CN103395794A - Preparation method of monodispersed silicon dioxide grains with uniform grain sizes - Google Patents
Preparation method of monodispersed silicon dioxide grains with uniform grain sizes Download PDFInfo
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- CN103395794A CN103395794A CN2013103219162A CN201310321916A CN103395794A CN 103395794 A CN103395794 A CN 103395794A CN 2013103219162 A CN2013103219162 A CN 2013103219162A CN 201310321916 A CN201310321916 A CN 201310321916A CN 103395794 A CN103395794 A CN 103395794A
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Abstract
The invention relates to a preparation method of monodispersed silicon dioxide grains with uniform grain sizes, belonging to the technical field of preparation of granular monolithic columns. According to the preparation method disclosed by the invention, the granular monolithic column formed by spherical grains in mutual adhesion is firstly prepared, and the grains with weak adhesion are very easy to be used for preparing the regular spherical monodispersed silicon dioxide grains with great monodispersity through a grinding method. The method has the advantages of simple steps, short time and good repeatability. The monodispersed spherical grains have great monodispersity and uniform grain sizes, and the determination of absorbance on an ultraviolet spectrophotometer or an atomic absorption spectrophotometer shows that the monodispersed spherical grains particularly have a good adsorption effect against acid dyes, as well as a good adsorption effect against dyes and heavy metal ions.
Description
Technical field
The invention belongs to granule type integral post preparing technical field, relate to a kind of preparation method of granule type integral post, also relate to integral post thus and grind the application of earth silicon material aspect absorption that makes.
Background technology
The silicon-dioxide integral post has that post effect is high, and pressure is low, and velocity of separation is fast, can remove the advantages such as complicated processes of synthetic particle from, is therefore more applied.The people such as Ko adopt a kind of novel method to prepare integral post, then integral post are simply ground, and C18 recharges in capillary column after modifying, and becomes a kind of novel filling stationary phase.But, owing to adopting the method to obtain particle, be irregular, thereby when they were subject to elevated pressures in chromatographic column after, bed was easy to just loosening, causes the pillar lost of life.
Summary of the invention
Order of the present invention is the preparation method who proposes the uniform monodisperse silica particle of a kind of particle diameter.
The present invention includes following steps:
1) under the envrionment temperature of temperature≤0 ℃, after first polyoxyethylene glycol, urea and aqueous acetic acid being uniformly mixed, then sneak into tetramethoxy-silicane, under the condition of ice-water bath, after supersound process 10 min, obtain mixed sols;
3) goods after aging being placed in to the air dry oven of 120 ℃ together with mould dries;
4) will carry out calcination from the silicon-dioxide integral post of taking out mould;
4) will be from the silicon-dioxide integral post calcination of taking out mould;
5) monolithic silica column is ground, obtain the uniform monodisperse silica particle of particle diameter.
The present invention, in conjunction with the advantage of two kinds of stationary phase, provides a kind of preparation method of granule type integral post.First prepare the granule type integral post that is formed by inter-adhesive spheroidal particle, the particle of these weak adhesions is easy to make good, the regular spherical monodisperse nano-particle silica dioxide granule of monodispersity by the method for grinding.This method step is simple, prepares required time short, and reproducible.This monodisperse spherical particle monodispersity is good, and the particle diameter of homogeneous is arranged, and is about 5 μ m, can be used as stationary phase and separates for liquid chromatography, also can be used as the processing that sorbing material carries out waste water from dyestuff.Through on New UV Spectrophotometric absorptiometer or atomic absorption photometer, carrying out the mensuration of absorbancy, especially to the advantages of good adsorption effect of matching stain, maximum adsorption capacity to tropeolin-D is 657.06 mg/g, to Congo red adsorptive capacity up to 672.11 mg/g, adsorptive capacity to sodium alizarinsulfonate has also reached 507.43 mg/g, and the visible uniform monodisperse silica particle of particle diameter has good adsorptivity to the dye well heavy metal ion.
