CN101804985A - Method for preparing high-purity nanometer silicon dioxide by taking high-purity silicon tetrachloride as material - Google Patents
Method for preparing high-purity nanometer silicon dioxide by taking high-purity silicon tetrachloride as material Download PDFInfo
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Abstract
The invention discloses a method for preparing high-purity nanometer silicon dioxide by taking high-purity silicon tetrachloride as the material, which includes the steps of adding high-purity silicon tetrachloride to absolute ethanol solution or methanol solution while stirring under minus 20-20 DEG C, dripping ultrapure water-ethanol solution or methanol solution which contains 0.1-0.5wt% of polyvinyl alcohol to above mixture according to the reaction proportion to produce colorless transparent sol; seasoning or condensing under reduced pressure to obtain colorless transparent gel; and alcohol leaching and deacidifying the colorless transparent gel until the pH reaches 4-7, then filtrating, freezing, drying and dealcoholizing to obtain high-purity nanometer silicon dioxide powder, wherein the ethanol or methanol filtered out in the alcohol leaching process and the ethanol or methanol removed in the freezing and drying processes are rectified to obtain ethanol or methanol which is returned for use again. Through the method, no metal impurity is introduced into the production; the purity of the nanometer silicon dioxide prepared through the method can be above 99.999%; the total content of metal impurities is less than 10ppm; the grain size can reach 20nm-80nm; the production process is simple; the equipment investment is less; the production cost is low; and the method is easy for industrial production.
Description
Technical field
The present invention relates to a kind of is the method for feedstock production high-purity nm high-purity silicon dioxide with the high purity silicon tetrachloride.
Background technology
It is low especially that high-purity silicon dioxide typically refers to the metals content impurity that contains in the silicon-dioxide, generally at 10ppm and even below the 1ppm, its purposes mainly is the raw material as the filler of unicircuit encapsulants and manufacturing pure quartz glass, fiber optics instrument, silicon dioxide film and low-cost solar level polysilicon.Along with the fast development of photovoltaic industry, the continuous progress of solar-grade polysilicon production technology, the demand of high-purity silicon dioxide differential constantly increases.
The method for preparing at present nano silica powder mainly contains following several: (1) silicon tetrachloride t method: the shortcoming of this method is to need to carry out at the high temperature greater than 1000 ℃, and facility investment is big, particle is big, and product purity is difficult to reach requirement; (2) be chemical precipitation method, carburizing reagent method, the inverse micellar solution method of raw material with silicate,, all have shortcomings such as complex manufacturing, product purity be wayward though these method raw materials cost are low; (3) be raw material spray-drying process or gelling-desiccating method with the silicon sol, production technique is simple, but because in the commercial silicon sol as raw material, metals content impurity is higher, be difficult to remove, product purity is low, is that raw material also can cause the production cost height if adopt expensive high-purity silicasol; (4) be the sol-gel method of raw material with tetraethyl silicate (ETOS), be that tetraethyl silicate generates silicon dioxide gel, gel through hydrolysis, make the silicon-dioxide superfine powder through pyroprocessing again, the product purity height, metal ion content can be controlled at below the 10ppm, shortcoming is that the raw silicon acetoacetic ester costs an arm and a leg, and causes the production cost height.
Summary of the invention
It is the method for feedstock production high-purity nm silicon-dioxide with the lower silicon tetrachloride of price that the technical problem to be solved in the present invention provides a kind of, and this method is not introduced metallic impurity, and production technique is simple, facility investment is few, and production cost is lower, is easy to suitability for industrialized production
Technical solution of the present invention is:
A kind of is the method for feedstock production high-purity nm silicon-dioxide with the high purity silicon tetrachloride, its special character is: under-20～20 ℃ of temperature, high purity silicon tetrachloride is under agitation joined in dehydrated alcohol or the methanol solvate, and the volume ratio of silicon tetrachloride and dehydrated alcohol or methyl alcohol is 4: 1～1: 2; Measure than being added dropwise to ultrapure water-ethanol or the methanol solution that contains 0.1～0.5wt% polyvinyl alcohol by the reaction of setting again, the mol ratio of described silicon tetrachloride and ultrapure water is 1: 3.6～1: 4.4, the volume ratio of ultrapure water and ethanol or methyl alcohol is 2: 1～1: 2, described ethanol or methyl alcohol are dehydrated alcohol or methyl alcohol, also can be 95% ethanol or 95% methyl alcohol, generate the water white transparency silicon sol, ageing or concentrating under reduced pressure obtain colorless transparent gel; Colorless transparent gel is under agitation carried out pure wash-out acid to pH value with dehydrated alcohol or methyl alcohol rise to 4～7, filter then, carry out the lyophilize dealcoholysis again and obtain the high-purity nm silicon-dioxide powdery; Alcohol is washed ethanol and the methyl alcohol that the ethanol that filters out or methyl alcohol and lyophilize are deviate from, and gets ethanol or methyl alcohol and hydrogenchloride through rectifying, and ethanol or methyl alcohol return repeated use.
