空心二氧化硅孔径分布曲线。
实施例2
一种快速制备纳米空心二氧化硅的方法，包括如下步骤：
按SiO2/CaCO3的比例为20％(质量比)往CaCO3固含量为6wt％的悬浮液加入Na2SiO3·9H2O并溶解，搅拌均匀，记为料液A；按HCl/Na2SiO3·9H2O比例为1.6/1(摩尔比)配置稀HCl溶液，配置成稀盐酸溶液，记为料液B；将料液A和料液B通过进料口同时注入到超重力旋转填充床反应器中，流量比为1：1，转速为300rpm，使料液A和料液B充分混合反应，收集浆料并40℃保温陈化40min，过滤、洗涤得到CaCO3@SiO2复合粒子滤饼；将CaCO3@SiO2复合粒子滤饼置于酸性溶液中溶解纳米碳酸钙，过滤、洗涤、干燥得到纳米空心二氧化硅。图5为本实施例2所获得的透射电镜图。
实施例3
一种快速制备纳米空心二氧化硅的方法，包括如下步骤：
按SiO2/CaCO3的比例为20％(质量比)往CaCO3固含量为6wt％的悬浮液加入Na2SiO3·9H2O并溶解，搅拌均匀，记为料液A；按HCl/Na2SiO3·9H2O比例为1.6/1(摩尔比)配置稀HCl溶液，配置成稀盐酸溶液，记为料液B；将料液A和料液B通过进料口同时注入到超重力旋转填充床反应器中，流量比为1：1，转速为300rpm，使料液A和料液B充分混合反应，收集浆料并25℃保温陈化120min，过滤、洗涤得到CaCO3@SiO2复合粒子滤饼；将CaCO3@SiO2复合粒子滤饼置于酸性溶液中溶解纳米碳酸钙，过滤、洗涤、干燥得到纳米空心二氧化硅。图6为本实施例3所获得的透射电镜图。
实施例4
一种快速制备纳米空心二氧化硅的方法，包括如下步骤：
按SiO2/CaCO3的比例为20％(质量比)往CaCO3固含量为6wt％的悬浮液加入Na2SiO3·9H2O并溶解，搅拌均匀，记为料液A；按HCl/Na2SiO3·9H2O比例为1.6/1(摩尔比)配置稀HCl溶液，配置成稀盐酸溶液，记为料液B；将料液A和料液B通过进料口同时注 入到超重力旋转填充床反应器中，流量比为1：1，转速为1000rpm，使料液A和料液B充分混合反应，收集浆料并60℃保温陈化120min，过滤、洗涤得到CaCO3@SiO2复合粒子滤饼；将CaCO3@SiO2复合粒子滤饼置于酸性溶液中溶解纳米碳酸钙，过滤、洗涤、干燥得到纳米空心二氧化硅。图7为本实施例4所获得的透射电镜图。
实施例5
一种快速制备纳米空心二氧化硅的方法，包括如下步骤：
按SiO2/CaCO3的比例为20％(质量比)往CaCO3固含量为6wt％的悬浮液加入Na2SiO3·9H2O并溶解，搅拌均匀，记为料液A；按HCl/Na2SiO3·9H2O比例为1.6/1(摩尔比)配置稀HCl溶液，配置成稀盐酸溶液，记为料液B；将料液A和料液B通过进料口同时注入到超重力旋转填充床反应器中，流量比为1：1，转速为2000rpm，使料液A和料液B充分混合反应，收集浆料并60℃保温陈化20min，过滤、洗涤得到CaCO3@SiO2复合粒子滤饼；将CaCO3@SiO2复合粒子滤饼置于酸性溶液中溶解纳米碳酸钙，过滤、洗涤、干燥得到纳米空心二氧化硅。图8为本实施例5所获得的透射电镜图。
实施例6
一种快速制备纳米空心二氧化硅的方法，包括如下步骤：
按SiO2/CaCO3的比例为20％(质量比)往CaCO3固含量为4.5wt％的悬浮液加入Na2SiO3·9H2O并溶解，搅拌均匀，记为料液A；按HCl/Na2SiO3·9H2O比例为1.6/1(摩尔比)配置稀HCl溶液，配置成稀盐酸溶液，记为料液B；将料液A和料液B通过进料口同时注入到超重力旋转填充床反应器中，流量比为1：1，转速为300rpm，使料液A和料液B充分混合反应，收集浆料并60℃保温陈化20min，过滤、洗涤得到CaCO3@SiO2复合粒子滤饼；将CaCO3@SiO2复合粒子滤饼置于酸性溶液中溶解纳米碳酸钙，过滤、洗涤、干燥得到纳米空心二氧化硅。图9为本实施例1所获得的透射电镜图。
对比例1
重复实施例1：不同之处仅在于，料液A与料液B的流量比为2：1，其实验结果如下：由TEM电镜可看出(参见图10所示)所获得的纳米空心二氧化硅仍有大量的空心结构，但存在少量的实心颗粒。
对比例2
重复实施例1：不同之处仅在于，料液A与料液B的流量比为4：1，其实验结果如下：由TEM电镜可看出(参见图11所示)所获得的纳米空心二氧化硅仍有大量的空心结构，但实心颗粒较对比例1有所增加。
对比例3
重复实施例1：不同之处仅在于，料液A与料液B的流量比为20：1，其实验结果如下：由TEM电镜可看出(参见图12所示)所获得的纳米空心二氧化硅存在空心结构，出现大量的实心颗粒。
对比例4
重复实施例1：不同之处仅在于，料液A中CaCO3固含量为45wt％，其实验结果如下：由TEM电镜可看出(参见图13所示)所获得的纳米空心二氧化硅存在空心结构，但出现少许的实心颗粒。
对比例5