The mass ratio that feeds intake of polyoxyethylene glycol of the present invention, urea, aqueous acetic acid and tetramethoxy-silicane is 100 ︰ 90～92 ︰ 72～76 ︰ 600～650; In described aqueous acetic acid, the massfraction of acetic acid is 0.6%.Under this feed ratio, the adhesion of particle is the most weak and granular size is the most even, through hole and granule-morphology the best.
In air dry oven, processed 3 hours.With the mode that progressively heats up, by the material drying, prevent overplumping in heat-processed, destroy material through hole and pattern.
In order to keep the best pore structure of material, the temperature of described calcination is 600 ℃, and the calcination time is 6 hours.
In order further to improve adsorptivity, the present invention also can by the uniform monodisperse silica particle of particle diameter be warming up to backflow after toluene, 3-aminopropyl triethoxysilane (APTS) mix, after being cleaned with toluene or ethanol, phegma gets solid phase, dry under 40～60 ℃, obtain the silica dioxide granule of bonding amino.
The accompanying drawing explanation
Fig. 1 is the pattern photo of integral post.
Fig. 2 is the scanning electron microscope (SEM) photograph in integral post cross section.
Fig. 3 is the partial sweep Electronic Speculum figure of monolithic silica column after calcination.
Fig. 4 is the large area scanning Electronic Speculum figure of monolithic silica column after calcination.
Fig. 5 is particulate scan Electronic Speculum figure after grinding.
Fig. 6 is particulate scan Electronic Speculum figure after grinding.
Fig. 7 is the graphic representations such as the front nitrogen adsorption-desorption of calcining.
Fig. 8 is calcining front aperture distribution plan.
Fig. 9 is the graphic representations such as the rear nitrogen adsorption-desorption of calcining.
Figure 10 is calcining back aperture distribution plan.
Embodiment
Embodiment 1
1, prepare silica dioxide granule:
Taking polyethylene glycol 0.66 g, urea 0.60 g and massfraction are 0.6% aqueous acetic acid 8.0 mL(0.01 M) in round-bottomed flask, in ice-water bath, stir 20 min, the tetramethoxy-silicane that adds 4.0 mL, 40 min are stirred in continuation in ice-water bath, follow under the condition of ice-water bath ultrasonic 10 min, then ultrasonic good colloidal sol is injected to the tetrafluoroethylene mould, in the water-bath of 30 ℃, aging 24 h of gel, 120 ℃ of baking 3 h in air dry oven.From mould, taking out the silicon-dioxide integral post prepare, then the integral post of gained is put into to retort furnace, be heated to 600 ℃, keep 6 h, obtain the monolithic silica column after calcination, as shown in Figure 1.
As seen from Figure 1: synthetic integral post pattern is regular, but a little bending is arranged endways.
Scanning electron microscope (SEM) photograph by the integral post cross section of Fig. 2 can be found out the granule-morphology homogeneous, and weak adhesion is arranged between particle.
Partial sweep Electronic Speculum figure by monolithic silica column after the calcination of Fig. 3 is visible: considerable change does not occur in pattern.
Large area scanning Electronic Speculum figure by monolithic silica column after the calcination of Fig. 4 is visible: the particle overall distribution is even, and pattern meets the expected requirements.
By diagram shows such as nitrogen adsorption-desorptions before the calcining of Fig. 7: by figure, calculating specific surface area before calcination is 153 m
2/ g.
Calcining front aperture distribution plan by Fig. 8 is visible: in particle, have the hole larger than multiple aperture.
Visible by graphic representations such as nitrogen adsorption-desorptions after the calcining of Fig. 9: by figure, calculating specific surface area before calcination is 453m
2/ g.
Calcining back aperture distribution plan by Figure 10 is visible: the macropore after calcining in particle disappears substantially.
By the integral post that obtains after calcination in agate mortar with slower speed, more uniform dynamics is ground, and obtains the silica dioxide granule of uniform grading.
The material that the present embodiment is obtained carries out BET and characterizes and obtain its specific surface area and reach 453 m
2/ g, have larger pore volume.
By particulate scan Electronic Speculum figure after the grinding of Fig. 5, illustrated: the particle monodispersity is good, and whole pattern does not have larger damage.
