CN104556057B - Method for preparing nano-porous light silicon oxide microspheres - Google Patents
Method for preparing nano-porous light silicon oxide microspheres Download PDFInfo
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- CN104556057B CN104556057B CN201510018324.2A CN201510018324A CN104556057B CN 104556057 B CN104556057 B CN 104556057B CN 201510018324 A CN201510018324 A CN 201510018324A CN 104556057 B CN104556057 B CN 104556057B
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Abstract
The invention discloses a method for preparing nano-porous light silicon oxide microspheres. The nano-porous light silicon oxide microspheres are prepared by adding a surfactant to form an emulsion system and carrying out chemical reaction by mainly adopting water glass as a precursor, a solvent with a low surface tension as a replacement solvent and an organic silane compound as a hydrophobic modifier in the presence of inorganic acid as a catalyst. The method for preparing the nano-porous light silicon oxide microspheres is simple in process flow; in addition, the production raw materials are low in price, the solvent is easy to recover, and low production cost and high yield are achieved; in the preparation process adopted in the invention, no cation exchange resin is needed in the ion-exchange process, so that large-scale industrial production is facilitated; and the nano-porous light silicon oxide microspheres prepared by the method are of a typical nano-porous structure and can be applied to the fields, such as thermal insulation, chromatographic separation, catalysis and biological drug loading.
Description
Technical field
The present invention relates to field of material preparation, and in particular to a kind of preparation side of nanoporous light silicon dioxide microsphere
Method.
Background technology
Nanoporous light silicon dioxide is also referred to as SiO2Aeroge, SiO2Aeroge is one kind with nanometer scale particle
Mutually aggregation constitutes nanoporous network structure, and a kind of high dispersive solid-state material full of gaseous state disperse medium in hole,
The features such as there is nano-porous structure, low-density, low-k, low thermal conductivity, high porosity, high-specific surface area because of which,
Peculiar property is shown in aspects such as mechanics, acoustics, calorifics, optics, space flight, military affairs, oil, chemical industry, mineral products, communication,
The various fields such as medical, building materials, electronics, metallurgy have extensive and huge using value, are referred to as " changing the magical material in the world
Material ".
At present, SiO2Aeroge has obtained extensively should in heat-insulated, dielectric layer, the biological field such as medicine and space technology that carries
And have received the great attention of material researchers.At present, SiO2The research of aeroge is concentrated mainly on aerogel block body
On irregular shape powder body.And spherical SiO2Aeroge microparticle has well-regulated shape, the powder body aeroge being made up of which
Material has higher apparent density and preferable mobility, be conducive to which heat-insulated, and the aspect such as chromatographic isolation and catalysis is answered
With.In addition, spherical SiO2Aeroge microparticle has also obtained important application in terms of the controllable release of medicine.Therefore, develop
Spherical SiO2The novel preparation method of aeroge microparticle has important practical significance.
In spherical SiO2In terms of the preparation method research of aeroge microparticle, people have carried out substantial amounts of research work, wish
Prestige can develop low cost, process is simple, it is time-consuming it is short, and be capable of achieving the preparation method of large-scale production.At present, spherical SiO2
The preparation method of aeroge microparticle mainly includes supercritical drying and constant pressure and dry two ways.Prepared by supercritical methanol technology
SiO2 aeroge performances are more excellent, but the power consumption of equipment complex and expensive, drying process is high, dangerous big.It is prepared by constant pressure and dry
Without the need for large number quipments, workable, safety and environmental protection, the large-scale industrial production for SiO2 aeroges are provided SiO2 aeroges
May.But the normal pressure preparation technology of report is loaded down with trivial details at present, need to replace through prolonged surface-hydrophobicized modified and solvent
Process.Chinese patent CN101200293A and Chinese patent CN1011649881A disclose two kinds and prepare spherical SiO2Aeroge
The method of microparticle, it is main that spherical wet gel is obtained using stirring spherical container shaping method and liquid spherical container shaping method, but will be through the solvent of 5 ~ 6 days
Displacement and Process of Surface Modification time.Chinese patent 201310046976.8 is disclosed one kind and is quickly made using constant pressure and dry technology
Standby SiO2The method of aerogel microball, which adopts silicate aqueous solution/non-polar solven inverse emulsion system to carry out reaction and obtains SiO2
Aerogel microball, but its presoma silicate solution is to need water glass solution is carried out ion friendship through cation exchange resin
Change, the loaded down with trivial details time-consuming and high cost of the process.Generally speaking, current spherical SiO2The technology of preparing of aeroge microparticle is yet suffered from
Complex process, time-consuming, the shortcomings of high cost, continues a kind of low cost of research and development, process is simple and is capable of achieving scale
The technology of production prepares spherical SiO2Aeroge microparticle is of great practical significance.
