CN115340100B - Method for preparing silicon dioxide by utilizing dust recovered from silicon production - Google Patents
Method for preparing silicon dioxide by utilizing dust recovered from silicon production Download PDFInfo
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- CN115340100B CN115340100B CN202111499567.4A CN202111499567A CN115340100B CN 115340100 B CN115340100 B CN 115340100B CN 202111499567 A CN202111499567 A CN 202111499567A CN 115340100 B CN115340100 B CN 115340100B
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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
- C01B33/181—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process
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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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Abstract
The invention relates to the technical field of C01B chemical production, and in particular provides a method for preparing silicon dioxide by utilizing dust recovered from silicon production. A method for preparing silica from dust recovered from silicon production, comprising the steps of: (1) preparation of dust: preparing dust obtained by silicon production and recovery; (2) high temperature preparation of silica: and putting the prepared dust into a high-temperature furnace, then inputting oxygen into the high-temperature furnace, and carrying out high-temperature oxidation on the dust in the high-temperature furnace to obtain the silicon dioxide. The invention uses the waste material produced by silicon as the raw material, has the characteristics of environmental protection, truly realizes the recycling between the raw material and the product, is a complete gas-solid reaction in the preparation process, does not need to add additional liquid phase components, and effectively avoids the problems of equipment corrosion and waste liquid aftertreatment.
Description
Technical Field
The invention relates to the technical field of C01B chemical production, and in particular provides a method for preparing silicon dioxide by utilizing dust recovered from silicon production.
Technical Field
Silica is a nontoxic, light and porous fine powder with good dispersibility, is widely used in the fields of rubber, organic silicon materials, adhesives, papermaking, medicine and the like, and glass cement is used as a common adhesive and has good light and wear resistance, and in order to increase the performance of the glass cement, the silica is often added into the glass cement.
In the prior art, some chemical synthesis methods are often used for preparing the silicon dioxide, but the environmental protection of the methods is poor, so that some researches often use some recovered dust or liquid to prepare the silicon dioxide. Patent CN103342366a provides a method for purifying silica from industrial hot residues, but it requires the use of acids to treat the residues during the reaction, which acids not only generate a lot of waste acid liquid, but also may affect the surface properties of the silica during calcination, which makes the silica easy to be tacky on the glass surface when used in glass cement; the patent CN111252779B, after reacting oxygen with dust suspended in oxygen by electromagnetic waves, gives silica, but the silica is prepared in a spherical shape with a relatively single particle size, and cannot be used well in glass cement due to a limited amount of addition.
Disclosure of Invention
In order to solve the above technical problems, a first aspect of the present invention provides a method for preparing silica using dust recovered from silicon production, comprising the steps of:
(1) Preparation of dust: preparing dust obtained by silicon production and recovery;
(2) High temperature preparation of silica: and putting the prepared dust into a high-temperature furnace, then inputting oxygen into the high-temperature furnace, and carrying out high-temperature oxidation on the dust in the high-temperature furnace to obtain the silicon dioxide.
For step (1)
In the production process of silicon powder, silicon powder is prepared by reducing silicon dioxide with carbon at 870-1728 ℃ under high temperature. Under the condition of 1500-1710 ℃, silicon dioxide is easy to evaporate to form SiO, dust such as SiO, carbon powder, silicon powder and the like is obtained in a dust recycling device, the silicon dioxide is prepared by utilizing the obtained dust recovered in the production of silicon, and the process takes waste materials in the production of silicon as raw materials and has the characteristics of environmental protection.
For step (2)
Preferably, the high temperature oxidation is three-stage heating; the temperature of the first stage of high-temperature oxidation is 100-400 ℃ (preferably 200-300 ℃, and more preferably 250 ℃); the temperature of the second stage high temperature oxidation is 500-800 ℃ (preferably 650-750 ℃ and more preferably 700 ℃); the temperature of the third stage high-temperature oxidation is 900-1300 ℃ (preferably 1100-1250 ℃ and further preferably 1200 ℃)
The inventors have found that the purity of silica produced using a specific three-stage elevated temperature in the present system is higher, probably because some competing relationships of oxidation and reduction reactions in the reaction system can be effectively controlled so that oxidation reactions can occur more.
Meanwhile, by controlling the three-stage reaction, the silicon dioxide with higher purity can be obtained, and meanwhile, the application performance is better, probably because the silicon dioxide does not undergo a reduction reaction with carbon when the temperature of the first stage is lower and is better fully oxidized with oxygen by adopting a specific three-stage heating mode, so that the silicon dioxide can be fully formed, and carbon can be fully oxidized into carbon dioxide instead of carbon monoxide when the temperature of the second stage is lower, so that the reduction reaction in a high-temperature furnace is reduced; at the reaction temperature of the third stage, the defect that silicon cannot react sufficiently due to the deposition of silicon dioxide can be effectively avoided; meanwhile, in the second stage, because carbon dust is arranged in the dust, the carbon dust has a porous structure, and is easy to adsorb and then react with oxygen, the reduction reaction of silicon dioxide can be effectively avoided, and the purity of the silicon dioxide is effectively increased.
