CN113318714A - Monodisperse silicon dioxide microsphere for chromatography and preparation method and application thereof - Google Patents
Monodisperse silicon dioxide microsphere for chromatography and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a monodisperse silicon dioxide microsphere for chromatography and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) soaking silicate minerals in a hydrochloric acid solution to obtain pretreated silicate minerals; 2) mixing the pretreated silicate mineral with a sodium hydroxide solution and filtering to obtain a sodium silicate solution; 3) mixing the sodium silicate solution with a silane coupling agent to obtain a silicic acid solution; 4) preparing a suspension by the silicic acid solution and an ethanol water solution of a surfactant; 5) standing to separate out a white precipitate, pickling the white precipitate to be neutral, and drying to obtain white powder; 6) and calcining the white powder to obtain the monodisperse silica microspheres for chromatography. The method is simple to prepare and low in cost, and the formed silicon dioxide microspheres have the particle size range of 1-10 mu m, are free of agglomeration, and have the characteristics of high monodispersity and small particle size.
Description
Technical Field
The invention relates to the field of preparation of silica microspheres, in particular to monodisperse silica microspheres for chromatography and a preparation method and application thereof.
Background
Silica microspheres belong to inorganic porous materials, and according to the definition of the international association of pure and applied chemistry, the porous materials can be classified into the following three types: the pore diameter of the microporous material is less than 2 nm; the pore diameter of the macroporous material is more than 50 mn; the aperture of the mesoporous material is between that of the micropores and the macropores. In 1968, Stober adopts alkali-catalyzed tetraethoxysilane in an ethanol water system to prepare monodisperse silicon dioxide, the silica gel microspheres prepared by the method have high purity and good monodispersity, but are microspheres with a non-porous structure, and subsequent research is improved on the basis, and various surfactants are used as templates to prepare porous silicon dioxide microspheres. At present, silicon sources used for preparing the silica microspheres are generally sodium metasilicate nonahydrate and monocrystalline silicon powder, but the preparation cost is increased due to the higher price of the silicon sources, and researches show that precursors obtained by acidizing minerals containing silicate contain silica, the reserves of the silicate minerals in China are rich, the sources are wide, and if the silicate minerals can be used as the silicon sources for preparing the silica microspheres, the preparation cost of the silica microspheres is greatly reduced. The silica microspheres have the characteristics of stable property, high mechanical strength, large specific surface area and the like, and are important to be applied to catalyst carriers, biomedical materials, optical materials and filling materials.
In the literature on the preparation methods of silica microspheres at present, research on synthesis of mesoporous silica by PICA method (journal of chemical industry, 2007,21 (10): 1-3) of Shengfengjun and Linbaoping, preparation and functionalization of silica microspheres (China ceramics, 2013, 49 (7): 19-23) of Wangbui, Liyouxin, Jianmin, preparation of monodisperse high-purity silica gel column packing (advanced school chemistry report, 2012, 33 (4): 689-694), research on synthesis and coating performance of modified epoxy resin (Shandong university, 2012) of Yujunlin, preparation of high-purity monodisperse silica nanoparticles (silicate, 2012, 31 (4): 870-875) of Yanjunjing, Qingjunyu, Liubannan, Liujun, preparation and characterization of mixed silica gel matrix high-performance liquid chromatography (2013), 40(4): 80-85), Guo rui, "preparation and characterization of mesoporous silica spherical particles" (university of Wuhan's rational, 2004), also discloses research results relating to methods for preparing silica microspheres.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention aims to provide monodisperse silica microspheres for chromatography, and a preparation method and use thereof, wherein the silica microspheres have the advantages of simple and easily available raw materials, simple and convenient preparation, and wide application, and are used for solving the problems in the prior art.
To achieve the above objects and other related objects, the present invention is achieved by the following technical solutions.