By particulate scan Electronic Speculum figure explanation after the grinding of Fig. 6: between particle weak adhesion destroyed, form the monodisperse spherical silica dioxide granule, the material pattern that requires with expection conforms to.
2, application:
Get silica dioxide granule 0.0100～0.1000g that the present embodiment obtains, add in the 50mL solution that contains methylene blue 30～240 mg/L, stir for some time, after centrifugal, get supernatant liquid, with ultraviolet photometer, measure absorbancy, obtaining this material is 298.88 mg/g to the maximum adsorption capacity of methylene blue.
Embodiment 2
Application: get silica dioxide granule 0.0100～0.1000 g that the present embodiment one obtains, in in pH is 2～11 environment, adding the 50 mL solution that contain rhodamine B 30～240 mg/L, stir for some time, after centrifugal, get supernatant liquid and measure absorbancy with ultraviolet photometer, obtaining this material is 131.96 mg/g to the maximum adsorption capacity of rhodamine B.
Embodiment 3
Get silica dioxide granule 0.0100～0.1000 g that the present embodiment one obtains, in in pH is 2～11 environment, adding the 50 mL solution that contain rhodamine B 30～240 mg/L, constant speed stirs for some time, after centrifugal, get supernatant liquid and measure absorbancy with ultraviolet photometer, obtaining this material is 131.96 mg/g to the maximum adsorption capacity of rhodamine B.
Embodiment 4
Get silica dioxide granule 2.0000 g that the present embodiment one obtains, the toluene that adds 50 mL, the 3-aminopropyl triethoxysilane (APTS) that adds again 3.2 mL, 8 h reflux, under water-less environment, with toluene, ethanol reagent, clean, dry 12 h under 40～60 ℃, obtain the silica dioxide granule of bonding amino.
Embodiment 5
Get silica dioxide granule 0.0100～0.1000 g that the present embodiment four obtains, in in pH is 2～11 environment, adding the 50 mL solution that contain sodium alizarinsulfonate 30～240 mg/L, stir for some time, after centrifugal, get supernatant liquid and measure absorbancy with ultraviolet photometer, obtaining this material is 507.43 mg/g to the maximum adsorption capacity of sodium alizarinsulfonate.
Embodiment 6
Get silica dioxide granule 0.0100～0.1000 g that the present embodiment four obtains, in in pH is 2～11 environment, adding the 50 mL solution that contain tropeolin-D 30～240 mg/L, stir for some time, after centrifugal, get supernatant liquid and measure absorbancy with ultraviolet photometer, obtaining this material is 657.06 mg/g to the maximum adsorption capacity of tropeolin-D.
Embodiment 7
Get silica dioxide granule 0.0100～0.1000 g that the present embodiment four obtains, in in pH is 2～11 environment, adding the 50 mL solution that contain Congo red 30～240 mg/L, constant speed stirs for some time at a certain temperature, after centrifugal, get supernatant liquid and measure absorbancy with ultraviolet photometer, obtaining this material is 672.11 mg/g to Congo red maximum adsorption capacity.
Embodiment 8
Get silica dioxide granule 0.0100～0.1000 g that the present embodiment four obtains, in pH is the environment of 2-10, adds and contain Cu
2+In the 50 mL solution of 30～240 mg/L, stir for some time, get supernatant liquid after centrifugal to measure absorbancy with flame atomic absorption spectrophotometer, obtain this material to Cu
2+Maximum adsorption capacity be 99.04 mg/g.
Embodiment 9
Get silica dioxide granule 0.0100～0.1000 g that the present embodiment four obtains, in pH is 2～10 environment, adds and contain Pb
2+In the 50 mL solution of 30～240 mg/L, stir for some time, get supernatant liquid after centrifugal to measure absorbancy with flame atomic absorption spectrophotometer, obtain this material to Pb
2+Maximum adsorption capacity be 163.71 mg/g.