Preferably, the temperature rise rate is 20 to 50℃per minute (preferably 30 to 45℃per minute, more preferably 35℃per minute). The temperature rise rate in the present invention refers to a rate of rising from room temperature to the temperature of the first-stage high-temperature oxidation, a rate of rising from the temperature of the first-stage high-temperature oxidation to the temperature of the second-stage high-temperature oxidation, and a rate of rising from the temperature of the second-stage high-temperature oxidation to the temperature of the third-stage high-temperature oxidation.
Preferably, the residence time of the first stage high temperature oxidation is 30 to 70 minutes (preferably 40 to 60 minutes; more preferably 50 minutes); the residence reaction time of the second stage high-temperature oxidation is 20-60 min (preferably 30-50 min); the residence reaction time of the third stage high temperature oxidation is 60-120 min (preferably 70-90 min); wherein, the residence reaction time refers to the reaching of a reaction temperature starting meter.
Extensive research and development experiments have found that the need to strictly control the reaction time, too long or too short a reaction time may affect the forward progress of the oxidation reaction.
Preferably, the pressure of the input oxygen is 0.5 to 2MPa (preferably 0.8 to 1.2MPa; more preferably 1 MPa). Wherein, the pressure of the input oxygen refers to the pressure of the input oxygen in such an amount that the high temperature furnace reaches.
Preferably, the concentration of dust suspended in oxygen is greater than 0.5g/m 3 The method comprises the steps of carrying out a first treatment on the surface of the Further preferably, the concentration of the dust suspended in the oxygen is 60 to 80g/m 3 (preferably 70 g/m) 3 )。
In the prior art, in order to enable the oxidation reaction to fully occur, a very excessive oxygen gas is often used, but research shows that the higher the pressure of oxygen is, the better the pressure of oxygen is, and when the pressure of oxygen is too high, the performance of the prepared silicon dioxide is rather poor, probably because the content of oxygen is too high, the pressure in the system is too high, so that some reactions with increased volume are easier to reversely proceed, so that the silicon dioxide is easier to reduce, and meanwhile, the influence of the pressure on the reaction of silicon monoxide and carbon in the process of reacting to generate silicon and carbon dioxide is smaller, and the reaction can be continuously performed.
In a second aspect the invention provides silica prepared by any of the methods described above for preparing silica from dust recovered from the production of silicon.
The third aspect of the present invention provides the use of silica as a filler for polymers, such as a filler for polymer coatings, a filler for polymer adhesives, a filler for polymer glass cement, and the like.
Compared with the prior art, the invention at least comprises the following beneficial effects:
1. the invention uses the waste material of silicon production as the raw material, has the characteristics of environmental protection, truly realizes the recycling between the raw material and the product, is a complete gas-solid reaction in the preparation process, does not need to add additional liquid phase components, and effectively avoids the problems of equipment corrosion and waste liquid aftertreatment.
2. In the prior art, when simple substance silicon is used for high-temperature sintering, crushing, ball milling, acid washing, water washing and dehydration are needed, then high-temperature melting is performed, and finally oxidation reaction is performed, so that the process flow is complicated, a large amount of waste acid is generated, and during the oxidation process, the influence of gas generated by some acidic impurities on a reaction system is possibly caused.
3. In the prior art, when the recovered silica fume is used for preparing the silica, templates such as a surfactant are used for promoting the growth of the silica, but the dispersibility of the surfactant on the silica is difficult to control.
4. Because some templates are not used for controlling the particle size of the silicon dioxide in the invention, the inventor unexpectedly found that by setting a specific three-stage high-temperature oxidation mode in the invention, the oxidation reaction in a system can be better promoted, silicon monoxide and silicon powder can fully generate the silicon dioxide, and the reduction reaction of the silicon dioxide can be prevented, so that the prepared silicon dioxide can be effectively generated and has higher purity.
5. By controlling the oxygen adding pressure, the forward reaction can be better promoted, so that the reaction rate and the purity of the silicon dioxide are better improved.
Drawings
FIG. 1 is a scanning electron microscope image of silica prepared in example 1;
FIG. 2 is a scanning electron microscope image of the silica prepared in example 2;
FIG. 3 is a scanning electron microscope image of the silica prepared in example 3.
Detailed Description
The specific surface area of silica was measured using an Autosorb IQ-XR full-automatic specific surface area and porosity analyzer, instruments, U.S. Kang Da.