The content of the invention
The present invention prepares method complex process, the high cost of nanoporous light silicon dioxide microsphere in being directed to prior art
Technical problem, it is therefore intended that a kind of low cost, process is simple are provided and the constant pressure and dry technology system of large-scale production is capable of achieving
The method of standby nanoporous light silicon dioxide microsphere.
The purpose of the present invention is in the following manner completing：
A kind of preparation method of nanoporous light silicon dioxide microsphere that the present invention is provided：Waterglass is adopted for forerunner
Body, low surface tension solvent are replacement solvent, carry out chemical reaction by adding surfactant to form emulsion system, wherein with
Used as catalyst, organic silane compound is hydrophobic modifier to mineral acid, and process is carried out in the steps below successively：
（1）Waterglass is mixed homogeneously at room temperature with deionized water, organic silane compound and low surface tension is added
Solvent, is uniformly mixing to obtain mixed solution；
（2）Surfactant is added in mixed solution, after high-speed stirred makes System forming emulsion, thereto plus
Enter inorganic acid catalyst, heated and stirred reaction after reaction terminates, stands, filters, obtain white depositions；
（3）White depositions are carried out washing, constant pressure and dry, obtain nanoporous light silicon dioxide microsphere.
In the step（1）In, waterglass, deionized water, organic silane compound and low surface tension in mixed solution
The mass ratio of solvent is 1：（3~10）：（0.1~2）：（3~15）；
In the step（2）In, surfactant with the mass ratio of waterglass is（0.01~0.5）：1；
In the step（2）In, inorganic acid catalyst with the mass ratio of waterglass is（0.1~1）：1；
In order to the present invention is better achieved, described mineral acid is at least in hydrochloric acid, sulphuric acid, nitric acid and perchloric acid
Kind；
In order to be better achieved the present invention, in described low surface tension solvent normal heptane, normal hexane and normal octane extremely
Few one kind；
In order to the present invention is better achieved, described organic silane compound is dimethyldiethoxysilane, dimethyl
Dimethoxysilane, hexamethyl disiloxane, hexamethyldisiloxane, MTES, MTMS,
Dodecyltrimethoxysilane, dodecyl triethoxysilane, hexadecyl trimethoxy silane, three ethoxy of cetyl
At least one in base silane, octamethylcy-clotetrasiloxane, hexamethyl cyclotrisiloxane；
In order to be better achieved the present invention, described surfactant is tween 20, Tween-40, Tween-60, tween-
80, Tween-65, tween 85, Span -20, Span -40, Span -60, Span -65, span-80, at least one of Span -85；
In order to the present invention is better achieved, in the step（2）Described in high-speed stirred, refer to 400 ~ 1500rpm turn
Fast stirring condition；In the step（2）Described in heated and stirred reaction, refer to reaction temperature for 30 ~ 70 DEG C, the response time is
0.5h~5h；In the step（3）In constant pressure and dry refer in atmospheric conditions, at 80 ~ 180 DEG C be dried 1 ~ 6h.
Nanoporous light silicon dioxide microsphere prepared by the present invention is regular spherical granule, and particle diameter is 1 ~ 1000 μm,
Specific surface area is 300 ~ 1200 m2/ g, aperture are 10 ~ 100nm.
Relative to prior art, the invention has the advantages that and beneficial effect：
1st, nanoporous light silicon dioxide microspheres flow process of the present invention is simple；In addition, production is former
Material is cheap, and solvent is easily reclaimed, low production cost, and yield is high.
2nd, nanoporous light silicon dioxide microsphere preparation process of the present invention is with cheap waterglass as former material
Material, it is not necessary to carry out ion exchange process through cation exchange resin, be easy to scale industrial production.
3rd, the nanoporous light silicon dioxide microsphere prepared by the present invention is regular spherical granule, mean diameter can 1 ~
Regulation and control in 1000 μ ms, and there is typical nano-porous structure, can be applicable to heat-insulated, chromatographic isolation, catalysis and biological load
The fields such as medicine.
Description of the drawings
Fig. 1 is the SEM figures of the nanoporous light silicon dioxide microsphere prepared by the embodiment of the present invention 1.
Fig. 2 is the SEM of the nanoporous light silicon dioxide microsphere surface microstructure prepared by the embodiment of the present invention 1
Figure.
Fig. 3 is the EDS figures of the nanoporous light silicon dioxide microsphere prepared by the embodiment of the present invention 1.
