CN102976343B - Preparation method for nano-silicon dioxide with low specific surface area - Google Patents
Preparation method for nano-silicon dioxide with low specific surface area Download PDFInfo
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- CN102976343B CN102976343B CN201210583696.6A CN201210583696A CN102976343B CN 102976343 B CN102976343 B CN 102976343B CN 201210583696 A CN201210583696 A CN 201210583696A CN 102976343 B CN102976343 B CN 102976343B
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Abstract
The invention discloses a preparation method for nano-silicon dioxide with low specific surface area. The preparation method comprises the steps as follows: melting silicon in a crucible furnace; adding pure oxygen into the surface of the molten silicon; carrying out gas-phase reaction on atom-state silicon steam and oxygen molecules to generate silicon monoxide; bringing the generated silicon monoxide from the crucible furnace to a tubular reactor by gas stream; further oxidizing the silicon monoxide into silicon dioxide in the tubular reactor; and after the silicon dioxide leaves from the tubular reactor, quickly mixing the silicon dioxide with normal-temperature air in a mixer, cooling and collecting powdery products in the gas stream. The particle size and the specific surface area of the products can be conveniently adjusted by adjusting process parameters.
Description
Technical field
The present invention relates to a kind of preparation method of nano silicon, belong to field of inorganic material preparing technology.
Background technology
Nano silicon application widely, usually with the silane such as silicon tetrachloride, methyl chlorosilane for raw material, prepared by use gas-phase process, this technique is in the combustion flame of hydrogen and air or oxygen, silane generation hydrolysis reaction generates silicon-dioxide, be characterized in that particle diameter can be low to moderate 10-20nm, product has huge specific surface area, and (common specific surface area is 100-400m
2/ g).This ultra-fine granularity and huge specific surface area impart the special character of fumed silica (also referred to as thermal silica) just, have a wide range of applications in fields such as electronics, paper, makeup, silicon rubber, tackiness agent, paint, coating, ink, medicine, food, agriculturals.
Different from above-mentioned high-ratio surface silicon-dioxide, the nano silicon using specific surface area lower is needed in other field.This to traditional take chlorosilane as the gas-phase process of raw material be a kind of challenge greatly.Offshore company and researcher, to this has been large quantifier elimination, are that the vapor phase process of raw material prepares specific surface area for 25m as DE-A-10139320 discloses with hexamethyldisiloxane
2the method of/g preparing spherical SiO 2; Goldschmidt chemical corporation is in the disclosed CN102256898A patent of China, and describe and utilize liquid polyorganosiloxane to prepare the gas-phase process of low specific surface nano silicon for raw material, the specific surface area before unmodified is 20-35m
2/ g.The preparation technology of the above-mentioned low specific surface silicon-dioxide mentioned is all take siloxanes as the vapor phase process of raw material, and the weak point of this method is that the source of raw material hexamethyldisiloxane, octamethyltrisiloxane or the siloxanes containing more Siliciumatoms that (1) uses is limited; (2) product of this explained hereafter has more flourishing pore texture, and in specific surface area, considerable part is the internal surface provided by internal void, and the specific surface area that particle exterior surface provides only accounts for a wherein part.Table 1 lists spherical SiO under the specific surface area of several fumed silica disclosed in market sale and patent, granularity and the equal particle diameter of Theoretical Calculation
2outer surface area parameter.
Table 1 particle diameter and specific surface area parameter
As shown in Table 1, if make silicon dioxide granule not contain or contain pore texture less, then effectively will reduce specific surface under equal particle diameter, this is the thinking that this patent solves existing technique weak point; Simultaneously in order to solve an existing raw materials technology source difficult problem, this patent adopts the silicon of abundance to be that nano silicon prepared by raw material.
Summary of the invention
The invention is intended to provide a kind of method preparing nano silicon, is that a kind of silicon that utilizes to generate the method for low specific surface nano silicon for raw material in gas phase and oxygen reaction more specifically.
For achieving the above object, the present invention is realized by following technique means:
Be liquid by silicon melting in the crucible oven of argon shield, then control silicon liquid temp 1800-2600 DEG C; Pure oxygen is passed into the upper space of silicon liquid, the gaseous state Siliciumatom in silicon liquid upper space and oxygen molecule react and generate silicon monoxide; The air-flow going out crucible enters tubular reactor, stops 0.1-30 second in tubular reactor, and the temperature in tubular reactor controls at 800-1100 DEG C, and in tubular reactor, silicon monoxide and oxygen continue reaction generation silicon-dioxide; Go out air-flow and the normal temperature air short mix in a mixer of tubular reactor, make gas flow temperature drop to less than 200 DEG C, cooled air-flow collects silicon dioxide granule powder through cloth bag equipment.
In order to obtain the satisfactory silicon-dioxide of purity, mass content≤0.5% of metallic impurity iron, aluminium, calcium in raw silicon, meets this silicon raw material required and comprises chemical grade metallic silicon, solar-grade polysilicon etc.
