CN101837979A - Method for preparing solar-grade high-purity polycrystalline silicon - Google Patents
Method for preparing solar-grade high-purity polycrystalline silicon Download PDFInfo
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- CN101837979A CN101837979A CN200910249945A CN200910249945A CN101837979A CN 101837979 A CN101837979 A CN 101837979A CN 200910249945 A CN200910249945 A CN 200910249945A CN 200910249945 A CN200910249945 A CN 200910249945A CN 101837979 A CN101837979 A CN 101837979A
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- silica flour
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Abstract
The invention provides a method for preparing solar-grade high-purity polycrystalline silicon and relates to a production method for preparing the solar-grade high-purity polycrystalline silicon by a physical-chemical method. The method comprises the following steps of: smashing metallurgical-grade industrial silicon serving as a raw material to obtain a silicon powder material of which the water content is less than 3 percent and the particle size is between 50 and 100 nanometers; leaching the silicon powder material in acid for two times; cleaning the acid-leached powder material; drying the cleaned powder material; smelting the dried powder material in vacuum; and directionally solidifying the smelted powder material to obtain a polycrystalline silicon product of which the purity is as high as over 99.999 percent. The preparation method has the advantages of easy operation, low power consumption, low production cost and easy realization of large-scale and industrial production.
Description
Technical field
The invention provides a kind of method for preparing solar-grade high-purity polycrystalline silicon, especially a kind of method of using physicochemical treatment method to prepare high purity polycrystalline silicon.
Background technology
Along with industrial expansion, energy problem has become the problem of globalization.The extreme exploitation and the use of fossil energy cause ecological damage and environmental pollution, and the finiteness of fossil energy reserves more and more cause the extensive concern in the world.
Sun power is a kind of cleaning, the reproducible energy, more and more is subjected to paying close attention to widely and using.Along with the fast development of photovoltaic industry in this year, the problem that there is lack of raw materials has appearred.The silicon suitable for solar purposes material is mainly from the waste material and the substandard products of semi-conductor industry at present, and existing chlorination purification production solar grade polycrystalline silicon material production technique cost is too high and possibility that reduce is little.Existing situation exigence is developed the novel method that a kind of HIGH-PURITY SILICON is purified.
The present invention proposes a kind of low power consuming, less investment, high purity polycrystalline silicon technology of preparing that production cost is low, for the production of solar-grade polysilicon provides high quality raw material.Technical security height, contaminative that the present invention proposes are little, are a kind of eco-friendly green clearer production technologies.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of solar-grade high-purity polycrystalline silicon, promptly adopting the metallurgical grade industrial silicon is raw material, handles through physico-chemical process, obtains high purity polycrystalline silicon, the purity of its silicon is more than 99.999%.
The preparation method of a kind of solar-grade high-purity polycrystalline silicon provided by the invention may further comprise the steps:
(1) pulverize:
Adopt nano grinder that the industrial silica fume of 150～840 μ m is broken to 50～100nm, the material after the pulverizing makes its water content be lower than 3% through spraying drying;
(2) pickling:
Silica flour material after the pulverizing is put into reactor, carries out acidleach with concentration 5～8mol/L hydrochloric acid and handles, and silica flour is 1: 0.5～2.5 (weight ratios) with the adding proportion that leaches acid, and extraction temperature is at 20～80 ℃, and extraction time is 0.5～2 day; Clean 5～10 times with the nanometer washing plant then, and silica flour is separated with leach liquor and drying;
After the drying silica flour is put into reactor, employing concentration is that the hydrofluoric acid of 3～8mol/L carries out the acidleach processing to the silica flour material, silica flour is 1: 0.5～2.5 (weight ratios) with the adding proportion that leaches acid, extraction temperature is at 20～80 ℃, extraction time is 0.5～2 day, removes the impurity such as silicon-dioxide in the silica flour; Clean with the nanometer washing plant then and be washed till neutrality 3～10 times, and silica flour is separated with leach liquor, silica flour is removed moisture in 80～120 ℃ of following dryings of spray drying device;
(3) vacuum melting:
Dried silica flour material is added in the vacuum oven, utilize induction heating, keep interior temperature 1450-1600 ℃ of stove, vacuum tightness 10 material melting
3-10
4Pa feeds the mixed gas of argon gas and water vapour, melting 2-9 hour then; Control vacuum tightness 10 then
-2-10
-5Pa, interior temperature 1450-1600 ℃ of stove, refining 2-10 hour;
(4) directional freeze:
Keep stove vacuum tightness 10
-2-10
-5Pa, 1450-1600 ℃ of silica flour material melt portion temperature, speed of cooling is 0.5-1.0 centimetre/hour.
