CN101381083A - Method for preparing high pure spherical silica by means of vacuum carbothermal reduction - Google Patents
Method for preparing high pure spherical silica by means of vacuum carbothermal reduction Download PDFInfo
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- CN101381083A CN101381083A CNA2008102334637A CN200810233463A CN101381083A CN 101381083 A CN101381083 A CN 101381083A CN A2008102334637 A CNA2008102334637 A CN A2008102334637A CN 200810233463 A CN200810233463 A CN 200810233463A CN 101381083 A CN101381083 A CN 101381083A
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- silicon dioxide
- spherical
- silicon
- vacuum
- carbothermal reduction
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000009467 reduction Effects 0.000 title claims abstract description 12
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 239000003610 charcoal Substances 0.000 claims abstract description 6
- 238000007323 disproportionation reaction Methods 0.000 claims abstract description 6
- 239000003245 coal Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 230000003647 oxidation Effects 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 239000002028 Biomass Substances 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 238000004380 ashing Methods 0.000 claims description 6
- 239000010881 fly ash Substances 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- 239000000571 coke Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 230000002829 reductive effect Effects 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 abstract description 33
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 239000002956 ash Substances 0.000 abstract 1
- 239000010883 coal ash Substances 0.000 abstract 1
- 239000002006 petroleum coke Substances 0.000 abstract 1
- 239000012798 spherical particle Substances 0.000 abstract 1
- 239000002023 wood Substances 0.000 abstract 1
- 229960001866 silicon dioxide Drugs 0.000 description 27
- 238000006722 reduction reaction Methods 0.000 description 7
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
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Abstract
The invention relates to a method for preparing high-purity ball spherical silicon dioxide through vacuum carbothermic reduction. The method comprises the following steps: carrying outa carbothermic reduction in a vacuum furnace to produce a silicon monoxide gas by using biological ash, pulverized coal ash, silicon dioxide ore as raw materials, and using wood charcoal, petroleum coke, or coal as a carbon reducer; cooling the silicon monoxide gas and carrying out a disproportionation reaction to produce spherical nano silicon dioxide and nano silicon; carrying out oxidation treatment to produce spherical silicon dioxide with high purity which is more than 99.99 percent. The method has the advantages of spherical particle rate of more than 90 percent, uniformly distributed granularity, grain diameters between 20 and 200 nano meters and can satisfy the demands for functional fillings of electronic, electric and chemical products.
Description
One, technical field
The present invention relates to a kind of method of preparing high pure spherical silica by means of vacuum carbothermal reduction.Belong to the vacuum metallurgy technology field.
Two, background technology
High-purity spherical nano SiO
2As a kind of type material, owing to have high-performances such as high dielectric, high heat-resisting, high moisture-proof, high filler loading capacity, low bulk, low-stress, low impurity, low-friction coefficient, have broad application prospects at numerous areas such as electronics, electrical equipment, chemical industry, it is the high-quality functional stuffing of a kind of ideal electronics, electrical equipment, Chemicals, market potential is huge, and economic benefit is obvious.At present, the high-purity spherical nano-silicon dioxide of domestic application depends on import substantially.The research of high-purity spherical nano-silicon dioxide powder is extremely important for the shelves upgrading carried of many industry products, also will change the situation that high-purity spherical nano-silicon dioxide only depends on import greatly.
In recent years, China is rapid to the progress of nano silicon, but also at the early-stage to the research of high-purity spherical nano-silicon dioxide.At present, the method for preparing high-purity spherical nano-silicon dioxide mainly contains high-temperature melting method, mechanical shaping method, chemical Vapor deposition process and sol-gel method or the like, but effect is not very desirable, balling ratio as the high-purity spherical nano-silicon dioxide of high-temperature melting method production can only reach about 80%, and temperature height, matching requirements is harsh, the difficult control of technical parameter, is difficult for obtaining higher degree, even-grained product.Chemical Vapor deposition process raw material costliness, energy consumption height, technical sophistication, to the equipment requirements harshness, the application of the silicon-dioxide that it makes is also limited.The inventive method is compared with these methods, has the advantage that technology is simple, cost is low, economic benefit is high, effectively utilize secondary resource more.