Above-mentioned is the method for feedstock production high-purity nm silicon-dioxide with the high purity silicon tetrachloride, and smart distilled hydrogenchloride absorbs with ultrapure water and obtains high purity hydrochloric acid.
The advantage of this method is: the cost of material of employing is low, does not introduce metallic impurity in the production, and production technique is simple, facility investment is few, and production cost is lower, is easy to suitability for industrialized production.The purity of the high-purity nm silicon-dioxide that makes reaches more than 99.999%, particle diameter evenly can reach 20-80nm, and below the resultant metal ion content 10ppm, purity is controlled easily, is easy to suitability for industrialized production.
Embodiment
Embodiment 1
In the time of 20 ℃, in the 200ml dehydrated alcohol, be added dropwise to 100ml silicon tetrachloride (purity is 99.9999%); Stir down, measure than being added dropwise to the ultrapure water-ethanolic soln that contains 0.5wt% (in the gross weight of ultrapure water-ethanolic soln) polyvinyl alcohol by the reaction of setting, described ethanol is dehydrated alcohol or 95% ethanol, the mol ratio of silicon tetrachloride/ultrapure water is 1: 3.6, ultrapure water/ethanol volume ratio is 1: 2, generate water white transparency colloidal sol, ageing obtains colorless transparent gel; With colorless transparent gel is 4 with dehydrated alcohol alcohol wash-out acid to pH value under agitation, and filtration is carried out the lyophilize dealcoholysis again and obtained the high-purity nm silicon-dioxide powdery then, and the purity that records high-purity nm silicon-dioxide is 99.9995%, median size is 75nm.
Alcohol is washed ethanol that the ethanol that filters out and methyl alcohol and lyophilize deviates from and methyl alcohol through rectifying, ethanol or methyl alcohol and hydrogenchloride, ethanol or methyl alcohol return repeated use.The hydrogenchloride that rectifying is told absorbs with ultrapure water and obtains high purity hydrochloric acid.
Embodiment 2
10 ℃, in the 100ml dehydrated alcohol, be added dropwise to the 100ml high purity silicon tetrachloride; Stir down, measure than being added dropwise to the ultrapure water-ethanolic soln that contains the 0.3wt% polyvinyl alcohol by the reaction of setting, described ethanol is dehydrated alcohol or 95% ethanol, the mol ratio of silicon tetrachloride/ultrapure water is 1: 4, ultrapure water/ethanol volume ratio is 2: 1, generate water white transparency colloidal sol, ageing obtains colorless transparent gel; With colorless transparent gel is 6 with dehydrated alcohol alcohol wash-out acid to pH value under agitation, and filtration is carried out the lyophilize dealcoholysis again and obtained the high-purity nm silicon-dioxide powdery then, and the purity that records high-purity nm silicon-dioxide is 99.9991%, median size is 80nm.
Alcohol is washed ethanol that the ethanol that filters out and lyophilize deviate from through rectifying, ethanol and hydrogenchloride, ethanol returns repeated use.The hydrogenchloride that rectifying is told absorbs with ultrapure water and obtains high purity hydrochloric acid.
Embodiment 3
0 ℃, in the 100ml dehydrated alcohol, be added dropwise to the 100ml high purity silicon tetrachloride; Stir down, measure than being added dropwise to the ultrapure water-ethanolic soln that contains the 0.3wt% polyvinyl alcohol by the reaction of setting, described ethanol is dehydrated alcohol or 95% ethanol, the mol ratio of silicon tetrachloride/ultrapure water is 1: 4, ultrapure water/ethanol volume ratio is 1: 1, generate water white transparency colloidal sol, ageing obtains colorless transparent gel; With colorless transparent gel is 5 with dehydrated alcohol alcohol wash-out acid to pH value under agitation, filters then, carries out the lyophilize dealcoholysis again, must the high-purity nm silicon-dioxide powdery, and the purity that records high-purity nm silicon-dioxide is 99.9993%, median size is 40nm.
Alcohol is washed ethanol that the ethanol that filters out and lyophilize deviate from through rectifying, ethanol and hydrogenchloride, ethanol returns repeated use.The hydrogenchloride that rectifying is told absorbs with ultrapure water and obtains high purity hydrochloric acid.