Example 1
A first aspect of the present embodiment provides a method for preparing silica from dust recovered from silicon production, comprising the steps of:
(1) Preparation of dust: preparing dust obtained by silicon production and recovery;
(2) High temperature preparation of silica: the prepared dust was put into a high temperature furnace, and then oxygen was fed into the high temperature furnace (the pressure of the fed oxygen was 0.8MPa, the concentration of the dust suspended in the oxygen was 60 g/m) 3 ) Then heating to 200 ℃ at a speed of 30 ℃/min, and oxidizing at a high temperature of 200 DEG CAfter 40min, the temperature is increased to 650 ℃ at the speed of 30 ℃/min, the high-temperature oxidation reaction is carried out for 30min at the temperature of 650 ℃, the temperature is increased to 1100 ℃ at the speed of 30 ℃/min, and the high-temperature oxidation reaction is carried out for 70min at the temperature of 1100 ℃ to obtain the silicon dioxide.
FIG. 1 is a scanning electron microscope image of the prepared silica;
the specific surface area of the obtained silicon dioxide is 80.2m after test 2 /g。
Example 2
A first aspect of the present embodiment provides a method for preparing silica from dust recovered from silicon production, comprising the steps of:
(1) Preparation of dust: preparing dust obtained by silicon production and recovery;
(2) High temperature preparation of silica: the prepared dust was put into a high temperature furnace, and then oxygen was fed into the high temperature furnace (the pressure of the fed oxygen was 1.2MPa, the concentration of the dust suspended in the oxygen was 80 g/m) 3 ) Then heating to 300 ℃ at a speed of 40 ℃/min, carrying out high-temperature oxidation reaction for 60min at 300 ℃, heating to 750 ℃ at a speed of 40 ℃/min, carrying out high-temperature oxidation reaction for 40min at 750 ℃, heating to 1250 ℃ at a speed of 40 ℃/min, and carrying out high-temperature oxidation reaction for 80min at 1250 ℃ to obtain the silicon dioxide.
FIG. 2 is a scanning electron microscope image of the prepared silica;
the specific surface area of the obtained silicon dioxide is 100.6m after test 2 /g。
Example 3
A first aspect of the present embodiment provides a method for preparing silica from dust recovered from silicon production, comprising the steps of:
(1) Preparation of dust: preparing dust obtained by silicon production and recovery;
(2) High temperature preparation of silica: putting the prepared dust into a high temperature furnace, and then introducing oxygen into the high temperature furnace (the pressure of the introduced oxygen is 1MPa, and the concentration of the dust suspended in the oxygen is 70 g/m) 3 ) Then heating to 250deg.C at a rate of 35deg.C/min, at 250deg.CAnd (3) after the high-temperature oxidation reaction is carried out for 50min, the temperature is raised to 700 ℃ at the speed of 35 ℃/min, the high-temperature oxidation reaction is carried out for 40min at the temperature of 700 ℃, the temperature is raised to 1200 ℃ at the speed of 35 ℃/min, and the high-temperature oxidation reaction is carried out for 80min at the temperature of 1200 ℃ to obtain the silicon dioxide.
FIG. 3 is a scanning electron microscope image of the prepared silica;
the specific surface area of the obtained silicon dioxide is 70.5m after test 2 /g。
Example 4
A first aspect of the present embodiment provides a method for preparing silica from dust recovered from silicon production, comprising the steps of:
(1) Preparation of dust: preparing dust obtained by silicon production and recovery;
(2) High temperature preparation of silica: putting the prepared dust into a high temperature furnace, and then introducing oxygen into the high temperature furnace (the pressure of the introduced oxygen is 1MPa, and the concentration of the dust suspended in the oxygen is 70 g/m) 3 ) Then heating to 1000 ℃ at a speed of 35 ℃/min, and carrying out high-temperature oxidation reaction at 1000 ℃ for 170min to obtain the silicon dioxide.
In a first aspect, the present embodiment provides a silica prepared by the above method.
Example 5
A first aspect of the present embodiment provides a method for preparing silica from dust recovered from silicon production, comprising the steps of:
(1) Preparation of dust: preparing dust obtained by silicon production and recovery;
(2) High temperature preparation of silica: putting the prepared dust into a high temperature furnace, and then introducing oxygen into the high temperature furnace (the pressure of the introduced oxygen is 5MPa, and the concentration of the dust suspended in the oxygen is 70 g/m) 3 ) Then heating to 1000 ℃ at a speed of 35 ℃/min, and carrying out high-temperature oxidation reaction at 1000 ℃ for 300min to obtain the silicon dioxide.
In a first aspect, the present embodiment provides a silica prepared by the above method.