Pure oxygen passes into the speed on silicon liquid surface and silicon liquid level amasss relevant, and on every square metre of silicon liquid, pure oxygen passes into rate-controlling at 1-30Nm
3/ min.In order to the gas of using tubular reactor cools rapidly, stop the transition coalescence of silicon dioxide granule, the volume entering normal temperature air in mixing tank with final mixed gas temperature lower than 200 DEG C for Con trolling index.
The silicon steam that the present invention utilizes molten silicon to produce in gas phase is silicon source, and in the gas phase of molten silicon surface, silicon exists with atom form.From Si-O system phase diagram, after higher than 1180 DEG C, in gas phase existence is silicon monoxide instead of silicon-dioxide.There is oxidizing reaction further in silicon monoxide and oxygen in tubular reactor, and the temperature of reaction of silicon monoxide and oxygen is preferably at 800-1100 DEG C, excessively slow lower than speed of reaction during this temperature.Use above-mentioned processing condition, silicon monoxide is finally fully oxidized as silicon-dioxide.In order to obtain particle diameter at 50-120nm, specific surface area is at 30-12m
2silicon-dioxide between/g, the control of the residence time is very crucial, when needing to obtain should adopting the shorter residence time when granularity amasss relatively high silicon-dioxide compared with small specific surface, otherwise then uses the longer residence time.That is granularity and the specific surface area of final silicon-dioxide can be controlled easily by controlling the residence time of particle in tubular reactor.
Embodiment
Below by embodiment, more specific description is carried out to the specific embodiment of the present invention, but it is only for illustration of embodiments more of the present invention, and should not be construed as limiting the scope of the present invention.
Embodiment 1
Under argon shield, be, in the crucible of 500mm, the Pure Silicon Metal melting of impurity metal content≤0.1% is warmed up to 1850 DEG C at diameter, pure oxygen is with 1.5Nm
3the speed of/min passes into silicon liquid surface.The residence time of air-flow in tubular reactor going out crucible is 15 seconds, and temperature controls at 950 DEG C.The air-flow and the normal temperature air that go out tubular reactor mix in a mixer, control the intake of normal temperature air make mixing after gas flow temperature be 180 ± 20 DEG C.Cloth bag is utilized to collect product, by analysis, D
50median particle is 105nm, specific surface area 15.3m
2/ g.Close to preparing spherical SiO 2 outer surface area 12.9m under equal particle diameter
2the numerical value of/g.
Embodiment 2
Under argon shield, be, in the crucible of 500mm, the Pure Silicon Metal melting of impurity metal content≤0.1% is warmed up to 2200 DEG C at diameter, pure oxygen is with 5Nm
3the speed of/min passes into silicon liquid surface.The residence time of air-flow in tubular reactor going out crucible is 30 seconds, and temperature controls at 900 DEG C.The air-flow and the normal temperature air that go out tubular reactor mix in a mixer, control the intake of normal temperature air make mixing after gas flow temperature be 180 ± 20 DEG C.Cloth bag is utilized to collect product, by analysis, D
50median particle is 120nm, specific surface area 12m
2/ g.Close to preparing spherical SiO 2 outer surface area 11.25m under equal particle diameter
2the numerical value of/g.
Embodiment 3
Under argon shield, be, in the crucible of 500mm, the solar-grade polysilicon silicon melting of impurity metal content≤0.001% is warmed up to 2600 DEG C at diameter, pure oxygen is with 2Nm
3the speed of/min passes into silicon liquid surface.The residence time of air-flow in tubular reactor going out crucible is 5 seconds, and temperature controls at 1000 DEG C.The air-flow and the normal temperature air that go out tubular reactor mix in a mixer, control the intake of normal temperature air make mixing after gas flow temperature be 180 ± 20 DEG C.Cloth bag is utilized to collect product, by analysis, D
50median particle is 65nm, specific surface area 25.0m
2/ g.Close to preparing spherical SiO 2 outer surface area 20.8m under equal particle diameter
2the numerical value of/g.
Embodiment 4
Under argon shield, be, in the crucible of 500mm, the solar-grade polysilicon silicon melting of impurity metal content≤0.001% is warmed up to 2000 DEG C at diameter, pure oxygen is with 2Nm
3the speed of/min passes into silicon liquid surface.The residence time of air-flow in tubular reactor going out crucible is 10 seconds, and temperature controls at 1100 DEG C.The air-flow and the normal temperature air that go out tubular reactor mix in a mixer, control the intake of normal temperature air make mixing after gas flow temperature be 180 ± 20 DEG C.Cloth bag is utilized to collect product, by analysis, D
50median particle is 90nm, specific surface area 16.8m
2/ g.Close to preparing spherical SiO 2 outer surface area 15m under equal particle diameter
2the numerical value of/g.
