CN110683552B - Preparation method of nano silicon dioxide microspheres with particle size of 10-20nm - Google Patents
Preparation method of nano silicon dioxide microspheres with particle size of 10-20nm Download PDFInfo
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- CN110683552B CN110683552B CN201910988430.1A CN201910988430A CN110683552B CN 110683552 B CN110683552 B CN 110683552B CN 201910988430 A CN201910988430 A CN 201910988430A CN 110683552 B CN110683552 B CN 110683552B
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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
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- 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
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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
- C01B33/16—Preparation of silica xerogels
- C01B33/163—Preparation of silica xerogels by hydrolysis of organosilicon compounds, e.g. ethyl orthosilicate
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- 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
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- 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
Abstract
The invention discloses a preparation method of nano silicon dioxide microspheres with particle sizes of 10-20nm, which relates to the technical field of inorganic oxide processing, and takes tetraethoxysilane as a silicon source, prepares nano silicon dioxide through hydrolysis reaction under the combined action of ammonia water, ethanol and water, and leads the prepared nano silicon dioxide microspheres to present unique advantages of regular sphere, good monodispersity and narrow particle size distribution range through the addition of N-hydroxymethyl acrylamide, thereby avoiding the problems of irregular sphere, poor monodispersity and wide particle size distribution range of the prepared nano silicon dioxide in the conventional technical scheme for preparing nano silicon dioxide, and further meeting the market demand for the nano silicon dioxide microspheres with particle sizes of 10-20 nm.
Description
The technical field is as follows:
the invention relates to the technical field of inorganic oxide processing, in particular to a preparation method of nano silicon dioxide microspheres with particle sizes of 10-20 nm.
Background art:
the nano silicon dioxide is a non-toxic, tasteless and pollution-free non-metallic functional material, and has the specific functions in the aspects of thermal resistance and resistance due to small particle size, large specific surface area, strong surface adsorption capacity, large surface energy, high chemical purity and good dispersion property, and can be widely used as a catalyst carrier, a separating agent, an adsorbent and the like.
At present, the preparation method of nano silicon dioxide is divided into a dry method and a wet method. The dry method comprises a gas phase method and an electric arc method, and has the disadvantages of high energy consumption, complex technology and high equipment requirement. The wet method includes a precipitation method and a gel method: (1) a precipitation method: the water glass is adopted to react with acid, particles can further agglomerate and grow up in the aging, washing and drying processes, finally, the obtained product particles usually reach micron level, and the obtained silicon dioxide product has low quality, nonuniform particle size, large particle size and poor dispersibility, and is not beneficial to the wide application of the mechanical property and the optical property of the nano silicon dioxide in industry. (2) Gel method: silicate ester is hydrolyzed under the action of a catalyst to form sol, and the sol is dried and calcined to prepare the nano silicon dioxide, but the particle size cannot be controlled in a narrow distribution range, so that the process needs to be optimized.
The invention content is as follows:
the technical problem to be solved by the invention is to provide a preparation method of nano silicon dioxide microspheres with the particle size of 10-20nm, which is simple and convenient to operate and can effectively control the particle size distribution and the dispersity.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a method for preparing nanometer silica microsphere with particle diameter of 10-20nm comprises dissolving ethyl orthosilicate in ethanol to obtain solution A, dissolving ammonia water in ethanol to obtain solution B, and dissolving dispersant in ethanol to obtain solution C; dripping the solution A and the solution C into the solution B at the same time, and reacting to obtain wet gel; the wet gel is dried and foamed at constant temperature in the air atmosphere to obtain dry gel, and the dry gel is heated and calcined in stages in the air atmosphere to obtain the nano silicon dioxide microspheres.
The volume concentration of the ammonia water is 20-30%.
The molar ratio of the ethyl orthosilicate to the ammonia water to the dispersant is 1:1.5-2: 0.1-0.5.
The temperature of the constant-temperature drying foaming is controlled to be 125-135 ℃.
The temperature control of the step-by-step temperature-rising calcination comprises the following steps: the preheating temperature of the calcining furnace is 400 ℃ at 300-.
The invention controls the particle size distribution range of the prepared nano silicon dioxide microspheres by the operation of step-by-step heating and calcining.
The dispersing agent is prepared by the esterification reaction of N-hydroxymethyl acrylamide and 3-mercaptopropionic acid.
The dispersing agent enables the nano silicon dioxide generated by hydrolysis reaction to be instantly monodisperse in the solution by forming the wrapping layer outside the nano silicon dioxide microspheres, so that the influence of particle aggregation on the monodispersity and the distribution granularity of the prepared nano silicon dioxide microspheres is avoided, and the dispersing agent can be removed during subsequent high-temperature calcination.
In order to accelerate the generation speed of the nano-silica microspheres and improve the generation amount of the nano-silica, the invention also uses a cocatalyst, namely the invention also provides another technical scheme:
a method for preparing nanometer silica microsphere with particle diameter of 10-20nm comprises dissolving ethyl orthosilicate in ethanol to obtain solution A, dissolving ammonia water in ethanol to obtain solution B, and dissolving dispersant in ethanol to obtain solution C; adding a cocatalyst into the solution B, then simultaneously dropwise adding the solution A and the solution C, and reacting to obtain wet gel; the wet gel is dried and foamed at constant temperature in the air atmosphere to obtain dry gel, and the dry gel is heated and calcined in stages in the air atmosphere to obtain the nano silicon dioxide microspheres.
The cocatalyst is titanium diboride, and the molar ratio of the cocatalyst to ammonia water is 0.01-0.05: 1. The titanium diboride does not belong to the catalysts which are known in the field and can be applied to hydrolysis reaction, and the inventor unexpectedly finds that the technical effect of improving the conversion rate of ethyl orthosilicate and the generation rate of nano silicon dioxide can be achieved after the titanium diboride is applied to the hydrolysis reaction as the catalyst in the test process.
