JPS638043B2 - - Google Patents
Info
- Publication number
- JPS638043B2 JPS638043B2 JP14690880A JP14690880A JPS638043B2 JP S638043 B2 JPS638043 B2 JP S638043B2 JP 14690880 A JP14690880 A JP 14690880A JP 14690880 A JP14690880 A JP 14690880A JP S638043 B2 JPS638043 B2 JP S638043B2
- Authority
- JP
- Japan
- Prior art keywords
- silicon
- sodium
- silicofluoride
- purity
- fluoride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229910052708 sodium Inorganic materials 0.000 claims description 34
- 239000011734 sodium Substances 0.000 claims description 34
- 229910052710 silicon Inorganic materials 0.000 claims description 33
- 239000010703 silicon Substances 0.000 claims description 33
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 32
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- 239000011775 sodium fluoride Substances 0.000 claims description 16
- 235000013024 sodium fluoride Nutrition 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 235000010755 mineral Nutrition 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 2
- 150000003385 sodium Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
Description
【発明の詳細な説明】
本発明は珪弗化ナトリウムよりシリコンを製造
する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing silicon from sodium silicofluoride.
最近、エネルギーの多様化に伴い、各種電池の
開発が我が国内外を問わず盛んに行なわれてい
る。特に太陽電池は国家資本を投入し、開発研究
を進めている場合も少なくない。太陽電池の基盤
として現在最も多く使われているシリコンには結
晶質シリコンとアモルフアスシリコンとがある
が、どれもエネルギー変換率が低いことや製造コ
ストが高過ぎることがシリコン普及のネツクにな
つている。 Recently, with the diversification of energy, various types of batteries have been actively developed both inside and outside Japan. In particular, there are many cases in which national capital is invested in research and development of solar cells. The silicones currently most commonly used as the base for solar cells include crystalline silicon and amorphous silicon, but both have low energy conversion rates and high manufacturing costs, which are the obstacles to their widespread use. There is.
太陽電池に用いるシリコン基盤の原料となる金
属シリコンは従来二酸化珪素を還元して製造する
ために多くのエネルギーが必要となる。またこの
方法では純度の低いものしか得られないため、精
製工程数成が多くなり、コストアツプの一因とな
つている。 Metallic silicon, which is the raw material for silicon substrates used in solar cells, conventionally requires a lot of energy to produce by reducing silicon dioxide. Furthermore, since this method only yields products with low purity, the number of purification steps increases, which is one of the causes of increased costs.
そこで最近では珪弗化ナトリウムを原料とし、
これと金属ナトリウムとの反応によりシリコンを
造る方法が開発された。例えば珪弗化ナトリウム
を熱分解せしめて得た弗化珪素と金属ナトリウム
または金属ナトリウム融液とを反応せしめるか、
または珪弗化ナトリウムと金属ナトリウムとの混
合物を加熱反応せしめる方法などにより弗化ナト
リウムとシリコンとを生成せしめ、(イ)この混合物
を真空中または不活性ガス中で加熱して溶融せし
めた後、室温迄冷却し凝固体よりシリコンを分離
取得するか、または(ロ)この混合物中の弗化ナトリ
ウムを鉱酸溶液にて溶解せしめてシリコンを分離
する方法などが行なわれている。しかしながらこ
れらの方法によればシリコンの製造原料として高
純度の珪弗化ナトリウムを使用しなければ高純度
のシリコンが得られないので、珪弗化ナトリウム
の製造に高純度の珪酸原料を使用する必要があ
る。またこの方法により副生する弗化ナトリウム
はシリコン製造の系外に出されるために直接シリ
コンの製造コストの低減に寄与せしめることがで
きない。 Therefore, recently, sodium silifluoride has been used as a raw material,
A method was developed to produce silicon by reacting this with metallic sodium. For example, by reacting silicon fluoride obtained by thermally decomposing sodium silicofluoride with metallic sodium or a metallic sodium melt,
Alternatively, sodium fluoride and silicon are generated by a method of heating a mixture of sodium silicofluoride and sodium metal, and (a) after heating and melting this mixture in a vacuum or an inert gas, The methods used include cooling the mixture to room temperature and separating the silicon from the solidified product, or (b) dissolving the sodium fluoride in the mixture in a mineral acid solution to separate the silicon. However, according to these methods, high purity silicon cannot be obtained unless high purity sodium silicofluoride is used as a raw material for silicon production, so it is necessary to use a high purity silicate raw material for the production of sodium silicofluoride. There is. Moreover, the sodium fluoride produced as a by-product by this method is discharged outside the silicon manufacturing system, and therefore cannot directly contribute to reducing the silicon manufacturing cost.