(5) crop is handled:
After the material cooling, carry out crop and handle, excise last cooling segment, obtain the solar-grade polysilicon product.
The present invention has the following advantages:
1. equipment is simple, less investment; 2. current consumption is little, and production cost is low; 3. environmental pollution is little.
Description of drawings
Fig. 1 is the solar-grade high-purity polycrystalline silicon preparation method schematic flow sheet that the present invention provides.
Embodiment:
Embodiment one:
Using silicone content is that 99.4% metallurgical grade industrial silicon is raw material, its major impurity composition iron level 3300ppm, aluminium content 1500ppm, calcium contents 900ppm.
Adopt nano grinder with raw material pulverizing to 50～100nm, the material after the pulverizing makes its water content be lower than 3% through spraying drying; Silica flour material after the pulverizing is put into reactor, carries out acidleach with concentration 6mol/L hydrochloric acid and handles, and silica flour is 1: 1 (weight ratio) with the adding proportion that leaches acid, and extraction temperature is at 50 ℃, and extraction time is 1 day; Clean 5 times with the nanometer washing plant then, and silica flour is separated with leach liquor and drying; After the drying silica flour is put into reactor, employing concentration is that the hydrofluoric acid of 6mol/L carries out the acidleach processing to the silica flour material, and silica flour is 1: 1 (weight ratio) with the adding proportion that leaches acid, and extraction temperature is at 50 ℃, extraction time is 1 day, removes the impurity such as silicon-dioxide in the silica flour; Clean with the nanometer washing plant then and be washed till neutrality 5 times, and silica flour is separated with leach liquor, silica flour is removed moisture in 80～120 ℃ of following dryings of spray drying device; Dried silica flour material is added in the vacuum oven, utilize induction heating, keep 1450 ℃ of the interior temperature of stove, vacuum tightness 10 material melting
3-10
4Pa feeds the mixed gas of argon gas and water vapour, melting 9 hours then; Control vacuum tightness 10 then
-2-10
-5Temperature is 1450 ℃ in the Pa, stove, refining 10 hours; Keep stove vacuum tightness 10
-2-10
-5Pa, 1450 ℃ of silica flour material melt portion temperature, speed of cooling is 1.0 centimetres/hour; After the material cooling, carry out crop and handle, excise last cooling segment, obtain purity and be 99.99956% solar-grade polysilicon product.
Embodiment two:
Using silicone content is that 99.5% metallurgical grade industrial silicon is raw material, its major impurity composition iron level 1800ppm, aluminium content 1500ppm, calcium contents 620ppm.
Adopt nano grinder with raw material pulverizing to 50～100nm, the material after the pulverizing makes its water content be lower than 3% through spraying drying; Silica flour material after the pulverizing is put into reactor, carries out acidleach with concentration 5mol/L hydrochloric acid and handles, and silica flour is 1: 1.5 (weight ratio) with the adding proportion that leaches acid, and extraction temperature is at 60 ℃, and extraction time is 1.5 days; Clean 5 times with the nanometer washing plant then, and silica flour is separated with leach liquor and drying; After the drying silica flour is put into reactor, employing concentration is that the hydrofluoric acid of 5mol/L carries out the acidleach processing to the silica flour material, and silica flour is 1: 1.5 (weight ratio) with the adding proportion that leaches acid, and extraction temperature is at 60 ℃, extraction time is 1.5 days, removes the impurity such as silicon-dioxide in the silica flour; Clean with the nanometer washing plant then and be washed till neutrality 5 times, and silica flour is separated with leach liquor, silica flour is removed moisture in 80～120 ℃ of following dryings of spray drying device; Dried silica flour material is added in the vacuum oven, utilize induction heating, keep 1500 ℃ of the interior temperature of stove, vacuum tightness 10 material melting
3-10
4Pa feeds the mixed gas of argon gas and water vapour, melting 2 hours then; Control vacuum tightness 10 then
-2-10
-5Temperature is 1500 ℃ in the Pa, stove, refining 2 hours; Keep stove vacuum tightness 10
-2-10
-5Pa, 1500 ℃ of silica flour material melt portion temperature, speed of cooling is 0.5 centimetre/hour; After the material cooling, carry out crop and handle, excise last cooling segment, obtain 99.99978% solar-grade polysilicon product.
