JP2010052951A - Method for producing silicon - Google Patents
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- JP2010052951A JP2010052951A JP2008216224A JP2008216224A JP2010052951A JP 2010052951 A JP2010052951 A JP 2010052951A JP 2008216224 A JP2008216224 A JP 2008216224A JP 2008216224 A JP2008216224 A JP 2008216224A JP 2010052951 A JP2010052951 A JP 2010052951A
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Abstract
Description
本発明は、ＳｉＯ２を原料として、高純度の金属シリコンを製造する方法に関するものである。 The present invention relates to a method for producing high-purity metallic silicon using SiO 2 as a raw material.
近年、半導体や太陽電池などの普及により、その主要な材料であるシリコンの需要は拡大している。シリコンは、珪石とコークスを混合し、カーボン電極のアークにより溶解還元して製造される。この製造法は電力消費量が大きいこと、ある程度純度の高いシリコンを得るためには純度の高い珪石が必要なことから、産地が限定される。この製造法は以下のような反応による。 In recent years, with the spread of semiconductors and solar cells, the demand for silicon, which is the main material, has been increasing. Silicon is produced by mixing silica and coke, and dissolving and reducing the carbon electrode arc. This manufacturing method has a large power consumption, and high purity silica is necessary to obtain silicon with a certain degree of purity, so the production area is limited. This production method is based on the following reaction.
ＳｉＯ２ ＋ ２Ｃ → Ｓｉ ＋ ２ＣＯ または、
２ＳｉＯ２ ＋ ２Ｃ → ２Ｓｉ ＋ ２ＣＯ２
この製造法の電力消費量が大きいのは、以下の理由による。すなわち、珪石自身は溶融状態でも導電性が殆どないため、アークによる溶解が効率良く進行せず、実際は珪石と混合したコークスが電極と放電し、コークスの温度上昇で間接的に珪石が加熱されるため、珪石を溶解するのに非常に高いエネルギーを投入する必要がある。さらに導電性は、原料珪石の純度が高いほど低くなるので、最近の高純度化の需要により、ますます電力消費量が大きくなるという問題がある。
SiO 2 + 2C → Si + 2CO or
2SiO 2 + 2C → 2Si + 2CO 2
The reason for the large power consumption of this manufacturing method is as follows. In other words, since the silica itself has almost no electrical conductivity even in the molten state, melting by the arc does not proceed efficiently, and actually, the coke mixed with the silica discharges with the electrode, and the silica is indirectly heated by the temperature increase of the coke. Therefore, it is necessary to input very high energy to dissolve the silica. Furthermore, since the conductivity becomes lower as the purity of the raw material silica is higher, there is a problem that the power consumption is increased more and more due to the recent demand for high purity.
この問題を解決するために、最近ではハロゲン化シランを金属によって還元する方法（特許文献１参照）、ＳｉＯ２を電解還元する方法（特許文献２参照）、あるいは酸素濃度や温度の反応条件を最適化する方法（特許文献３参照）等が提案されている。
例えば上記の特開２００８−１５６２０８号公報に記載されているような、ハロゲン化シランを原料とするものは、ハロゲン化シランの原料に、既存の溶解還元によるシリコンを使用するものである。従ってこれらの方法は、シリコンの高純度化というべきであり、問題の解決にはなっていない。 For example, as described in the above-mentioned Japanese Patent Application Laid-Open No. 2008-156208, a material using a halogenated silane as a raw material uses silicon existing by dissolution and reduction as a raw material for the halogenated silane. Therefore, these methods should be high purity of silicon and do not solve the problem.
また、上記特開２００６−３２１６８８号公報に記載のものは、陰極に粗シリコンを用いて、陽極に高純度シリコンを析出するものであり、上記特開２００８−１５６２０８号公報記載のものと同じ問題があるばかりか、バッチ式となり大量生産には向かない。 Further, the one described in JP-A-2006-321688 uses crude silicon for the cathode and deposits high-purity silicon on the anode, which is the same problem as that described in JP-A-2008-156208. In addition, there is a batch type that is not suitable for mass production.