The invention provides a preparation method of monodisperse silicon dioxide microspheres for chromatography, which comprises the following steps:
1) soaking silicate minerals in a hydrochloric acid solution to obtain pretreated silicate minerals;
2) mixing the pretreated silicate mineral with a sodium hydroxide solution and filtering to obtain a sodium silicate solution;
3) mixing the sodium silicate solution with a silane coupling agent to obtain a silicic acid solution;
4) preparing the sodium silicate solution and an ethanol water solution of a surfactant into a suspension;
5) standing to separate out a white precipitate, pickling the white precipitate to be neutral, and drying to obtain white powder;
6) and calcining the white powder to obtain the monodisperse silica microspheres for chromatography.
In the present application, the solvent of the hydrochloric acid solution and the sodium hydroxide solution is water.
Further, the silicate mineral is one or more of diatomite, white carbon black, kaolin, montmorillonite and attapulgite.
Further, the silicate mineral is 1 to 10 wt% of the mass of the hydrochloric acid solution.
Preferably, the silicate mineral is 10-40 wt% of the mass of the sodium hydroxide solution.
Preferably, the concentration of the hydrochloric acid solution is 1 to 5 mol/L.
Preferably, the concentration of the sodium hydroxide solution is 2 to 10 mol/L.
Further, the surfactant is any one or more of N-dodecyl-N, N dimethyl-N carboxymethyl betaine, octadecylamine, triglyceride, polyoxyethylene dodecylamine, Triton X100 and octadecyl trimethyl ammonium chloride. More preferably, the surfactant is a mixture of any one or two of N-dodecyl-N, N-dimethyl-N-carboxymethyl betaine, octadecylamine, triglyceride, polyoxyethylene dodecylamine, Triton X100 and octadecyl trimethyl ammonium chloride in a mass ratio of 1: 1.
Preferably, the concentration of the surfactant in the suspension is 5-15 g/L.
Further, the ratio of the ethanol to the water is (1-5): 1.
Further, the mass ratio of the sodium silicate solution to the ethanol water solution of the surfactant is (2-10): 100.
preferably, the silane coupling agent is selected from one or more of bis- [3- (triethoxysilyl) propyl ] -disulfide, bis- [3- (triethoxysilyl) propyl ] -tetrasulfide, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriacetoxysilane, and vinyltributyl-silane-tri-peroxide.
Preferably, the mass ratio of the silane coupling agent to the sodium silicate solution is (0.5-1): 1.
preferably, the mixture is prepared into a suspension at the temperature of 20-50 ℃; and or, standing at 20-50 ℃; and/or the standing time is 12-36 h.
Preferably, the temperature of calcination is 400-650 ℃. Calcining to remove the surfactant and form pores on the surface of the silica particles, thereby being helpful to increase the specific surface area of the silica and improve the column efficiency of the chromatographic packing.
Preferably, the calcination is carried out in a muffle furnace, and the temperature is kept at 400-650 ℃ for 4-7 h.
The application also discloses the monodisperse silicon dioxide microsphere obtained by the preparation method.
Preferably, the particle size range of the monodisperse silicon dioxide microspheres is 1-10 μm.
The invention also discloses the application of the monodisperse silica microsphere as a chromatographic filler for separating dicyandiamide, 5-azacytosine, melamine and ammeline or as a chromatographic filler for separating uracil, uridine, adenosine and cytidine.
According to the technical scheme, cheap and easily-obtained silicate minerals are used as silicon sources, silane coupling agents are used as assistance, surfactants such as N-dodecyl-N, N-dimethyl-N-carboxymethyl betaine, octadecylamine and triglyceride are used as pore-forming agents to prepare the silicon dioxide microspheres, the method is simple to prepare and low in cost, the particle size range of the formed silicon dioxide microspheres is 1-10 microns, no agglomeration exists, and the silicon dioxide microspheres have the characteristics of high monodispersity and small particle size, are stable in chemical properties and high in mechanical strength, have high column efficiency when being used as fillers in chromatographic columns, and are very suitable for being widely used as chromatographic column fillers.
Drawings
FIG. 1 is an SEM electron micrograph of silica microspheres prepared according to example 5;
FIG. 2 is a graph showing a particle size distribution of silica microspheres prepared in example 5.
FIG. 3 is an elution profile of silica microspheres prepared in example 5.
FIG. 4 is a pore size distribution curve of the silica microspheres prepared in example 5.