Claims (2)
1. the preparation method of a solar-grade high-purity polycrystalline silicon may further comprise the steps:
(1) pulverize:
Adopt nano grinder that the industrial silica fume of 150～840 μ m is broken to 50～100nm, the material after the pulverizing makes its water content be lower than 3% through spraying drying;
(2) pickling:
Silica flour material after the pulverizing is put into reactor, carries out acidleach with concentration 5～8mol/L hydrochloric acid and handles, and silica flour is 1: 0.5～2.5 (weight ratios) with the adding proportion that leaches acid, and extraction temperature is at 20～80 ℃, and extraction time is 0.5～2 day; Clean 5～10 times with the nanometer washing plant then, and silica flour is separated with leach liquor and drying;
After the drying silica flour is put into reactor, employing concentration is that the hydrofluoric acid of 3～8mol/L carries out the acidleach processing to the silica flour material, silica flour is 1: 0.5～2.5 (weight ratios) with the adding proportion that leaches acid, extraction temperature is at 20～80 ℃, extraction time is 0.5～2 day, removes the impurity such as silicon-dioxide in the silica flour; Clean with the nanometer washing plant then and be washed till neutrality 3～10 times, and silica flour is separated with leach liquor, silica flour is removed moisture in 80～120 ℃ of following dryings of spray drying device;
(3) vacuum melting:
Dried silica flour material is added in the vacuum oven, utilize induction heating, keep interior temperature 1450-1600 ℃ of stove, vacuum tightness 10 material melting
3-10
4Pa feeds the mixed gas of argon gas and water vapour, melting 2-9 hour then; Control vacuum tightness 10 then
-2-10
-5Pa, interior temperature 1450-1600 ℃ of stove, refining 2-10 hour;
(4) directional freeze:
Keep stove vacuum tightness 10
-2-10
-5Pa, 1450-1600 ℃ of silica flour material melt portion temperature, speed of cooling is 0.5-1.0 centimetre/hour;
(5) crop is handled:
After the material cooling, carry out crop and handle, excise last cooling segment, obtain the solar-grade polysilicon product.
2. the preparation method of a kind of solar-grade high-purity polycrystalline silicon according to claim 1, it is characterized in that: described raw material is the metallurgical grade industrial silicon of purity 98～99.5%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910249945A CN101837979A (en) | 2009-12-07 | 2009-12-07 | Method for preparing solar-grade high-purity polycrystalline silicon |
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| CN200910249945A CN101837979A (en) | 2009-12-07 | 2009-12-07 | Method for preparing solar-grade high-purity polycrystalline silicon |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173424A (en) * | 2011-01-31 | 2011-09-07 | 大连理工大学 | Method and equipment for removing phosphorus and metal impurities in ganister sand through vacuum induction melting |
| CN103043664A (en) * | 2012-12-13 | 2013-04-17 | 青岛隆盛晶硅科技有限公司 | Method and device for directionally solidifying and purifying polysilicon by vacuum extraction of tailing |
| CN104973601A (en) * | 2015-07-06 | 2015-10-14 | 杭州钦耀纳米科技有限公司 | Production method for hyperpure ultrafine metallic silicon powder |
| CN105417545A (en) * | 2015-09-29 | 2016-03-23 | 南京大学 | Method for preparing high-purity silicon particles |
-
2009
- 2009-12-07 CN CN200910249945A patent/CN101837979A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173424A (en) * | 2011-01-31 | 2011-09-07 | 大连理工大学 | Method and equipment for removing phosphorus and metal impurities in ganister sand through vacuum induction melting |
| CN102173424B (en) * | 2011-01-31 | 2013-10-30 | 大连理工大学 | Method and equipment for removing phosphorus and metal impurities in ganister sand through vacuum induction melting |
| CN103043664A (en) * | 2012-12-13 | 2013-04-17 | 青岛隆盛晶硅科技有限公司 | Method and device for directionally solidifying and purifying polysilicon by vacuum extraction of tailing |
| CN103043664B (en) * | 2012-12-13 | 2014-08-27 | 青岛隆盛晶硅科技有限公司 | Method and device for directionally solidifying and purifying polysilicon by vacuum extraction of tailing |
| CN104973601A (en) * | 2015-07-06 | 2015-10-14 | 杭州钦耀纳米科技有限公司 | Production method for hyperpure ultrafine metallic silicon powder |
| CN105417545A (en) * | 2015-09-29 | 2016-03-23 | 南京大学 | Method for preparing high-purity silicon particles |
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Application publication date: 20100922 |