Embodiment 4
-10 ℃, in the 100ml anhydrous methanol, be added dropwise to the 400ml high purity silicon tetrachloride; Stir down, measure than being added dropwise to the ultrapure water-methanol solution that contains the 0.1wt% polyvinyl alcohol by the reaction of setting, described ethanol is dehydrated alcohol or 95% ethanol, the mol ratio of silicon tetrachloride/ultrapure water is 1: 4.4, ultrapure water/methyl alcohol volume ratio is 1: 2, generate water white transparency colloidal sol, ageing obtains colorless transparent gel; With colorless transparent gel is 4.5 with anhydrous methanol alcohol wash-out acid to pH value under agitation, filters then, carries out the lyophilize dealcoholysis again, must the high-purity nm silicon-dioxide powdery, and the purity that records high-purity nm silicon-dioxide is 99.9996%, median size is 65nm.
Alcohol is washed ethanol that the ethanol that filters out and lyophilize deviate from through rectifying, ethanol and hydrogenchloride, ethanol returns repeated use.The hydrogenchloride that rectifying is told absorbs with ultrapure water and obtains high purity hydrochloric acid.
Embodiment 5
-20 ℃, in the 150ml dehydrated alcohol, be added dropwise to the 100ml high purity silicon tetrachloride; Add the dissolving of 0.2wt% polyvinyl alcohol, stir down, measure than being added dropwise to the ultrapure water-ethanolic soln that contains the 0.2wt% polyvinyl alcohol by the reaction of setting, described ethanol is dehydrated alcohol or 95% ethanol, the mol ratio of silicon tetrachloride/ultrapure water is 1: 4, and water/ethanol volume ratio is 1: 2, generates water white transparency colloidal sol, ageing obtains colorless transparent gel; With colorless transparent gel is 7 with dehydrated alcohol alcohol wash-out acid to pH value under agitation, filters then, carries out the lyophilize dealcoholysis again, must the high-purity nm silicon-dioxide powdery, and the purity that records high-purity nm silicon-dioxide is 99.9990%, median size is 20nm.
Alcohol is washed ethanol that the ethanol that filters out and lyophilize deviate from through rectifying, ethanolic hydrogen chloride, ethanol returns repeated use.The hydrogenchloride that rectifying is told absorbs with ultrapure water and obtains high purity hydrochloric acid.
Embodiment 6
Dehydrated alcohol in the first step of embodiment 1-embodiment 5 substitutes with anhydrous methanol; Ethanol in second step substitutes with anhydrous methanol or 95% methyl alcohol, and other is constant.
Claims (2)
1. one kind is the method for feedstock production high-purity nm silicon-dioxide with the high purity silicon tetrachloride, it is characterized in that: under-20～20 ℃ of temperature, high purity silicon tetrachloride is under agitation joined in dehydrated alcohol or the methanol solvate, and the volume ratio of silicon tetrachloride and dehydrated alcohol or methyl alcohol is 4: 1～1: 2; Measure than being added dropwise to ultrapure water-ethanol or the methanol solution that contains 0.1～0.5wt% polyvinyl alcohol by the reaction of setting again, the mol ratio of described silicon tetrachloride and ultrapure water is 1: 3.6～1: 4.4, the volume ratio of ultrapure water and ethanol or methyl alcohol is 2: 1～1: 2, described ethanol or methyl alcohol are dehydrated alcohol or methyl alcohol, also can be 95% ethanol or 95% methyl alcohol, generate the water white transparency silicon sol, ageing or concentrating under reduced pressure obtain colorless transparent gel; Colorless transparent gel is under agitation carried out pure wash-out acid to pH value with dehydrated alcohol or methyl alcohol rise to 4～7, filter then, carry out the lyophilize dealcoholysis again and obtain the high-purity nm silicon-dioxide powdery; Alcohol is washed ethanol and the methyl alcohol that the ethanol that filters out or methyl alcohol and lyophilize are deviate from, and gets ethanol or methyl alcohol and hydrogenchloride through rectifying, and ethanol or methyl alcohol return repeated use.