Specific embodiment
Son is described in further detail to the specific embodiment of the present invention with reference to the accompanying drawings and examples, but this
Bright embodiment not limited to this.
Embodiment 1
By 100g waterglass（Modulus is 3.0）Mixed homogeneously with 300g deionized waters at room temperature, add 50g hydrochloric acid (37
Wt%) and 300g normal hexane, it is uniformly mixing to obtain mixed solution；10g tween 20 surfactants are added in mixed solution, is led to
The quick stirring under 400rpm rotating speeds is crossed so that after System forming emulsion, 10g dimethyldiethoxysilanes are added to which,
Stirring reaction 3h under 30 DEG C of heating conditions, after reaction terminates, stands, filters, obtain white depositions；White is washed with normal hexane
Precipitate 3 times, is then placed in air dry oven, dried 6h under the conditions of 100 DEG C, and the nanoporous for obtaining white are light
Matter silicon dioxide microsphere.
As shown in Figures 1 and 2, granule is the scanning electron microscope (SEM) photograph of prepared nanoporous light silicon dioxide microsphere
Spherical shape, particle size distribution between 10 ~ 20 μm, by accompanying drawing 2 as can be seen that obtained nanoporous light silicon dioxide
Microsphere is the porous material with contiguous network structure, and pore size is 5 ~ 50nm, and nano aperture is evenly distributed.Accompanying drawing 3 is
The EDS figures of product are prepared, by accompanying drawing 3 as can be seen that not having in prepared nanoporous light silicon dioxide microsphere sample
The appearance of Na elements, illustrates, in after chemical reaction modifying process, to can reach Na+Ion exchange, sol-gel process, table
The synchronization of the processes such as face hydrophobization modification, solvent displacement is carried out.
Test result：
Particle diameter：10~20μm；
Apparent density：0.1g/cm3；
Specific surface area：1200 m2/g；
Average pore size：50nm.
Embodiment 2
By 100g waterglass（Modulus is 3.0）Mixed homogeneously with 800g deionized waters at room temperature, add 120g perchloric acid
((50 wt %) and 600g normal heptane, are uniformly mixing to obtain mixed solution；1g Tween-40 surface activitys are added in mixed solution
Agent, after quick stirring causes System forming emulsion under 1500rpm rotating speeds, adds four silica of 90g prestoxs ring to which
Alkane, stirring reaction 1.5h under 60 DEG C of heating conditions after reaction terminates, stand, filter, obtain white depositions；Use normal heptane
Washing white depositions 3 times, are then placed in air dry oven, dried 3h under the conditions of 80 DEG C, obtain receiving for white
Rice porous light silicon dioxide microsphere.
Test result：
Particle diameter：50~120μm；
Apparent density：0.15g/cm3；
Specific surface area：1000 m2/g；
Average pore size：80nm.
Embodiment 3
By 100g waterglass（Modulus is 3.2）Mixed homogeneously with 600g deionized waters at room temperature, add 100g hydrochloric acid (37
Wt%) and 1200g normal octanes, it is uniformly mixing to obtain mixed solution；20g Tween-60 surfactants are added in mixed solution,
After quick stirring causes System forming emulsion under 800rpm rotating speeds, 80g dodecyl triethoxysilicanes are added to which
Alkane, stirring reaction 1.5h under 50 DEG C of heating conditions after reaction terminates, stand, filter, obtain white depositions；Use normal octane
Washing white depositions 3 times, are then placed in air dry oven, dried 2h under the conditions of 180 DEG C, obtain receiving for white
Rice porous light silicon dioxide microsphere.
Test result：
Particle diameter：1~20μm；
Apparent density：0.05g/cm3；
Specific surface area：1200 m2/g；
Average pore size：10nm.
Embodiment 4
By 100g waterglass（Modulus is 3.3）Mixed homogeneously with 450g deionized waters at room temperature, add 80g sulphuric acid (50
Wt %) and 800g normal hexane, it is uniformly mixing to obtain mixed solution；50g Tween-65 surfactants are added in mixed solution,
After quick stirring causes System forming emulsion under 1000rpm rotating speeds, 150g MTMSs are added to which,
Stirring reaction 1.5h under 45 DEG C of heating conditions, after reaction terminates, stands, filters, obtain white depositions；Washed with normal hexane
White depositions 3 times, are then placed in air dry oven, dried 6h under the conditions of 90 DEG C, and the nanometer for obtaining white is more
Hole light silicon dioxide microsphere.
Test result：
Particle diameter：100~500μm；
Apparent density：0.15g/cm3；
Specific surface area：800 m2/g；
Average pore size：100nm.