Performance testing
Silica was added to the same formulation of glass cement (formulation of glass cement comprising 107 cement, simethicone, methyl mixed ketoxime type cross-linking agent, dibutyltin dilaurate, silane coupling agent, silica, prepared by mechanical stirring and mixing under vacuum state), and then the properties were tested, and the results are shown in table 1:
TABLE 1
Claims (5)
1. A method for preparing silica from dust recovered from silicon production, comprising the steps of:
(1) Preparation of dust: preparing dust obtained by silicon production and recovery;
(2) High temperature preparation of silica: putting the prepared dust into a high-temperature furnace, then inputting oxygen into the high-temperature furnace, and carrying out high-temperature oxidation on the dust in the high-temperature furnace to obtain silicon dioxide;
high-temperature oxidation is three-stage heating; the temperature of the first stage high-temperature oxidation is 200-300 ℃; the temperature of the second stage high-temperature oxidation is 650-750 ℃; the temperature of the third stage high temperature oxidation is 1100-1250 ℃;
the residence reaction time of the first stage high temperature oxidation is 40-60 min;
the residence reaction time of the second stage high temperature oxidation is 30-50 min;
the residence reaction time of the third stage high temperature oxidation is 70-90 min;
the pressure of the input oxygen is 0.8-1.2 MPa.
2. The method for preparing silicon dioxide by utilizing the dust recovered from silicon production according to claim 1, wherein the heating rate is 20-50 ℃/min.
3. A method for preparing silicon dioxide by utilizing dust recovered from silicon production as set forth in claim 1The method is characterized in that the concentration of dust suspended in oxygen is greater than 0.5g/m 3 。
4. A silica prepared by the method for preparing silica from the dust recovered from the production of silicon according to any one of claims 1 to 3.
5. Use of the silica according to claim 4 in a glass cement.
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| JP2001354409A (en) * | 2000-06-07 | 2001-12-25 | Denki Kagaku Kogyo Kk | Method for manufacturing ultrafine powder silica |
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| WO2012153897A1 (en) * | 2011-05-12 | 2012-11-15 | 충남대학교 산학협력단 | Method for producing high-purity porous silica and silicon derived from rice husks |
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| JP2020040861A (en) * | 2018-09-12 | 2020-03-19 | 株式会社クボタ | Method and apparatus for producing amorphous silica |
| CN111252779A (en) * | 2020-04-08 | 2020-06-09 | 汤姆逊新材料科技(嘉兴)有限公司 | Preparation method of spherical nano silicon dioxide |
| CN111268685A (en) * | 2020-03-09 | 2020-06-12 | 邓咏兰 | Synthesis process of fumed silica |
| CN111732108A (en) * | 2020-06-12 | 2020-10-02 | 安徽壹石通材料科技股份有限公司 | Porous amorphous silicon dioxide powder and preparation method and application thereof |
| CN212915406U (en) * | 2020-05-22 | 2021-04-09 | 福建创威新材料科技有限公司 | Mixing apparatus is used in fumed silica production |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011017587A1 (en) * | 2011-04-27 | 2012-10-31 | Evonik Degussa Gmbh | Silica powder with a large pore length |
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- 2021-12-09 CN CN202111499567.4A patent/CN115340100B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001354409A (en) * | 2000-06-07 | 2001-12-25 | Denki Kagaku Kogyo Kk | Method for manufacturing ultrafine powder silica |
| JP2006312583A (en) * | 2006-07-18 | 2006-11-16 | Denki Kagaku Kogyo Kk | Manufacturing method of superfine powder silica |
| WO2012153897A1 (en) * | 2011-05-12 | 2012-11-15 | 충남대학교 산학협력단 | Method for producing high-purity porous silica and silicon derived from rice husks |
| CN109319800A (en) * | 2017-07-31 | 2019-02-12 | 李桂玉 | A kind of method that high-salt wastewater sulfating roasting two-step method prepares silicate |
| JP2020040861A (en) * | 2018-09-12 | 2020-03-19 | 株式会社クボタ | Method and apparatus for producing amorphous silica |
| CN111268685A (en) * | 2020-03-09 | 2020-06-12 | 邓咏兰 | Synthesis process of fumed silica |
| CN111252779A (en) * | 2020-04-08 | 2020-06-09 | 汤姆逊新材料科技(嘉兴)有限公司 | Preparation method of spherical nano silicon dioxide |
| CN212915406U (en) * | 2020-05-22 | 2021-04-09 | 福建创威新材料科技有限公司 | Mixing apparatus is used in fumed silica production |
| CN111732108A (en) * | 2020-06-12 | 2020-10-02 | 安徽壹石通材料科技股份有限公司 | Porous amorphous silicon dioxide powder and preparation method and application thereof |
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