Embodiment 5
Under argon shield, be, in the crucible of 500mm, the solar-grade polysilicon silicon melting of impurity metal content≤0.001% is warmed up to 2000 DEG C at diameter, pure oxygen is with 2Nm
3the speed of/min passes into silicon liquid surface.The residence time of air-flow in tubular reactor going out crucible is 0.5 second, and temperature controls at 850 DEG C.The air-flow and the normal temperature air that go out tubular reactor mix in a mixer, control the intake of normal temperature air make mixing after gas flow temperature be 180 ± 20 DEG C.Cloth bag is utilized to collect product, by analysis, D
50median particle is 50nm, specific surface area 30m
2/ g.Close to preparing spherical SiO 2 outer surface area 27m under equal particle diameter
2the numerical value of/g.
Claims (7)
1. prepare the method for low specific surface nano silicon, it is characterized in that by silicon melting in crucible oven be liquid state, pure oxygen is passed into the upper space of silicon liquid, gaseous state Siliciumatom and oxygen molecule react and generate silicon monoxide, the air-flow going out crucible oven stops 0.1-30 second in tubular reactor, in tubular reactor, silicon monoxide and oxygen continue reaction generation silicon-dioxide, go out air-flow and the normal temperature air short mix in a mixer of tubular reactor, make gas flow temperature drop to less than 200 DEG C, cooled air-flow collects silicon dioxide granule powder through cloth bag equipment.
2., according to the method for the low specific surface nano silicon of preparation according to claim 1, it is characterized in that silicon melting in crucible oven to use argon gas to protect for needing time liquid.
3., according to the method for the low specific surface nano silicon of preparation according to claim 1, it is characterized in that silicon liquid temp is 1800-2600 DEG C.
4., according to the method for the low specific surface nano silicon of preparation according to claim 1, it is characterized in that on every square metre of silicon liquid, the speed that passes into of pure oxygen is 1-30Nm
3/ min.
5., according to the method for the low specific surface nano silicon of preparation according to claim 1, it is characterized in that mass content≤0.5% of metallic impurity iron, aluminium and calcium in raw silicon.
6., according to the method for the low specific surface nano silicon of preparation according to claim 1, it is characterized in that the temperature of reaction of silicon monoxide and oxygen in tubular reactor is 800-1100 DEG C.
7. according to the method for the low specific surface nano silicon of preparation according to claim 1, it is characterized in that the median size of silicon-dioxide is between 50-120nm, corresponding specific surface area is between 30-12m
2/ g.
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| 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 |
| CN108128781A (en) * | 2018-01-12 | 2018-06-08 | 宁波广新纳米材料有限公司 | A kind of production method of nano-silica powder |
| HUE063806T2 (en) * | 2018-06-12 | 2024-02-28 | Evonik Operations Gmbh | Spherical stannous compatible silica particles for reduced rda |
| CN109809414A (en) * | 2019-03-25 | 2019-05-28 | 江苏中江材料技术研究院有限公司 | A kind of solar panel cutting waste material recycling processing method |
| CN110357115B (en) * | 2019-08-12 | 2022-12-27 | 东北大学 | Method for preparing nano silicon dioxide by using crystalline silicon diamond wire cutting waste material |
| CN110282634B (en) * | 2019-08-12 | 2022-11-04 | 东北大学 | Method for preparing micron-sized silicon dioxide by using crystalline silicon diamond wire cutting waste |
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| US4123229A (en) * | 1976-05-07 | 1978-10-31 | John S. Pennish | Method and apparatus for making vitreous silica |
| EP1106582A2 (en) * | 1999-12-10 | 2001-06-13 | Corning Incorporated | Silica soot and process for producing it |
| JP2004076120A (en) * | 2002-08-21 | 2004-03-11 | Shin Etsu Chem Co Ltd | Silicon oxide for vapor deposition of film and method for manufacturing the same |
| CN101139095A (en) * | 2006-04-24 | 2008-03-12 | 信越化学工业株式会社 | Method for producing silicon oxide powder |
| CN101381083A (en) * | 2008-10-22 | 2009-03-11 | 昆明理工大学 | Method for preparing high pure spherical silica by means of vacuum carbothermal reduction |
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2012
- 2012-12-31 CN CN201210583696.6A patent/CN102976343B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4123229A (en) * | 1976-05-07 | 1978-10-31 | John S. Pennish | Method and apparatus for making vitreous silica |
| EP1106582A2 (en) * | 1999-12-10 | 2001-06-13 | Corning Incorporated | Silica soot and process for producing it |
| JP2004076120A (en) * | 2002-08-21 | 2004-03-11 | Shin Etsu Chem Co Ltd | Silicon oxide for vapor deposition of film and method for manufacturing the same |
| CN101139095A (en) * | 2006-04-24 | 2008-03-12 | 信越化学工业株式会社 | Method for producing silicon oxide powder |
| CN101381083A (en) * | 2008-10-22 | 2009-03-11 | 昆明理工大学 | Method for preparing high pure spherical silica by means of vacuum carbothermal reduction |
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