FIG. 5 is a graph showing the separation effect of the silica microspheres prepared in example 5 on a chromatographic packing.
FIG. 6 is a graph showing the separation effect of silica microspheres prepared in comparative example of example 5 on a chromatographic packing.
Fig. 7 is an SEM photograph of the silica microspheres prepared in example 6.
FIG. 8 is a graph showing a particle size distribution of silica microspheres prepared in example 6.
FIG. 9 is an elution profile of silica microspheres prepared in example 6.
FIG. 10 is a pore size distribution curve of the silica microspheres prepared in example 6.
FIG. 11 is a graph showing the separation effect of silica microspheres prepared in example 6 on a chromatographic packing.
FIG. 12 is a graph showing the separation effect of silica microspheres prepared in comparative example of example 6 on a chromatographic packing. .
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
Before the present embodiments are further described, it is to be understood that the scope of the invention is not limited to the particular embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the invention in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and with the description of the invention.
The applicant provides a novel preparation method of monodisperse silica microspheres for chromatography, which adopts cheap and easily-obtained silicate minerals as silicon sources, takes silane coupling agents as assistance, and takes surfactants as pore-forming agents to prepare the silica microspheres, and the silica microspheres formed by the method have the particle size range of 1-10 mu m, are free from agglomeration, have the characteristics of high monodispersity and small particle size, are stable in chemical properties and high in mechanical strength, have high column efficiency when being used as a filler in a chromatographic column, and are very suitable for being widely used as the filler of the chromatographic column.
The surfactant is any one or more of N-dodecyl-N, N dimethyl-N carboxymethyl betaine, octadecylamine, triglyceride, polyoxyethylene dodecylamine, Triton X100 and octadecyl trimethyl ammonium chloride. More preferably, the surfactant is a mixture of any one or two of N-dodecyl-N, N-dimethyl-N-carboxymethyl betaine, octadecylamine, triglyceride, polyoxyethylene dodecylamine, Triton X100 and octadecyl trimethyl ammonium chloride in a mass ratio of 1: 1.
Preferably, the silicate mineral is one or more of diatomite, white carbon black, kaolin, montmorillonite and attapulgite.
Preferably, the silane coupling agent is selected from one or more of bis- [3- (triethoxysilyl) propyl ] -disulfide, bis- [3- (triethoxysilyl) propyl ] -tetrasulfide, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriacetoxysilane, and vinyltributyl-silane-tri-peroxide.
The specific preparation process in this example is as follows:
(1) washing silicate minerals twice with deionized water, soaking in hydrochloric acid solution for a period of time, taking out the samples, washing with deionized water again, drying at 50-90 ℃ to obtain pretreated silicate mineral samples, fully mixing the pretreated silicate mineral samples with sodium hydroxide solution, and filtering to obtain sodium silicate solution; mixing a sodium silicate solution with a silane coupling agent to obtain a silicic acid solution;
(2) adding a surfactant, ethanol and distilled water in a certain proportion into a beaker, and stirring to dissolve the surfactant to obtain a surfactant solution with the percentage concentration of 0.5-10 wt%; adding the surfactant solution with the percentage concentration of 0.5-10 wt% into the silicic acid solution with a certain concentration at a certain temperature, stirring, and stopping stirring when the reaction system is changed from clear to turbid to obtain a silica sol solution;
(3) standing the silica sol solution at a certain temperature for a period of time, pouring out supernatant to obtain white precipitate at the bottom of a beaker, and washing the white precipitate with distilled water and ethanol for several times to obtain the silica surfactant composite microspheres;
(4) soaking the silicon dioxide surfactant composite microspheres in a hydrochloric acid solution with a certain concentration for a period of time, washing to be neutral, and putting the microspheres into a vacuum oven for drying to obtain acidified silicon dioxide surfactant composite microspheres;
(5) and putting the acidified silicon dioxide surfactant composite microspheres into a muffle furnace to obtain the high-monodispersity silicon dioxide microspheres.
Preferably, the silicate mineral is 1-10 wt% of the mass of the hydrochloric acid solution.