Three, summary of the invention
The method that the purpose of this invention is to provide a kind of preparing high pure spherical silica by means of vacuum carbothermal reduction, adopt the biomass fuel ashing, flyash, silicon dioxide mine is a raw material, charcoal, refinery coke or coal are carbonaceous reducing agent, in vacuum oven, carry out carbothermic reduction reaction, generate silicon monoxide gas, disproportionation reaction takes place and generates spherical nano-silicon dioxide and ball shaped nano silicon in the cooling back, through oxide treatment, generate high-purity spherical nano-silicon dioxide, its purity is greater than 99.99%, balling ratio reaches more than 90%, even particle size distribution, particle diameter are between the 50-200 nanometer, to satisfy electronics, electrical equipment, the needs of the functional stuffing of Chemicals.
The present invention finishes by following steps
1), pre-treatment: will contain silica material and carbonaceous reducing agent and wear into the following fine powder of 50 orders separately, by containing silica material: the proportioning of carbonaceous reducing agent=12:0.8-2.5 is prepared burden, and mixes briquetting; The described silica material that contains comprises a kind of in biomass fuel ashing, flyash and the silicon dioxide mine, and described carbonaceous reducing agent is charcoal, refinery coke or coal;
2), vacuum carbothermal reduction: the piece material that will handle well places the crucible of vacuum oven to carry out vacuum carbothermal reduction, and control vacuum oven internal pressure is 1-4000Pa, and temperature is 800-1800 ℃, and the reaction times is 5-75 minute, and following reaction takes place in crucible:
C+SiO
2＝SiO↑+CO↑
Generate silicon monoxide gas and CO (carbon monoxide converter) gas;
3), the cooling disproportionation reaction: the process that the silicon monoxide gas of generation rises in crucible, along with temperature is reduced between 200 ℃-700 ℃, the vacuum oven internal pressure is 1-4000Pa, and disproportionation reaction takes place:
2SiO＝Si+SiO
2
Generate preparing spherical SiO 2 and spherical silicon.
4), oxide treatment: the spherical nano-silicon dioxide of generation and the material of ball shaped nano silicon are carried out the oxidation of oxygen blast gas, and the rate-controlling of oxygen blast gas is 0.25-10L/min, and the time is 10-60 minute, obtains high pure spherical silica at last.
Compare the advantage that the present invention has with the method for existing preparation high-purity spherical nano-silicon dioxide:
1), in vacuum oven, carry out carbothermic reduction reaction, disproportionation reaction give birth to and oxide treatment after just can generate high-purity spherical nano-silicon dioxide, technology is simple;
2), the raw material that uses of this technology is cheap as fuel-burning power plant biomass fuel ashing, power plant fly ash and silicon dioxide mine, and solved environmental issue, the carbonaceous reducing agent low price, obtain easily, the consumption of the energy also reduces, not only solve environmental issue but also satisfied the needs of the functional stuffing of electronics, electrical equipment, Chemicals, received obvious economic benefit.
Four, description of drawings: Fig. 1 is a process flow sheet of the present invention.
Five, embodiment:
Embodiment one: use the fuel-burning power plant dioxide-containing silica to be raw material as the biomass fuel ashing of 90wt%, charcoal is a reductive agent, wear into the following fine powder of 80 orders separately, mass ratio with 12:1.5 is prepared burden, mix, briquetting, and place the crucible of vacuum oven, control vacuum oven internal pressure is 10-150Pa, temperature is 1100 ℃, reacted 45 minutes, and obtained SiO gas, under the situation that vacuum furnace top vacuumizes, this gas enters condensate pans, and obtain condensation, when temperature drops to 300 ℃, be decomposed into spherical nano-silicon dioxide and ball shaped nano silicon, spherical nano-silicon dioxide and ball shaped nano silicon that condensation is obtained pass through oxygen blast gas oxide treatment, the speed of oxygen blast gas is 1.1L/min, and the time is 20 minutes, finally obtains high-purity spherical nano-silicon dioxide.The purity of resulting high-purity spherical nano-silicon dioxide is 99.99%, and balling ratio is 91%, and even particle size distribution, median size are 60 nanometers.