Claims (5)
1. the preparation method of the uniform monodisperse silica particle of particle diameter is characterized in that comprising the following steps:
1) under the envrionment temperature of temperature≤0 ℃, after first polyoxyethylene glycol, urea and aqueous acetic acid being uniformly mixed, then sneak into tetramethoxy-silicane, under the condition of ice-water bath, after supersound process 10 min, obtain mixed sols;
2) mixed sols is injected to the mould gel aging;
3) goods after aging being placed in to the air dry oven of 120 ℃ together with mould dries;
4) will carry out calcination from the silicon-dioxide integral post of taking out mould;
5) monolithic silica column is ground, obtain the uniform monodisperse silica particle of particle diameter.
2. the preparation method of the uniform monodisperse silica particle of particle diameter according to claim 1, the mass ratio that feeds intake that it is characterized in that described polyoxyethylene glycol, urea, aqueous acetic acid and tetramethoxy-silicane is 100 ︰ 90～92 ︰ 72～76 ︰ 600～650; In described aqueous acetic acid, the massfraction of acetic acid is 0.6%.
3. the preparation method of the uniform monodisperse silica particle of particle diameter according to claim 1, is characterized in that processing 3 hours in air dry oven.
4. the preparation method of the uniform monodisperse silica particle of particle diameter according to claim 1, the temperature that it is characterized in that described calcination is 600 ℃, the calcination time is 6 hours.
5. the preparation method of the uniform monodisperse silica particle of according to claim 1 and 2 or 3 or 4 described particle diameter, after it is characterized in that the uniform monodisperse silica particle of particle diameter that step 5) namely obtains and toluene, 3-aminopropyl triethoxysilane mixing, be warming up to backflow, after being cleaned with toluene or ethanol, phegma gets solid phase, dry under 40～60 ℃, obtain the silica dioxide granule of bonding amino.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211073A (en) * | 2014-09-19 | 2014-12-17 | 熊仕显 | Preparation method of monodisperse nano spherical silicon dioxide and nano silicon dioxide |
| CN107381586A (en) * | 2017-07-19 | 2017-11-24 | 东南大学 | The method that silica nanoparticle surface modifies amino |
| CN107552024A (en) * | 2017-08-06 | 2018-01-09 | 桂林理工大学 | Preparation method for the crosslinking casein porous microsphere of lead absorption |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1352670A (en) * | 1999-03-10 | 2002-06-05 | 伊塔卡陶瓷制造技术股份有限公司 | Silica and iron oxide based pigments and method for the production thereof |
| CN1483510A (en) * | 2003-05-11 | 2004-03-24 | 杨更亮 | Silica gel continuous bar and preparation process thereof |
| US20080063868A1 (en) * | 2006-09-09 | 2008-03-13 | Samsung Electronics Co., Ltd. | Functionalized silica nanoparticles having polyethylene glycol linkage and production method thereof |
| CN101898764A (en) * | 2010-07-30 | 2010-12-01 | 天津大学 | Method for transforming silicon tetrachloride to fine silica powder |
-
2013
- 2013-07-29 CN CN2013103219162A patent/CN103395794A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1352670A (en) * | 1999-03-10 | 2002-06-05 | 伊塔卡陶瓷制造技术股份有限公司 | Silica and iron oxide based pigments and method for the production thereof |
| CN1483510A (en) * | 2003-05-11 | 2004-03-24 | 杨更亮 | Silica gel continuous bar and preparation process thereof |
| US20080063868A1 (en) * | 2006-09-09 | 2008-03-13 | Samsung Electronics Co., Ltd. | Functionalized silica nanoparticles having polyethylene glycol linkage and production method thereof |
| CN101898764A (en) * | 2010-07-30 | 2010-12-01 | 天津大学 | Method for transforming silicon tetrachloride to fine silica powder |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211073A (en) * | 2014-09-19 | 2014-12-17 | 熊仕显 | Preparation method of monodisperse nano spherical silicon dioxide and nano silicon dioxide |
| CN107381586A (en) * | 2017-07-19 | 2017-11-24 | 东南大学 | The method that silica nanoparticle surface modifies amino |
| CN107552024A (en) * | 2017-08-06 | 2018-01-09 | 桂林理工大学 | Preparation method for the crosslinking casein porous microsphere of lead absorption |
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Application publication date: 20131120 |