Preferably, the silicate mineral is 10-40 wt% of the mass of the sodium hydroxide solution.
Preferably, the concentration of the hydrochloric acid solution is 1 to 5 mol/L.
Preferably, the concentration of the sodium hydroxide solution is 2 to 10 mol/L.
Further, the ratio of the ethanol to the water is (1-5): 1.
Preferably, the mass ratio of the sodium silicate solution to the ethanol water solution of the surfactant is (2-10): 100.
preferably, the mass ratio of the silane coupling agent to the sodium silicate solution is (0.5-1): 1.
preferably, the silane coupling agent is one or more of bis- [3- (triethoxysilyl) propyl ] -disulfide and bis- [3- (triethoxysilyl) propyl ] -tetrasulfide.
Preferably, the mixture is prepared into a suspension at the temperature of 20-50 ℃; and or, standing at 20-50 ℃; and/or the standing time is 12-36 h.
Preferably, the acidified silicon dioxide surfactant composite microspheres are placed in a muffle furnace and are subjected to heat preservation for 6 hours at the temperature of 400-650 ℃.
The technical solution and the technical effects thereof will be further explained by specific examples and implementation effect data.
Example 1
The preparation method of the monodisperse silica microspheres for chromatography in this embodiment includes the following steps:
1) washing 10g of diatomite twice with deionized water, soaking the diatomite in 150ml of hydrochloric acid solution (1mol/L) for 12 hours, taking out a sample, washing the sample with the deionized water again, and drying the sample at 70 ℃ to obtain a pretreated diatomite sample;
2) fully mixing the pretreated diatomite sample with 30ml of sodium hydroxide solution (5mol/L), and filtering to obtain sodium silicate solution; mixing the sodium silicate solution with a silane coupling agent to obtain a silicic acid solution; the silane coupling agent is bis- [3- (triethoxy silicon) propyl ] -tetrasulfide; the mass ratio of the silane coupling agent to the sodium silicate solution is 1: 1;
3) adding 200ml of distilled water and 600ml of absolute ethanol into 6g of N-dodecyl-N, N dimethyl-N carboxymethyl betaine, and stirring to dissolve the N-dodecyl-N, N dimethyl-N carboxymethyl betaine to prepare an ethanol aqueous solution of the N-dodecyl-N, N dimethyl-N carboxymethyl betaine; transferring the ethanol aqueous solution of N-dodecyl-N, N dimethyl-N carboxymethyl betaine into a beaker, adding 30ml of silicic acid solution into the ethanol aqueous solution of N-dodecyl-N, N dimethyl-N carboxymethyl betaine at 20 ℃ while violently stirring, and stopping stirring until white turbidity appears in the ethanol aqueous solution of N-dodecyl-N, N dimethyl-N carboxymethyl betaine;
4) keeping a standing state for 24 hours; pouring out the supernatant, filtering and washing white precipitates at the bottom of the beaker with ethanol and water respectively, putting the white precipitates into a vacuum drying oven for drying for 12 hours, preparing 0.1M hydrochloric acid, soaking a sample in the hydrochloric acid for 11 hours, filtering and washing the sample to be neutral, and drying the sample in the oven for 10 hours to obtain white powder;
5) calcining the mixture in a muffle furnace at 600 ℃ for 6 hours to obtain the monodisperse silicon dioxide microspheres.
An SEM electron micrograph of the silica microspheres obtained in this example is shown in fig. 1. As can be seen from FIG. 1, the silica microspheres after calcination are spherical, have good surface appearance, no breakage, no agglomeration and uniform particle size.