さらに、特開２００８−６９０６４号公報に記載されているものは、極端に低い酸素分圧下で微粒子化したシリカを還元するものであり、簡易な方法とは言い難い。 Furthermore, what is described in Japanese Patent Application Laid-Open No. 2008-69064 is to reduce the finely divided silica under an extremely low oxygen partial pressure, and is not a simple method.
このように、シリコンの需要が高まっているのにもかかわらず、簡易で純度の高いシリコンを生産する方法は未だに得られていないのが現状である。 Thus, in spite of the increasing demand for silicon, a simple method for producing high-purity silicon has not yet been obtained.
本発明は、ＳｉＯ２またはＳｉＯを含有する物質の粒子と、Ｃを含有する物質の粒子からなる混合粒子を、酸素燃焼炎を形成する燃焼炎ノズル中央部に供給することで、ＳｉＯ２またはＳｉＯを還元することを特徴とするシリコンの製造方法である。 The present invention supplies mixed particles composed of particles of a substance containing SiO 2 or SiO and particles of a substance containing C to the center of a combustion flame nozzle that forms an oxyfuel flame, so that SiO 2 or SiO This is a method for producing silicon, characterized in that the above is reduced.
また、上記微細混合粒子の径が５０〜５００μｍであることを特徴とする上記のシリコンの製造方法である。 Further, in the above silicon production method, the fine mixed particles have a diameter of 50 to 500 μm.
さらに、ＳｉＯ２またはＳｉＯを含有する物質の粒子を瞬間的に酸素燃焼することで、不純物を蒸発させることを特徴とする、上記のシリコンの製造方法である。 Furthermore, the silicon manufacturing method is characterized in that the impurities are evaporated by instantaneously oxygen burning the particles of the substance containing SiO 2 or SiO 2 .
本発明によれば、大量の電力を消費せずに、ＳｉＯ２から純度の高いシリコンを連続でかつ効率的に製造することが可能となる。 According to the present invention, it is possible to continuously and efficiently manufacture high-purity silicon from SiO 2 without consuming a large amount of power.
図１は、本発明を実施するのに用いる装置の基本的な構成の一例であり、ＳｉＯ２またはＳｉＯを含有する物質の粒子と、Ｃを含有する物質の粒子からなる混合粒子を燃焼炎ノズル２の中央部の原料供給口３から連続的に供給し、１５００〜３０００℃の酸素燃焼炎４を通過させる。この酸素燃焼炎を通過する間にＳｉＯ２は瞬時にＣ分と反応・還元されるためシリコンが生成し、そしてその生成シリコン６を排出口５より連続的に取り出すことができる。 FIG. 1 is an example of a basic configuration of an apparatus used for carrying out the present invention, and a combustion flame nozzle is formed by mixing mixed particles composed of particles of a substance containing SiO 2 or SiO and particles of a substance containing C. 2 is continuously supplied from the raw material supply port 3 at the center of 2 and the oxyfuel flame 4 at 1500 to 3000 ° C. is passed through. While passing through the oxygen combustion flame, SiO 2 is instantaneously reacted / reduced with the C component, so that silicon is generated, and the generated silicon 6 can be continuously taken out from the discharge port 5.
ここで、原料となる微細混合粒子の径は５０〜５００μｍとし、形成される混合粒子毎で変動が少なく、均一な粒子構成になることが望ましい。混合粒子が５０μｍ未満ではＳｉＯ２またはＳｉＯを含有する物質の粒子と、Ｃを含有する物質の粒子の粉砕に多大な時間やコストがかかるため望ましくない。また５００μｍを超えると、混合粒子の原料供給時の空気搬送が困難となり、また酸素燃焼炎中での還元効率が悪くなるため好ましくない。より好ましくは１００〜３００μｍである。 Here, it is desirable that the fine mixed particles used as a raw material have a diameter of 50 to 500 μm and have a uniform particle structure with little variation for each mixed particle to be formed. If the mixed particles are less than 50 μm, it is not desirable because it takes a lot of time and cost to grind the particles of the substance containing SiO 2 or SiO and the particles of the substance containing C. On the other hand, if it exceeds 500 μm, it is difficult to carry the air when the mixed particles are supplied, and the reduction efficiency in the oxyfuel flame is deteriorated. More preferably, it is 100-300 micrometers.