本発明者等は、このような欠点を除去せんとし
て種々研究した結果、上記の方法により生成した
弗化ナトリウムとシリコンの混合物よりシリコン
を分取した後弗化ナトリウムに二酸化珪素と塩
酸、硫酸、弗酸などの鉱酸を加えて反応せしめる
か、または弗化ナトリウムとシリコンの混合物に
上記と同じ鉱酸を加えて弗化ナトリウムを溶解せ
しめた後、濾過してその濾液に二酸化珪素を加え
て反応せしめるかして珪弗化ナトリウムを析出せ
しめると比較的不純な二酸化珪素を使用しても、
二酸化珪素中の不純物は分解液の方に移行するの
で高純度の珪弗化ナトリウムが得られることを知
見した。 The present inventors conducted various studies in an attempt to eliminate these drawbacks, and found that after separating silicon from the mixture of sodium fluoride and silicon produced by the above method, the sodium fluoride was combined with silicon dioxide, hydrochloric acid, sulfuric acid, Either add a mineral acid such as hydrofluoric acid to react, or add the same mineral acid as above to a mixture of sodium fluoride and silicon to dissolve the sodium fluoride, filter it, and add silicon dioxide to the filtrate. Even if relatively impure silicon dioxide is used, it can be reacted to precipitate sodium silicofluoride.
It was discovered that impurities in silicon dioxide migrate to the decomposition solution, resulting in highly pure sodium silicofluoride.
本発明はこれらの知見に基くものであつて、珪
弗化ナトリウムと金属ナトリウムとを反応せし
め、生成するシリコンと弗化ナトリウムとの混合
物よりシリコンを分離取得した後、残部の弗化ナ
トリウムに二酸化珪素と鉱酸溶液とを反応せし
め、生成した珪弗化ナトリウムを濾過水洗後上記
の金属ナトリウムとの反応に循環使用することを
特徴とする珪弗化ナトリウムよりシリコンを製造
する方法である。 The present invention is based on these findings, and consists of reacting sodium silicofluoride with sodium metal, separating silicon from the resulting mixture of silicon and sodium fluoride, and then adding oxidation to the remaining sodium fluoride. This is a method for producing silicon from sodium silicofluoride, which is characterized in that silicon and a mineral acid solution are reacted, and the produced sodium silifluoride is filtered, washed with water, and then recycled for the reaction with the metal sodium described above.
本発明において鉱酸としては塩酸、硫酸、弗酸
などが使用され、その使用量は二酸化珪素１モル
当り４モルまたはそれ以上である。 In the present invention, hydrochloric acid, sulfuric acid, hydrofluoric acid, etc. are used as mineral acids, and the amount used is 4 mol or more per 1 mol of silicon dioxide.
二酸化珪素は高純度のものほど好ましいが90％
以上ならば高純度の珪弗化ナトリウムを製造する
のに支障はない。二酸化珪素原料としては石英粉
末、無水珪酸、水ガラス、フエロシリコン製造時
の副生シリカ、リン酸工業の副生シリカなどが使
用され、特に無定形のものが好ましい。 The higher the purity of silicon dioxide, the better, but 90%
If the above conditions are met, there will be no problem in producing high-purity sodium silicofluoride. As the silicon dioxide raw material, quartz powder, silicic anhydride, water glass, by-product silica during the production of ferrosilicon, by-product silica from the phosphoric acid industry, etc. are used, and amorphous ones are particularly preferred.
本発明によれば、シリコン製造に使用する珪弗
化ナトリウムは不純な二酸化珪素を原料として循
環使用することができるのでシリコン製造コスト
を大巾に低減することができる。 According to the present invention, impure silicon dioxide can be recycled as a raw material for the sodium silicofluoride used in silicon production, so that silicon production costs can be significantly reduced.
実施例 １
珪弗化ナトリウム粉末（リン酸工業副生物）
（純度99.0％、粒度0.1mm以下）10Kgを600℃に加
熱し、発生した弗化珪素ガスを金属ナトリウムの
チツプ（３〜５mm）５Kgのベツド（直径10cm、高
さ50cm）に通し、500℃に加熱した後冷却してベ
ツドから取り出した。得られたシリコンと弗化ナ
トリウムとの混合物を黒鉛ルツボに充填後、アル
ゴン雰囲気中で1450℃で30分間加熱しこれらを溶
融した後室温まで冷却したところ、これらはシリ
コンと弗化ナトリウムの二層に分れ、シリコンと
弗化ナトリウムを分離することができた。得られ
たシリコンは1.1Kgで純度は99.9％であつた。ま
た得られた弗化ナトリウムは10Kgで純度は99％で
あつた。Example 1 Sodium silicofluoride powder (phosphoric acid industry by-product)
(Purity 99.0%, particle size 0.1mm or less) 10Kg is heated to 600℃, the generated silicon fluoride gas is passed through a 5Kg bed (diameter 10cm, height 50cm) of metallic sodium chips (3-5mm) and heated to 500℃. After heating, it was cooled and taken out from the bed. The resulting mixture of silicon and sodium fluoride was filled into a graphite crucible, heated at 1450°C for 30 minutes in an argon atmosphere to melt it, and then cooled to room temperature. It was possible to separate silicon and sodium fluoride. The silicon obtained weighed 1.1 kg and had a purity of 99.9%. The sodium fluoride obtained weighed 10 kg and had a purity of 99%.