Example 2
The preparation method of the monodisperse silica microspheres for chromatography in this embodiment includes the following steps:
1) washing 10g of white carbon black twice with deionized water, soaking in 150ml of hydrochloric acid solution (1mol/L) for 12h, taking out a sample, washing with deionized water again, and drying at 80 ℃ to obtain a pretreated white carbon black sample;
2) fully mixing the pretreated white carbon black sample with 30ml of sodium hydroxide solution (5mol/L), and filtering to obtain sodium silicate solution; mixing the sodium silicate solution with a silane coupling agent to obtain a silicic acid solution; the silane coupling agent is bis- [3- (triethoxy silicon) propyl ] -tetrasulfide; the mass ratio of the silane coupling agent to the sodium silicate solution is 1: 1;
3) adding 6g of octadecylamine into 220ml of distilled water and 630ml of absolute ethyl alcohol, and stirring to dissolve the octadecylamine to prepare an ethanol water solution of the octadecylamine; transferring the ethanol aqueous solution of octadecylamine into a beaker, adding 30ml of silicic acid solution into the ethanol aqueous solution of octadecylamine while vigorously stirring at 30 ℃, and stopping stirring until white turbidity appears in the ethanol aqueous solution of octadecylamine;
4) keeping a standing state for 24 hours; pouring out the supernatant, filtering and washing white precipitates at the bottom of the beaker with ethanol and water respectively, putting the white precipitates into a vacuum drying oven for drying for 12 hours, preparing 0.1M hydrochloric acid, soaking a sample in the hydrochloric acid for 12 hours, filtering and washing the sample to be neutral, and drying the sample in the oven for 10 hours to obtain white powder;
5) and (3) calcining the mixture in a muffle furnace for 6 hours at the temperature of 600 ℃ to obtain the monodisperse silicon dioxide microspheres.
Example 3
The preparation method of the monodisperse silica microspheres for chromatography in this embodiment includes the following steps:
1) washing 10g of kaolin twice with deionized water, soaking in 150ml of hydrochloric acid solution (1mol/L) for 12 hours, taking out a sample, washing with the deionized water again, and drying at 70 ℃ to obtain a pretreated kaolin sample;
2) fully mixing the pretreated kaolin sample with 30ml of sodium hydroxide solution (5mol/L), and filtering to obtain sodium silicate solution; mixing the sodium silicate solution with a silane coupling agent to obtain a silicic acid solution; the silane coupling agent is bis- [3- (triethoxy silicon) propyl ] -tetrasulfide; the mass ratio of the silane coupling agent to the sodium silicate solution is 1: 1;
3) adding 6.5g triglyceride and 6.5g octadecylamine into 210ml distilled water and 610ml anhydrous ethanol, stirring to dissolve triglyceride and octadecylamine to obtain ethanol water solution of triglyceride and octadecylamine; transferring the ethanol aqueous solution of triglyceride and octadecylamine into a beaker, adding 30ml of silicic acid solution into the ethanol aqueous solution of triglyceride and octadecylamine at 40 ℃ while vigorously stirring, and stopping stirring until white turbidity appears in the ethanol aqueous solution of triglyceride and octadecylamine;
4) keeping a standing state for 24 hours; pouring out the supernatant, filtering and washing white precipitates at the bottom of the beaker with ethanol and water respectively, putting the white precipitates into a vacuum drying oven for drying for 10 hours, preparing 0.1M hydrochloric acid, soaking a sample in the hydrochloric acid for 10 hours, filtering and washing the sample to be neutral, and drying the sample in the oven for 12 hours to obtain white powder;
5) calcining the mixture for 6 hours in a muffle furnace at the temperature of 600 ℃ to obtain the monodisperse silicon dioxide microspheres.
The analysis of the particle size distribution of the silica microspheres in this example is shown in FIG. 2. As can be seen from FIG. 2, the silica microspheres have uniform particle size distribution, the whole particle size is within the range of 1-10 μm, the particle size is concentrated on 3 μm, and the unicity is good.