重复实施例1：不同之处仅在于，料液A中CaCO3固含量为50wt％，其实验结果如下：由TEM电镜可看出(参见图14所示)所获得的纳米空心二氧化硅存在空心结构，出现大量的实心颗粒。
对比例6
重复实施例1：不同之处仅在于，按HCl/Na2SiO3·9H2O比例为2/1(摩尔比)配置料液B，其实验结果如下：由TEM电镜可看出(参见图15所示)所获得的纳米空心二氧化硅存在空心结构，但出现实心颗粒。
对比例7
重复实施例1：不同之处仅在于，按HCl/Na2SiO3·9H2O比例为2.4/1(摩尔比)配置料液B，其实验结果如下：由TEM电镜可看出(参见图16所示)基本不存在空心结构。
对比例8
重复实施例1：不同之处仅在于，陈化温度为15℃，陈化时间为2min，其实验结果如下：由TEM电镜可看出(参见图17所示)所获得的纳米材料空心结构不完整。
对比例9
为了研究超重力技术对纳米空心二氧化硅形貌的影响，实验在常规搅拌槽反应器(STR)中进行，反应条件与实施例1中超重力旋转填充床反应器相同，其实验结果如下：由TEM电镜可看出(参见图18所示)所获得的纳米材料的空心结构大量破碎，且产率、比表面积与超重力技术相比较低。图19为对比例9中纳米空心二氧化硅吸附脱附等温曲线。
对比例10
为了研究超重力技术对纳米空心二氧化硅形貌的影响，实验在常规搅拌槽反应器(STR)中进行，反应条件与实施例1中超重力反应器相同，不同之处仅在于采取滴加进料，滴加时间为30min，其实验结果如下：由TEM电镜可看出(参见图20所示)所获得的纳米材料存在实心的小颗粒，与超重力技术相比STR所需的时间大大延长。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无法对所有的实施方式予以穷举。凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。

Claims (10)

  1. 一种快速制备纳米空心二氧化硅的方法，其特征在于，包括如下步骤：
    S1、将纳米碳酸钙滤饼和硅酸钠按一定比例加入水中，配制成纳米碳酸钙和硅酸钠的悬浮液，记为料液A；
    S2、将有机酸或无机酸加入到水中，配置成酸性溶液，记为料液B；
    S3、将料液A和料液B通过进料口同时注入到超重力旋转填充床反应器中，使料液A和料液B充分混合反应，收集浆料并保温陈化，过滤、洗涤得到CaCO3@SiO2复合粒子滤饼；
    S4、将CaCO3@SiO2复合粒子滤饼置于有机酸或无机酸溶液中溶解纳米碳酸钙，过滤、洗涤、干燥得到纳米空心二氧化硅。
  2. 根据权利要求1所述快速制备纳米空心二氧化硅的方法，其特征在于：步骤S1中，所述纳米碳酸钙的形状为针状、纺锤状、球形、立方形、花瓣形或片状。
  3. 根据权利要求1所述快速制备纳米空心二氧化硅的方法，其特征在于：步骤S1中，所述料液A中的纳米碳酸钙浓度为2-40wt％；所述料液A中硅酸钠的浓度为2-40wt％。
  4. 根据权利要求1所述快速制备纳米空心二氧化硅的方法，其特征在于：步骤S2中，所述有机酸或无机酸为盐酸、硫酸、硝酸、醋酸、硒酸、磷酸、高氯酸、氢氟酸、氢溴酸、氢碘酸、氢氰酸、亚硫酸、亚硝酸、柠檬酸、乳酸、酒石酸、苹果酸、偏酒石酸、乙二酸、富马酸溶液的一种或多种。
  5. 根据权利要求1所述快速制备纳米空心二氧化硅的方法，其特征在于：步骤S2中，所述料液B的浓度为0.01mol/L-2mol/L。
  6. 根据权利要求1所述快速制备纳米空心二氧化硅的方法，其特征在于：步骤S3中，所述保温陈化的温度为20-90℃；更优选地，所述保温陈化的温度为30-80℃。
  7. 根据权利要求1所述快速制备纳米空心二氧化硅的方法，其特征在于：步骤S3中，所述保温陈化时间为5-120min。
  8. 根据权利要求1所述快速制备纳米空心二氧化硅的方法，其特征在于：步骤S3中，所述料液A进料流率为20-2000mL/min，料液B进料流率为20-2000mL/min；所述料液A与料液B进料流率比为1:3-3:1，且所述料液A与料液B通入超重力旋转填充床反应器的 体积流量比为0.3-3。
  9. 根据权利要求1所述快速制备纳米空心二氧化硅的方法，其特征在于：步骤S3中，所述超重力旋转填充床反应器的转子转速为300-3000rpm；更优选地，所述超重力旋转填充床反应器的转子转速为500-2500rpm。
  10. 根据权利要求1所述快速制备纳米空心二氧化硅的方法，其特征在于：步骤S4中，所述纳米空心二氧化硅的壳层厚度为1-30nm；
    优选地，步骤S4中，所述干燥为鼓风干燥，干燥温度为25-120℃，干燥时间为2-24h；更优选地，干燥温度为30-110℃，干燥时间为3-14h。
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