次にこの弗化ナトリウム10Kgに石英微粉末（純
度97％、粉末度44μ以下）２Kgと濃塩酸を加え加
熱して撹拌し反応せしめた後冷却して生成した珪
弗化ナトリウムを濾過、水洗し乾燥したところ純
度99％の珪弗化ナトリウム６Kgを得た。 Next, 2 kg of fine quartz powder (purity 97%, fineness 44μ or less) and concentrated hydrochloric acid were added to 10 kg of this sodium fluoride, heated and stirred to react, and then cooled and the generated sodium silicofluoride was filtered and washed with water. After drying, 6 kg of sodium silicofluoride with a purity of 99% was obtained.
この珪弗化ナトリウムを再び原料としてシリコ
ンの生成に使用したところ純度99.9％以上のシリ
コンが得られた。 When this sodium silicofluoride was used again as a raw material to produce silicon, silicon with a purity of over 99.9% was obtained.
実施例 ２
珪弗化ナトリウム粉末（リン酸工業副生物、純
度99％、粉末度0.1mm以下）４Kgと金属ナトリウ
ム粒（１mm以下）２Kgを混合し、反応容器中で
200℃に加熱して１時間保持した後、冷却し容器
より取り出した。得られたシリコンと弗化ナトリ
ウムの混合物に濃塩酸を加え、煮沸し、濾過洗浄
後シリコンを分離した。得られたシリコンは0.6
Kgで純度は99％以上であつた。Example 2 4 kg of sodium silifluoride powder (phosphoric acid industry by-product, purity 99%, fineness 0.1 mm or less) and 2 kg of metallic sodium particles (1 mm or less) were mixed and mixed in a reaction vessel.
After heating to 200°C and holding for 1 hour, it was cooled and taken out from the container. Concentrated hydrochloric acid was added to the obtained mixture of silicon and sodium fluoride, the mixture was boiled, and the silicon was separated after filtration and washing. The silicon obtained is 0.6
The purity was 99% or more in Kg.
次に上記濾液に、氷晶石製造時の副生シリカ
（ig.loss5.39％、SiO292.52％、Na0.3％、F0.72
％、Al2O30.02％、CaO0.06％、Fe2O30.02％、
MgO0.1％）１Kgを加え、加熱撹拌して反応せし
めた後、冷却して生成した珪弗化ナトリウムを濾
過水洗し乾燥して純度99％の珪弗化ナトリウム
2.8Kgを得た。 Next, silica by-product during cryolite production (ig.loss 5.39%, SiO 2 92.52%, Na 0.3%, F 0.72) was added to the above filtrate.
%, Al2O3 0.02 %, CaO0.06%, Fe2O3 0.02 %,
After adding 1 kg of MgO (0.1%) and reacting by heating and stirring, the sodium silifluoride produced by cooling was filtered, washed with water, and dried to obtain sodium silifluoride with a purity of 99%.
Obtained 2.8Kg.
この珪弗化ナトリウムを再び原料としてシリコ
ンの製造に使用したところ純度99.9％以上のシリ
コンを得ることができた。 When this sodium silicofluoride was used again as a raw material in the production of silicon, silicon with a purity of over 99.9% could be obtained.
Claims (1)
せしめ、生成するシリコンと弗化ナトリウムとの
混合物よりシリコンを分離取得した後、残部の弗
化ナトリウムに二酸化珪素と鉱酸溶液とを反応せ
しめ、生成した珪弗化ナトリウムを濾過水洗後、
上記金属ナトリウムとの反応に循環使用すること
を特徴とする珪弗化ナトリウムよりシリコンを製
造する方法。1. React sodium silicofluoride with metallic sodium, separate and obtain silicon from the resulting mixture of silicon and sodium fluoride, and then react the remaining sodium fluoride with silicon dioxide and a mineral acid solution. After filtering and washing sodium silicofluoride with water,
A method for producing silicon from sodium silicofluoride, characterized in that the sodium silicofluoride is used repeatedly in the reaction with the metal sodium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14690880A JPS5771813A (en) | 1980-10-22 | 1980-10-22 | Production of silicon from sodium silicofluoride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14690880A JPS5771813A (en) | 1980-10-22 | 1980-10-22 | Production of silicon from sodium silicofluoride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5771813A JPS5771813A (en) | 1982-05-04 |
| JPS638043B2 true JPS638043B2 (en) | 1988-02-19 |
Family
ID=15418283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14690880A Granted JPS5771813A (en) | 1980-10-22 | 1980-10-22 | Production of silicon from sodium silicofluoride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5771813A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5142211B2 (en) * | 2008-10-02 | 2013-02-13 | 国立大学法人東北大学 | Method for producing silicon crystal and method for producing solar cell film |
| CN106517246B (en) * | 2016-11-21 | 2018-08-07 | 衡阳市锦轩化工有限公司 | Method for continuously producing sodium fluoride |
-
1980
- 1980-10-22 JP JP14690880A patent/JPS5771813A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5771813A (en) | 1982-05-04 |
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