Example 4
The preparation method of the monodisperse silica microspheres for chromatography in this embodiment includes the following steps:
1) washing 10g of diatomite twice with deionized water, soaking the diatomite in 150ml of hydrochloric acid solution (1mol/L) for 12 hours, taking out a sample, washing the sample with the deionized water again, and drying the sample at 80 ℃ to obtain a pretreated diatomite sample;
2) fully mixing the pretreated diatomite sample with 30ml of sodium hydroxide solution (5mol/L), and filtering to obtain sodium silicate solution; mixing the sodium silicate solution with a silane coupling agent to obtain a silicic acid solution; the silane coupling agent is a mixture of bis- [3- (triethoxysilyl) propyl ] -tetrasulfide and bis- [3- (triethoxysilyl) propyl ] -disulfide according to the mass ratio of 1: 1; the mass ratio of the silane coupling agent to the sodium silicate solution is 1: 1;
3) adding 6.2g of polyoxyethylene lauryl amine into 250ml of distilled water and 600ml of absolute ethyl alcohol, stirring to dissolve the polyoxyethylene lauryl amine, and preparing an ethanol water solution of the polyoxyethylene lauryl amine; transferring the ethanol water solution of polyoxyethylene lauryl amine into a beaker, adding 30ml of silicic acid solution into the ethanol water solution of polyoxyethylene lauryl amine at 30 ℃ while violently stirring, and stopping stirring until white turbidity appears in the ethanol water solution of polyoxyethylene lauryl amine;
4) keeping a standing state for 24 hours; pouring out the supernatant, filtering and washing white precipitates at the bottom of the beaker with ethanol and water respectively, putting the white precipitates into a vacuum drying oven for drying for 12 hours, preparing 0.15M hydrochloric acid, soaking a sample in the hydrochloric acid for 11 hours, filtering and washing the sample to be neutral, and drying the sample in the oven for 10 hours to obtain white powder;
5) calcining the mixture for 6 hours in a muffle furnace at the temperature of 600 ℃ to obtain the monodisperse silicon dioxide microspheres.
Example 5
The preparation method of the monodisperse silica microspheres for chromatography in this embodiment includes the following steps:
1) washing 10g of diatomite twice with deionized water, soaking the diatomite in 150ml of hydrochloric acid solution (1mol/L) for 12 hours, taking out a sample, washing the sample with the deionized water again, and drying the sample at 80 ℃ to obtain a pretreated diatomite sample;
2) fully mixing the pretreated diatomite sample with 30ml of sodium hydroxide solution (5mol/L), and filtering to obtain sodium silicate solution; mixing the sodium silicate solution with a silane coupling agent to obtain a silicic acid solution; the silane coupling agent is bis- [3- (triethoxy silicon) propyl ] -tetrasulfide; the mass ratio of the silane coupling agent to the sodium silicate solution is 1: 1;
3) adding 250ml of distilled water and 620ml of absolute ethyl alcohol into 6g of octadecyl trimethyl ammonium chloride, and stirring to dissolve the octadecyl trimethyl ammonium chloride to prepare an ethanol water solution of the octadecyl trimethyl ammonium chloride; transferring the ethanol aqueous solution of octadecyl trimethyl ammonium chloride into a beaker, adding 30ml of silicic acid solution into the ethanol aqueous solution of octadecyl trimethyl ammonium chloride at the temperature of 20 ℃ while violently stirring, and stopping stirring until the ethanol aqueous solution of octadecyl trimethyl ammonium chloride is white and turbid;
4) keeping a standing state for 24 hours; pouring out the supernatant, filtering and washing white precipitates at the bottom of the beaker with ethanol and water respectively, putting the white precipitates into a vacuum drying oven for drying for 12 hours, preparing 0.1M hydrochloric acid, soaking a sample in the hydrochloric acid for 10 hours, filtering and washing the sample to be neutral, and drying the sample in the oven for 10 hours to obtain white powder;
5) calcining the mixture for 6 hours at 600 ℃ in a muffle furnace.
The analysis and characterization method comprises the following steps:
procedure for measuring specific surface area and pore Structure of silica microspheres prepared in example 5A sample of 0.15g was weighed, degassed under vacuum at 200 ℃ for 2h and measured with N2As an adsorbate, an adsorption-desorption curve was measured at a liquid nitrogen temperature (-196 ℃ C.). The specific surface area is calculated by adopting a BET method according to an adsorption branch of an adsorption-desorption curve, and the pore size distribution is calculated by adopting a BJH method through a desorption branch. As can be seen from fig. 3, the nitrogen adsorption and desorption curve of the silica microspheres prepared in example 5 is a type iv adsorption curve, a hysteresis loop appears in a high pressure region, and the silica microspheres are a typical mesoporous structure, and as can be seen from the pore size distribution curve in fig. 4, the prepared silica microspheres have a relatively uniform mesoporous structure.