ＳｉＯ２またはＳｉＯを含有する物質としては、天然原料である珪石や珪砂、あるいは合成シリカ、ケイ酸塩などＳｉＯ２またはＳｉＯ分を含有していれば問題ない。またこの粒子の径は１〜４００μｍとする。１μｍ未満では粒子の粉砕に多大な時間やコストがかかるため望ましくない。また４００μｍを超えると酸素燃焼炎中での還元が難しくなるため好ましくない。より好ましくは、５〜２５０μｍである。 As a substance containing SiO 2 or SiO, there is no problem as long as it contains SiO 2 or SiO content such as silica or silica sand, which is a natural raw material, or synthetic silica or silicate. The diameter of the particles is 1 to 400 μm. If it is less than 1 μm, it is not desirable because it takes much time and cost to pulverize the particles. Moreover, since it will become difficult to reduce | restore in an oxygen combustion flame when it exceeds 400 micrometers, it is unpreferable. More preferably, it is 5-250 micrometers.
Ｃを含有する物質の粒子としては、カーボン、セルロースパウダーなど他の物質を還元する物質であれば良く、また高温でＳｉＯ２またはＳｉＯを還元するようなＳｉＣでも問題無い。またこの粒子の径は５０〜４００μｍとする。５０μｍ未満では粒子の粉砕に多大な時間やコストがかかる上に、酸素燃焼炎中でＳｉＯ２またはＳｉＯを還元できずにすぐに燃焼してしまうため望ましくない。また４００μｍを超えると酸素燃焼炎中での効率良い還元が難しくなるため好ましくない。より好ましくは、５０〜２５０μｍである。 As the particles of the substance containing C, any substance that reduces other substances such as carbon and cellulose powder may be used, and there is no problem with SiC that reduces SiO 2 or SiO at a high temperature. The diameter of the particles is 50 to 400 μm. If it is less than 50 μm, it takes a lot of time and cost to pulverize the particles, and SiO 2 or SiO cannot be reduced in the oxyfuel combustion flame and burns immediately, which is not desirable. Moreover, since it will become difficult to perform efficient reduction | restoration in an oxyfuel flame when it exceeds 400 micrometers, it is unpreferable. More preferably, it is 50-250 micrometers.
さらに、前記粒子を粒状に成形して微細混合粒子を調製する方法としては、スプレードライ法などの方法が使用でき、各粒子を分散溶解させた水溶液を高温奮起中に噴霧させて瞬間的に乾燥固化させる方法が好ましい。 Furthermore, as a method for preparing finely mixed particles by forming the particles into granules, a method such as a spray drying method can be used, and an aqueous solution in which each particle is dispersed and dissolved is sprayed during high-temperature stimulation and dried instantaneously. A solidification method is preferred.
酸素燃焼においては、火炎温度が好ましくはＳｉＯ２またはＳｉＯが還元されやすくなる１８００℃以上で、かつ生成したシリコンが出来る限り揮発しないようにシリコンの沸点２３００℃以下になるように燃焼量などを調整する必要があり、また燃焼における酸素比は０．８０〜１．２０、ＳｉＯ２またはＳｉＯの還元効率や生成したシリコンの酸化を考慮して好ましくは０．９０〜１．１０程度にする。 In oxyfuel combustion, the amount of combustion is adjusted so that the flame temperature is preferably 1800 ° C. or higher at which SiO 2 or SiO is easily reduced, and the boiling point of silicon is 2300 ° C. or lower so that the generated silicon is not volatilized as much as possible. Further, the oxygen ratio in combustion is preferably 0.80 to 1.20, and preferably about 0.90 to 1.10 in consideration of the reduction efficiency of SiO 2 or SiO and the oxidation of the generated silicon.
還元され生成したシリコンは、融点以上である火炎内で液体状態となり、このときＢ、Ｃ、Ｐ等の不純物は、酸化生成物の蒸気圧が高く蒸発する。これにより、純度の高いシリコンを得ることが出来る。 The silicon produced by reduction is in a liquid state in a flame having a melting point or higher. At this time, impurities such as B, C, and P evaporate because the vapor pressure of the oxidation product is high. Thereby, high purity silicon can be obtained.