Embodiment 5
By 100g waterglass（Modulus is 3.4）Mixed homogeneously with 600g deionized waters at room temperature, add 100g nitric acid (50
Wt %), 20g hexamethyldisiloxane and 600g normal heptane, be uniformly mixing to obtain mixed solution；5g departments are added in mixed solution
- 20 surfactants of class, after quick stirring causes System forming emulsion under 600rpm rotating speeds, add 30g ten to which
Six alkyl trimethoxysilanes, stirring reaction 0.5h under 60 DEG C of heating conditions after reaction terminates, stand, filter, obtain white
Precipitate；White depositions 3 times are washed with normal heptane, is then placed in air dry oven, the dried under the conditions of 130 DEG C
5h, obtains the nanoporous light silicon dioxide microsphere of white.
Test result：
Particle diameter：100~1000μm；
Apparent density：0.09g/cm3；
Specific surface area：1100 m2/g；
Average pore size：70nm.
Embodiment 6
By 100g waterglass（Modulus is 3.0）Mixed homogeneously with 500g deionized waters at room temperature, add 50g perchloric acid
(50 wt %) and 1000g normal octanes, are uniformly mixing to obtain mixed solution；In mixed solution, add -40 surface of 40g Spans to live
Property agent, after quick stirring causes System forming emulsion under 900rpm rotating speeds, add two silicon nitrogen of 100g hexamethyl to which
Alkane, stirring reaction 1.5h under 40 DEG C of heating conditions after reaction terminates, stand, filter, obtain white depositions；Use normal octane
Washing white depositions 3 times, are then placed in air dry oven, dried 3h under the conditions of 120 DEG C, obtain receiving for white
Rice porous light silicon dioxide microsphere.
Test result：
Particle diameter：50~200μm；
Apparent density：0.08g/cm3；
Specific surface area：900 m2/g；
Average pore size：40nm.
Embodiment 7
By 100g waterglass（Modulus is 2.2）Mixed homogeneously with 300g deionized waters at room temperature, add 20g nitric acid (50
Wt %) and 1500g normal hexane, it is uniformly mixing to obtain mixed solution；- 60 surfactant of 15g Spans is added in mixed solution,
After quick stirring causes System forming emulsion under 700rpm rotating speeds, 200g hexamethyl disiloxanes are added to which,
Stirring reaction 1.5h under 50 DEG C of heating conditions, after reaction terminates, stands, filters, obtain white depositions；Washed in vain with normal hexane
Color precipitate 3 times, is then placed in air dry oven, dried 1h under the conditions of 180 DEG C, obtains the nanoporous of white
Light silicon dioxide microsphere.
Test result：
Particle diameter：50~100μm；
Apparent density：0.12g/cm3；
Specific surface area：600 m2/g；
Average pore size：40nm.
Embodiment 8
By 100g waterglass（Modulus is 3.7）Mixed homogeneously with 1000g deionized waters at room temperature, add 200g sulphuric acid
(50 wt%) and 400g normal heptane, are uniformly mixing to obtain mixed solution；30g span-80 surface activitys are added in mixed solution
Agent, after quick stirring causes System forming emulsion under 1200rpm rotating speeds, adds 50g dimethylformamide dimethyl epoxides to which
Silane, stirring reaction 0.5h under 70 DEG C of heating conditions after reaction terminates, stand, filter, obtain white depositions；Use positive heptan
Alkane washing white depositions 3 times, are then placed in air dry oven, dried 6h under the conditions of 80 DEG C, obtain white
Nanoporous light silicon dioxide microsphere.
Test result：
Particle diameter：60~120μm；
Apparent density：0.16g/cm3；
Specific surface area：300 m2/g；
Average pore size：100nm.
Claims (3)
1. a kind of preparation method of nanoporous light silicon dioxide microsphere, it is characterised in that：Waterglass is adopted for presoma, it is low
Surface tension solvent is replacement solvent, carries out chemical reaction by adding surfactant to form emulsion system, wherein with inorganic
Used as catalyst, organic silane compound is hydrophobic modifier for acid, and process is carried out in the steps below successively：
(1) waterglass is mixed homogeneously at room temperature with deionized water, adds inorganic acid catalyst and low surface tension solvent, stir
Mix；
(2) surfactant is added in mixed solution, after high-speed stirred makes System forming emulsion, be added thereto to
Organic silane compound, heated and stirred reaction after reaction terminates, stand, filter, obtain white depositions；
(3) white depositions are carried out washing, constant pressure and dry, obtain nanoporous light silicon dioxide microsphere；
Wherein, in the step (1), in mixed solution, waterglass, deionized water, inorganic acid catalyst and low surface tension are molten
The mass ratio of agent is 1：(3～10)：(0.1～1)：(3～15)；
In the step (2), surfactant is (0.01～0.5) with the mass ratio of waterglass：1；
In the step (2), organic silane compound is (0.1～2) with the mass ratio of waterglass：1；
High-speed stirred described in the step (2), refers in 400～1500rpm rotating speed stirring conditions；
Heated and stirred reaction described in the step (2), refers to reaction temperature for 30～70 DEG C, the response time be 0.5h～
5h；
Constant pressure and dry in the step (3) refers in atmospheric conditions, and 1～6h is dried at 80～180 DEG C；
Described low surface tension solvent is at least one in normal heptane, normal hexane and normal octane.