Filling the monodisperse silica microspheres in example 5 into a 2.1 x 150mm chromatographic column for separation test of dicyanodiamide, 5-azacytosine, melamine and ammeline, wherein the specific test method comprises the steps of filling the calcined filler into the 2.1 x 150mm chromatographic column and setting the flow rate to be 1 ml/min; dicyandiamide, 5-azacytosine, melamine and ammeline are taken as samples to be detected, and the mobile phase is water: acetonitrile in a ratio of 2:8 and 500ml as a mobile phase, and performing ultraviolet detection at a column temperature of 30 ℃ and a wavelength of 240 nm. It can be seen from fig. 5 that the chromatographic column filled with the silica microspheres prepared in example 5 has a good separation effect on dicyanodiamide, 5-azacytosine, melamine and ammeline.
As a comparative example of example 5, a difference from example 5 was that "mixing the sodium silicate solution with a silane coupling agent to obtain a silicic acid solution" was not included; the silane coupling agent is bis- [3- (triethoxy silicon) propyl ] -tetrasulfide; the mass ratio of the silane coupling agent to the sodium silicate solution is 1:1 "; and directly mixing sodium silicate solution with surfactant solution. The separation effect measured by the same method is shown in fig. 6, and it can be seen from fig. 6 that the separation effect is not as good as that of the dioxidized microspheres prepared in example 7 of the present application.
Example 6
The preparation method of the monodisperse silica microspheres for chromatography in this embodiment includes the following steps:
1) washing 10g of white carbon black twice with deionized water, soaking in 150ml of hydrochloric acid solution (1mol/L) for 12h, taking out a sample, washing with deionized water again, and drying at 80 ℃ to obtain a pretreated white carbon black sample;
2) fully mixing the pretreated white carbon black sample with 30ml of sodium hydroxide solution (5mol/L), and filtering to obtain sodium silicate solution; mixing the sodium silicate solution with a silane coupling agent to obtain a silicic acid solution; the silane coupling agent is vinyl triethoxysilane; the mass ratio of the silane coupling agent to the sodium silicate solution is 1: 1;
3) adding 6.3g of octadecylamine into 210ml of distilled water and 620ml of absolute ethyl alcohol, and stirring to dissolve the octadecylamine to prepare an ethanol water solution of the octadecylamine; transferring the ethanol aqueous solution of octadecylamine into a beaker, adding 30ml of silicic acid solution into the ethanol aqueous solution of octadecylamine while vigorously stirring at 30 ℃, and stopping stirring until white turbidity appears in the ethanol aqueous solution of octadecylamine;
4) keeping a standing state for 24 hours; pouring out the supernatant, filtering and washing white precipitates at the bottom of the beaker with ethanol and water respectively, putting the white precipitates into a vacuum drying oven for drying for 12 hours, preparing 0.1M hydrochloric acid, soaking a sample in the hydrochloric acid for 11 hours, filtering and washing the sample to be neutral, and drying the sample in the oven for 10 hours to obtain white powder;
5) calcining the mixture for 6 hours at 600 ℃ in a muffle furnace.
The analysis and characterization method comprises the following steps:
procedure for measuring specific surface area and pore Structure of silica microspheres prepared in example 6A sample of 0.15g was weighed, degassed under vacuum at 200 ℃ for 2h and measured with N2As an adsorbate, an adsorption-desorption curve was measured at a liquid nitrogen temperature (-196 ℃ C.). The specific surface area is calculated by adopting a BET method according to an adsorption branch of an adsorption-desorption curve, and the pore size distribution is calculated by adopting a BJH method through a desorption branch. As can be seen from FIG. 9, the nitrogen adsorption/desorption curve of the silica microspheres prepared in example 6 is a type IV adsorption curve, and a hysteresis loop appears in a high-pressure region, and the silica microspheres are a typical mesoporous structure, and are shown in the figureThe 10-aperture distribution curve shows that the prepared silica microspheres have relatively uniform mesoporous structures.