燃焼に使用する燃料はＬＮＧ、ＬＰＧや灯油などいずれでも良い。しかし、先に述べたように多くの不純物が蒸発されて除かれるとはいえ、生成したシリコンに出来る限り不純物が移行しないように、燃料中にはＢ、Ｃ、Ｐなどの不純物が少ない方が望ましい。 The fuel used for combustion may be LNG, LPG, kerosene, or the like. However, as described above, although many impurities are evaporated and removed, it is preferable that the fuel has less impurities such as B, C, and P so that the impurities are not transferred to the generated silicon as much as possible. desirable.
１ 炉体
２ 燃焼炎ノズル
３ 原料供給口
４ 酸素燃焼炎
５ 生成シリコン排出口
６ 生成シリコン
1 Furnace
2 Combustion flame nozzle
3 Raw material supply port
4 Oxyfuel flame
5 Generated silicon outlet
6 Generated silicon
Claims (3)
3. The method for producing silicon according to claim 1, wherein impurities are evaporated by instantaneously oxygen-combusting particles of a substance containing SiO 2 or SiO 2. 4 .
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| JP2008216224A JP2010052951A (en) | 2008-08-26 | 2008-08-26 | Method for producing silicon |
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| JP2008216224A JP2010052951A (en) | 2008-08-26 | 2008-08-26 | Method for producing silicon |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111422856A (en) * | 2020-04-03 | 2020-07-17 | 常州富烯科技股份有限公司 | Method for flame reduction of graphene oxide film and preparation method of graphene film |
| WO2020171132A1 (en) * | 2019-02-19 | 2020-08-27 | 有限会社南日本ウェルネス | Production method of water-soluble nanocolloidal silica, and water-soluble nanocolloidal silica |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5921516A (en) * | 1982-07-24 | 1984-02-03 | Nippon Steel Corp | Manufacture of silicon |
| JPS60251113A (en) * | 1984-05-23 | 1985-12-11 | Daido Steel Co Ltd | Process and device for preparing silicon |
| JPS616114A (en) * | 1984-06-20 | 1986-01-11 | Kawasaki Steel Corp | Process and apparatus for preparing metallic silicon |
| JPS63129009A (en) * | 1986-11-17 | 1988-06-01 | Nippon Sheet Glass Co Ltd | Production of metallic silicon |
| JP2001089130A (en) * | 1999-09-14 | 2001-04-03 | Denki Kagaku Kogyo Kk | Production of fine spherical silica powder |
| JP2009078937A (en) * | 2007-09-26 | 2009-04-16 | Daido Steel Co Ltd | Apparatus for manufacturing metallic silicon |
-
2008
- 2008-08-26 JP JP2008216224A patent/JP2010052951A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5921516A (en) * | 1982-07-24 | 1984-02-03 | Nippon Steel Corp | Manufacture of silicon |
| JPS60251113A (en) * | 1984-05-23 | 1985-12-11 | Daido Steel Co Ltd | Process and device for preparing silicon |
| JPS616114A (en) * | 1984-06-20 | 1986-01-11 | Kawasaki Steel Corp | Process and apparatus for preparing metallic silicon |
| JPS63129009A (en) * | 1986-11-17 | 1988-06-01 | Nippon Sheet Glass Co Ltd | Production of metallic silicon |
| JP2001089130A (en) * | 1999-09-14 | 2001-04-03 | Denki Kagaku Kogyo Kk | Production of fine spherical silica powder |
| JP2009078937A (en) * | 2007-09-26 | 2009-04-16 | Daido Steel Co Ltd | Apparatus for manufacturing metallic silicon |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020171132A1 (en) * | 2019-02-19 | 2020-08-27 | 有限会社南日本ウェルネス | Production method of water-soluble nanocolloidal silica, and water-soluble nanocolloidal silica |
| JPWO2020171132A1 (en) * | 2019-02-19 | 2020-08-27 | ||
| JP7388750B2 (en) | 2019-02-19 | 2023-11-29 | 有限会社南日本ウェルネス | Method for producing water-soluble nanocolloidal silica for ingestion by animals and plants, and water-soluble nanocolloidal silica for ingestion by animals and plants |
| CN111422856A (en) * | 2020-04-03 | 2020-07-17 | 常州富烯科技股份有限公司 | Method for flame reduction of graphene oxide film and preparation method of graphene film |
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