2. method according to claim 1, it is characterised in that：Described mineral acid is hydrochloric acid, sulphuric acid, nitric acid and perchloric acid
In at least one；
Described organic silane compound is dimethyldiethoxysilane, dimethyldimethoxysil,ne, two silica of hexamethyl
Alkane, hexamethyldisiloxane, MTES, MTMS, dodecyltrimethoxysilane, 12
Alkyl triethoxysilane, hexadecyl trimethoxy silane, hexadecyl, octamethylcy-clotetrasiloxane,
At least one in hexamethyl cyclotrisiloxane；Described surfactant be tween 20, Tween-40, Tween-60, tween-
80, Tween-65, tween 85, Span -20, Span -40, Span -60, Span -65, span-80, at least one of Span -85.
3. method according to claim 1, it is characterised in that：Described nanoporous light silicon dioxide microsphere is rule
Spheroidal particle, particle diameter are 1～1000 μm, and specific surface area is 300～1200m2/ g, aperture are 10～100nm.
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| CN105801886B (en) * | 2016-04-04 | 2018-08-31 | 刘云晖 | A kind of preparation method of dewatering nano porous cellulose microballoon |
| US10618920B2 (en) * | 2016-06-03 | 2020-04-14 | Agilent Technologies, Inc. | Functionalized particles having modified phases |
| CN106082243B (en) * | 2016-06-12 | 2018-11-23 | 伊科纳诺（北京）科技发展有限公司 | A kind of normal pressure fast preparation method of hydrophobic silica aerogel powder |
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| CN107311185B (en) * | 2017-06-23 | 2020-12-22 | 复旦大学 | Preparation method of ultrahigh-porosity porous silicon dioxide |
| CN107176612A (en) * | 2017-07-11 | 2017-09-19 | 蚌埠市万科硅材料科技有限公司 | A kind of preparation method of light silicon dioxide nanoparticle |
| CN108892144B (en) * | 2018-06-22 | 2021-09-28 | 南京亘闪生物科技有限公司 | Preparation method of functionalized porous particle size monodisperse silicon dioxide spherical material |
| CN111867974B (en) * | 2018-08-06 | 2022-11-01 | 浙江三时纪新材科技有限公司 | Precipitated white carbon black and preparation method thereof |
| CN108975342B (en) * | 2018-08-31 | 2022-01-04 | 武汉理工大学 | Method for continuously preparing silicon dioxide aerogel balls by utilizing vibration hydrophobic surface |
| CN112897532B (en) * | 2019-11-19 | 2022-09-20 | 吉林建筑大学 | Silicon dioxide aerogel powder and preparation method and application thereof |
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| CN114804689A (en) * | 2022-04-27 | 2022-07-29 | 廊谷(天津)新能源科技有限公司 | Preparation method of nano porous master batch for cement-based insulation board |
| CN115947361A (en) * | 2022-11-21 | 2023-04-11 | 江苏联瑞新材料股份有限公司 | Low-radioactivity alumina powder and preparation method thereof |
| CN115784245B (en) * | 2022-12-29 | 2024-01-16 | 苏州西丽卡电子材料有限公司 | Preparation method of hydrophobic high-purity micron-sized spherical silicon dioxide powder |
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| CN102020285A (en) * | 2009-09-16 | 2011-04-20 | 深圳大学 | Preparation method for hydrophobic silica aerogel |
| CN103531760A (en) * | 2013-10-28 | 2014-01-22 | 北京化工大学 | Porous silicon carbon composite microsphere with yolk-eggshell structure and preparation method therefor |
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| CN102020285A (en) * | 2009-09-16 | 2011-04-20 | 深圳大学 | Preparation method for hydrophobic silica aerogel |
| CN103531760A (en) * | 2013-10-28 | 2014-01-22 | 北京化工大学 | Porous silicon carbon composite microsphere with yolk-eggshell structure and preparation method therefor |
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