The invention has the beneficial effects that: the method takes tetraethoxysilane as a silicon source, prepares the nano-silicon dioxide through hydrolysis reaction under the combined action of ammonia water, ethanol and water, and leads the prepared nano-silicon dioxide microspheres to present unique advantages of regular sphere, good monodispersity and narrow particle size distribution range by adding N-hydroxymethyl acrylamide, thereby avoiding the problems of irregular sphere, poor monodispersity and wide particle size distribution range of the prepared nano-silicon dioxide in the conventional technical scheme for preparing the nano-silicon dioxide, and further meeting the market demand for the nano-silicon dioxide microspheres with the particle size of 10-20 nm.
The specific implementation mode is as follows:
in order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
Example 1
Dissolving 10mmol of ethyl orthosilicate in 5mL of ethanol to prepare a solution A, dissolving 15mmol of ammonia water with volume concentration of 28% in 5mL of ethanol to prepare a solution B, and dissolving 2.5mmol of dispersing agent in 10mL of ethanol to prepare a solution C; dropwise adding the solution A and the solution C into the solution B at the same time, and heating to 55 ℃ to react for 5 hours to obtain wet gel; the wet gel is dried and foamed for 2h at the constant temperature of 125 ℃ in the air atmosphere to obtain dry gel, the dry gel is subjected to stepwise heating and calcination in the air atmosphere to obtain nano silicon dioxide microspheres, the preheating temperature of a calciner is 400 ℃, the temperature is firstly increased to 550 ℃ at the heating rate of 5 ℃/min and is kept for 1h, and the temperature is continuously increased to 700 ℃ at the heating rate of 5 ℃/min and is kept for 1 h. The conversion rate of the ethyl orthosilicate is 98.2 percent, and the yield of the nano silicon dioxide is 97.4 percent.
Preparation of the dispersant: adding 10mmol of N-hydroxymethyl acrylamide and 10mmol of 3-mercaptopropionic acid into 15mL of water, then dropwise adding 0.5mL of concentrated sulfuric acid, heating to 80 ℃, preserving heat for reacting for 3h, standing for 1h, filtering, and drying the obtained solid in an oven at 70 ℃ to constant weight.1H NMR(CDCl3,400MHz),δ:9.36(s,1H),6.08-6.48(m,3H),5.74(s,2H),2.94(t,2H),2.51(t,2H),1.39(s,1H)；ESI-MS:m/z＝190.05[M]+.
Example 2
Dissolving 10mmol of ethyl orthosilicate in 5mL of ethanol to prepare a solution A, dissolving 15mmol of ammonia water with volume concentration of 28% in 5mL of ethanol to prepare a solution B, and dissolving 2.5mmol of dispersing agent in 10mL of ethanol to prepare a solution C; then adding 0.5mmol of cocatalyst titanium diboride into the solution B, then simultaneously dropwise adding the solution A and the solution C, heating to 55 ℃, and reacting for 5 hours to obtain wet gel; the wet gel is dried and foamed for 2h at the constant temperature of 125 ℃ in the air atmosphere to obtain dry gel, the dry gel is subjected to stepwise heating and calcination in the air atmosphere to obtain nano silicon dioxide microspheres, the preheating temperature of a calciner is 400 ℃, the temperature is firstly increased to 550 ℃ at the heating rate of 5 ℃/min and is kept for 1h, and the temperature is continuously increased to 700 ℃ at the heating rate of 5 ℃/min and is kept for 1 h. The conversion rate of the ethyl orthosilicate is 99.7 percent, and the yield of the nano silicon dioxide is 99.2 percent.
The dispersant was prepared as in example 1.
Comparative example 1
Comparative example 1 was prepared based on example 1 without using a dispersant, and the procedure was otherwise the same as in example 1.
Comparative example 2
Based on example 1, the procedure of comparative example 2 was repeated, in which "the preheating temperature of the calciner was set at 400 ℃, the temperature was first raised to 700 ℃ at a rate of 5 ℃/min and the temperature was maintained for 3 hours" in the calcination operation, and the rest of the procedure was the same as that of example 1.
The nano-silica was prepared using the above examples and comparative examples, respectively, and the particle size analysis was performed using a JCM-7000 scanning electron microscope, and the results are shown in table 1.
TABLE 1
| Item | Example 1 | Example 2 | Comparative example 1 | Comparative example 2 |
| Average particle diameter/nm | 10-20 | 10-20 | 30-120 | 20-80 |
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (3)
1. A preparation method of nano silicon dioxide microspheres with particle sizes of 10-20nm is characterized by comprising the following steps: dissolving ethyl orthosilicate in ethanol to prepare a solution A, dissolving ammonia water in ethanol to prepare a solution B, and dissolving a dispersing agent in ethanol to prepare a solution C; dripping the solution A and the solution C into the solution B at the same time, and reacting to obtain wet gel; drying and foaming the wet gel at constant temperature in the air atmosphere to obtain dry gel, and heating and calcining the dry gel in stages in the air atmosphere to obtain nano silicon dioxide microspheres;
the dispersing agent is prepared by the esterification reaction of N-hydroxymethyl acrylamide and 3-mercaptopropionic acid;
the molar ratio of the ethyl orthosilicate to the ammonia water to the dispersant is 1:1.5-2: 0.1-0.5;
the temperature control of the step-by-step temperature-rising calcination comprises the following steps: the preheating temperature of the calcining furnace is 400 ℃ at 300-.
2. The method of claim 1, wherein: the volume concentration of the ammonia water is 20-30%.
3. The method of claim 1, wherein: the temperature of the constant-temperature drying foaming is controlled to be 125-135 ℃.
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