Embodiment two: with the fuel-burning power plant dioxide-containing silica is that the flyash of 60wt% is raw material, refinery coke is a reductive agent, wear into the following fine powder of 180 orders separately, mass ratio with 12:0.8 is prepared burden, mix, briquetting, and place the crucible of vacuum oven, control vacuum oven internal pressure is 150-300Pa, temperature is 1300 ℃, reacted 60 minutes, and obtained SiO gas, under the situation that vacuum furnace top vacuumizes, this gas enters condensate pans, and obtain condensation, when temperature drops to 500 ℃, be decomposed into spherical nano-silicon dioxide and ball shaped nano silicon, spherical nano-silicon dioxide and ball shaped nano silicon that condensation is obtained pass through oxygen blast gas oxide treatment, the speed of oxygen blast gas is 1.8L/min, and the time is 15 minutes, finally obtains high-purity spherical nano-silicon dioxide.The purity of resulting high-purity spherical nano-silicon dioxide is 99.995%, and balling ratio is 90%, and even particle size distribution, median size are 120 nanometers.
Embodiment three: the silicon dioxide mine with 99wt% is a raw material, brown coal are reductive agent, wear into the following fine powder of 140 orders separately, mass ratio with 12:2.5 is prepared burden, mix, briquetting, and place the crucible of vacuum oven, control vacuum oven internal pressure is 300-500Pa, temperature is 1400 ℃, reacted 75 minutes, and obtained SiO gas, under the situation that vacuum furnace top vacuumizes, this gas enters condensate pans, and obtain condensation, when temperature drops to 600 ℃, be decomposed into spherical nano-silicon dioxide and ball shaped nano silicon, spherical nano-silicon dioxide and ball shaped nano silicon that condensation is obtained pass through oxygen blast gas oxide treatment, the speed of oxygen blast gas is 0.8L/min, and the time is 25 minutes, finally obtains high-purity spherical nano-silicon dioxide.The purity of resulting high-purity spherical nano-silicon dioxide is 99.993%, and balling ratio is 92%, and even particle size distribution, median size are 80 nanometers.
Claims (2)
1, a kind of method of preparing high pure spherical silica by means of vacuum carbothermal reduction, it is characterized in that: it is finished by following steps,
1) pre-treatment: will contain silica material and carbonaceous reducing agent and wear into the following fine powder of 50 orders separately, by containing silica material: the proportioning of carbonaceous reducing agent=12:0.8-2.5 is prepared burden, and mixes briquetting; The described silica material that contains comprises a kind of in biomass fuel ashing, flyash and the silicon dioxide mine, and described carbonaceous reducing agent is charcoal, refinery coke or coal;
2) vacuum carbothermal reduction: the piece material that will handle well places the crucible of vacuum oven to carry out vacuum carbothermal reduction, control vacuum oven internal pressure is 1-4000Pa, temperature is 800-1800 ℃, and the reaction times is 5-75 minute, generates silicon monoxide gas and CO (carbon monoxide converter) gas;
3) cooling disproportionation reaction: the process that the silicon monoxide gas of generation rises in crucible, along with temperature is reduced between 200 ℃-700 ℃, the vacuum oven internal pressure is 1-4000Pa, generates preparing spherical SiO 2 and spherical silicon;
4) oxide treatment: the preparing spherical SiO 2 of generation and the material of spherical silicon are carried out the oxidation of oxygen blast gas, and the rate-controlling of oxygen blast gas is 0.25-10L/min, and the time is 10-60 minute, obtains high pure spherical silica at last.