The monodisperse silica microspheres in example 6 were packed into a 2.1 × 50mm chromatographic column for separation testing of uracil, uridine, adenosine, and cytidine, by packing the calcined filler into a 2.1 × 50mm chromatographic column and setting a flow rate of 0.2 ml/min; uracil, uridine, adenosine and cytidine are used as samples to be detected, and the mobile phase is ammonium acetate: acetonitrile in a ratio of 1:9 and 500ml as a mobile phase, and performing ultraviolet detection at a column temperature of 30 ℃ and a wavelength of 254 nm. It can be seen from fig. 11 that the silica microspheres prepared in example 6 filled a chromatographic column, which can separate uracil, uridine, adenosine, and cytidine from each other well.
As a comparative example of example 6, a difference from example 6 was that "mixing the sodium silicate solution with a silane coupling agent to obtain a silicic acid solution" was not included; the silane coupling agent is bis- [3- (triethoxy silicon) propyl ] -tetrasulfide; the mass ratio of the silane coupling agent to the sodium silicate solution is 1:1 "; and directly mixing sodium silicate solution with surfactant solution. The separation effect measured by the same method is shown in fig. 12, and it can be seen from fig. 12 that the separation effect is not as good as that of the dioxidized microspheres prepared in example 6 of the present application.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A preparation method of monodisperse silicon dioxide microspheres for chromatography comprises the following steps:
1) soaking silicate minerals in a hydrochloric acid solution to obtain pretreated silicate minerals;
2) mixing the pretreated silicate mineral with a sodium hydroxide solution and filtering to obtain a sodium silicate solution;
3) mixing the sodium silicate solution with a silane coupling agent to obtain a silicic acid solution;
4) preparing a suspension by the silicic acid solution and an ethanol water solution of a surfactant;
5) standing to separate out a white precipitate, pickling the white precipitate to be neutral, and drying to obtain white powder;
6) and calcining the white powder to obtain the monodisperse silica microspheres for chromatography.
2. The preparation method according to claim 1, wherein the silicate mineral is one or more of diatomite, white carbon black, kaolin, montmorillonite and attapulgite.
3. The production method according to claim 1, wherein the silicate mineral is 1 to 10 wt% of the mass of the hydrochloric acid solution; and/or the silicate mineral accounts for 10-40 wt% of the mass of the sodium hydroxide solution.
4. The production method according to claim 1, wherein the concentration of the hydrochloric acid solution is 1 to 5 mol/L; and/or the concentration of the sodium hydroxide solution is 2-10 mol/L.
5. The method according to claim 1, wherein the surfactant is one or more of N-dodecyl-N, N-dimethyl-N-carboxymethylbetaine, octadecylamine, triglyceride, polyoxyethylenedodecylamine, Triton X100, and octadecyl trimethyl ammonium chloride.
6. The preparation method according to claim 1, wherein the concentration of the surfactant in the suspension is 5 to 15 g/L.
7. The preparation method according to claim 1, wherein the mass ratio of ethanol to water in the ethanol aqueous solution is (1-5): 1; and/or the mass ratio of the sodium silicate solution to the ethanol water solution of the surfactant is (2-10): 100, respectively; and/or preparing into suspension at the temperature of 20-50 ℃; and/or standing at 20-50 ℃; and/or standing for 12-36 h; and/or the calcination temperature is 400-650 ℃.
8. The method according to claim 1, wherein the silane coupling agent is one or more selected from the group consisting of bis- [3- (triethoxysilyl) propyl ] -disulfide, bis- [3- (triethoxysilyl) propyl ] -tetrasulfide, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriacetoxysilane, and vinyltributylsilane; and/or the mass ratio of the silane coupling agent to the sodium silicate solution is (0.5-1): 1.
9. monodisperse silica microspheres obtainable by the process according to any one of claims 1 to 8.
10. Use of monodisperse silica microspheres according to claim 9 as chromatography packing for the separation of dicyanodiamide, 5-azacytosine, melamine and ammeline, or as chromatography packing for the separation of uracil, uridine, adenosine and cytidine.
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