2. according to claim 1 is the method for feedstock production high-purity nm silicon-dioxide with the high purity silicon tetrachloride, it is characterized in that: smart distilled hydrogenchloride absorbs with ultrapure water and obtains high purity hydrochloric acid.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2447020C1 (en) * | 2010-10-05 | 2012-04-10 | Открытое акционерное общество "Государственный научно-исследовательский и проектный институт редкометаллической промышленности "Гиредмет" | Method of obtaining fine silica |
| CN102515481A (en) * | 2011-12-14 | 2012-06-27 | 渤海大学 | Method for preparing high-purity quartz glass precursor by sol-gel method |
| CN102897775A (en) * | 2011-07-25 | 2013-01-30 | 中国石油天然气股份有限公司 | Preparation method for high purity macroporous silica gel |
| CN103712951A (en) * | 2013-12-31 | 2014-04-09 | 清华大学深圳研究生院 | Preparation method and applications of three-dimensional structure-based nanoarray biochip |
| CN106395833A (en) * | 2016-08-31 | 2017-02-15 | 湖北金伟新材料有限公司 | Preparation method for preparing silica sol for catalyst high in purity and uniform in particle size |
| CN106744998A (en) * | 2017-01-17 | 2017-05-31 | 清华大学 | A kind of controllable amorphous monodisperse nano silicon dioxide raw powder's production technology of granularity |
| CN110280309A (en) * | 2019-06-28 | 2019-09-27 | 苏州仕净环保科技股份有限公司 | A kind of preparation process and catalyst of catalyst |
| WO2020228115A1 (en) * | 2019-05-14 | 2020-11-19 | 中天科技精密材料有限公司 | Quartz powder and preparation method therefor |
| CN112064195A (en) * | 2020-09-21 | 2020-12-11 | 新疆理工学院 | Method for preparing hydrophobic silicon dioxide nanofiber membrane by using silicon tetrachloride |
| CN113731415A (en) * | 2021-09-28 | 2021-12-03 | 江苏金聚合金材料有限公司 | Preparation method and application of ethylene glycol catalyst |
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| US4710368A (en) * | 1985-06-24 | 1987-12-01 | Gte Products Corporation | High purity high surface area alpha crystalline silicon nitride |
| CN1626440A (en) * | 2003-12-08 | 2005-06-15 | 北京化工大学 | Method for preparing Nano silicon dioxide |
| CN1712352A (en) * | 2004-06-25 | 2005-12-28 | 中国科学院过程工程研究所 | Preparation of high-purity nanometer silicon dioxide |
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2010
- 2010-04-11 CN CN 201010146559 patent/CN101804985B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4710368A (en) * | 1985-06-24 | 1987-12-01 | Gte Products Corporation | High purity high surface area alpha crystalline silicon nitride |
| CN1626440A (en) * | 2003-12-08 | 2005-06-15 | 北京化工大学 | Method for preparing Nano silicon dioxide |
| CN1712352A (en) * | 2004-06-25 | 2005-12-28 | 中国科学院过程工程研究所 | Preparation of high-purity nanometer silicon dioxide |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2447020C1 (en) * | 2010-10-05 | 2012-04-10 | Открытое акционерное общество "Государственный научно-исследовательский и проектный институт редкометаллической промышленности "Гиредмет" | Method of obtaining fine silica |
| CN102897775A (en) * | 2011-07-25 | 2013-01-30 | 中国石油天然气股份有限公司 | Preparation method for high purity macroporous silica gel |
| CN102897775B (en) * | 2011-07-25 | 2014-08-06 | 中国石油天然气股份有限公司 | Preparation method for high purity macroporous silica gel |
| CN102515481A (en) * | 2011-12-14 | 2012-06-27 | 渤海大学 | Method for preparing high-purity quartz glass precursor by sol-gel method |
| CN103712951A (en) * | 2013-12-31 | 2014-04-09 | 清华大学深圳研究生院 | Preparation method and applications of three-dimensional structure-based nanoarray biochip |
| CN103712951B (en) * | 2013-12-31 | 2016-03-09 | 清华大学深圳研究生院 | A kind of preparation method based on three-dimensional structure nano-array biochip and application thereof |
| CN106395833A (en) * | 2016-08-31 | 2017-02-15 | 湖北金伟新材料有限公司 | Preparation method for preparing silica sol for catalyst high in purity and uniform in particle size |
| CN106744998A (en) * | 2017-01-17 | 2017-05-31 | 清华大学 | A kind of controllable amorphous monodisperse nano silicon dioxide raw powder's production technology of granularity |
| WO2020228115A1 (en) * | 2019-05-14 | 2020-11-19 | 中天科技精密材料有限公司 | Quartz powder and preparation method therefor |
| CN110280309A (en) * | 2019-06-28 | 2019-09-27 | 苏州仕净环保科技股份有限公司 | A kind of preparation process and catalyst of catalyst |
| CN110280309B (en) * | 2019-06-28 | 2022-07-05 | 苏州仕净科技股份有限公司 | Preparation process of catalyst and catalyst |
| CN112064195A (en) * | 2020-09-21 | 2020-12-11 | 新疆理工学院 | Method for preparing hydrophobic silicon dioxide nanofiber membrane by using silicon tetrachloride |
| CN113731415A (en) * | 2021-09-28 | 2021-12-03 | 江苏金聚合金材料有限公司 | Preparation method and application of ethylene glycol catalyst |
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| CN101804985B (en) | 2012-03-07 |
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