2, the method for preparing high pure spherical silica by means of vacuum carbothermal reduction according to claim 1, it is characterized in that: the described silica material that contains comprises a kind of in biomass fuel ashing, flyash and the silicon dioxide mine, and described carbonaceous reducing agent is charcoal, refinery coke or coal.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102334637A CN101381083B (en) | 2008-10-22 | 2008-10-22 | Method for preparing high pure spherical silica by means of vacuum carbothermal reduction |
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|---|---|---|---|
| CN2008102334637A CN101381083B (en) | 2008-10-22 | 2008-10-22 | Method for preparing high pure spherical silica by means of vacuum carbothermal reduction |
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| Publication Number | Publication Date |
|---|---|
| CN101381083A true CN101381083A (en) | 2009-03-11 |
| CN101381083B CN101381083B (en) | 2010-10-13 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101792150A (en) * | 2010-03-26 | 2010-08-04 | 昆明理工大学 | Method for preparing stimuli-responsive silicon dioxide nano particle |
| CN102976343A (en) * | 2012-12-31 | 2013-03-20 | 宁夏胜蓝化工环保科技有限公司 | Preparation method for nano-silicon dioxide with low specific surface area |
| TWI392648B (en) * | 2009-08-12 | 2013-04-11 | Ru Yi Jian | Silicon manufacturing method |
| CN103201217A (en) * | 2010-08-19 | 2013-07-10 | 株式会社普利司通 | Method for producing silicon microparticles |
| CN103754888A (en) * | 2013-12-24 | 2014-04-30 | 四川坤森微纳科技股份有限公司 | Preparation process of high-purity spherical SiO2 nano powder |
| CN103974905A (en) * | 2012-10-16 | 2014-08-06 | Lg化学株式会社 | Silicon oxide-carbon composite and method for preparing same |
| CN103987660A (en) * | 2012-11-30 | 2014-08-13 | Lg化学株式会社 | Silicon oxide, and method for preparing same |
| CN104419792A (en) * | 2013-09-05 | 2015-03-18 | 鞍钢股份有限公司 | Pulverized coal and powdery silica mixed briquetting and preparation and furnace protection method thereof |
| CN105384177A (en) * | 2015-11-27 | 2016-03-09 | 江苏联瑞新材料股份有限公司 | Preparing method of submicrometer spherical silicon dioxide micropowder |
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2008
- 2008-10-22 CN CN2008102334637A patent/CN101381083B/en not_active Expired - Fee Related
Cited By (16)
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| TWI392648B (en) * | 2009-08-12 | 2013-04-11 | Ru Yi Jian | Silicon manufacturing method |
| CN101792150A (en) * | 2010-03-26 | 2010-08-04 | 昆明理工大学 | Method for preparing stimuli-responsive silicon dioxide nano particle |
| CN101792150B (en) * | 2010-03-26 | 2012-07-04 | 昆明理工大学 | Method for preparing stimuli-responsive silicon dioxide nano particle |
| CN103201217A (en) * | 2010-08-19 | 2013-07-10 | 株式会社普利司通 | Method for producing silicon microparticles |
| CN103201217B (en) * | 2010-08-19 | 2015-05-27 | 株式会社普利司通 | Method for producing silicon microparticles |
| CN103974905A (en) * | 2012-10-16 | 2014-08-06 | Lg化学株式会社 | Silicon oxide-carbon composite and method for preparing same |
| US9601768B2 (en) | 2012-11-30 | 2017-03-21 | Lg Chem, Ltd. | Silicon oxide and method of preparing the same |
| CN103987660A (en) * | 2012-11-30 | 2014-08-13 | Lg化学株式会社 | Silicon oxide, and method for preparing same |
| CN102976343B (en) * | 2012-12-31 | 2015-02-04 | 宁夏胜蓝化工环保科技有限公司 | Preparation method for nano-silicon dioxide with low specific surface area |
| CN102976343A (en) * | 2012-12-31 | 2013-03-20 | 宁夏胜蓝化工环保科技有限公司 | Preparation method for nano-silicon dioxide with low specific surface area |
| CN104419792A (en) * | 2013-09-05 | 2015-03-18 | 鞍钢股份有限公司 | Pulverized coal and powdery silica mixed briquetting and preparation and furnace protection method thereof |
| CN104419792B (en) * | 2013-09-05 | 2017-02-22 | 鞍钢股份有限公司 | Pulverized coal and powdery silica mixed briquetting and preparation and furnace protection method thereof |
| CN103754888A (en) * | 2013-12-24 | 2014-04-30 | 四川坤森微纳科技股份有限公司 | Preparation process of high-purity spherical SiO2 nano powder |
| CN103754888B (en) * | 2013-12-24 | 2016-03-02 | 四川坤森微纳科技股份有限公司 | A kind of high purity spherical SiO 2nano powder manufacture craft |
| CN105384177A (en) * | 2015-11-27 | 2016-03-09 | 江苏联瑞新材料股份有限公司 | Preparing method of submicrometer spherical silicon dioxide micropowder |
| CN105384177B (en) * | 2015-11-27 | 2018-04-13 | 江苏联瑞新材料股份有限公司 | The preparation method of submicron order preparing spherical SiO 2 micro mist |
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| CN101381083B (en) | 2010-10-13 |
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