CN102173421B - Production technique of low-phosphorus and low-boron 3N high-purity silicon by ore furnace - Google Patents
Production technique of low-phosphorus and low-boron 3N high-purity silicon by ore furnace Download PDFInfo
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- CN102173421B CN102173421B CN 201110058871 CN201110058871A CN102173421B CN 102173421 B CN102173421 B CN 102173421B CN 201110058871 CN201110058871 CN 201110058871 CN 201110058871 A CN201110058871 A CN 201110058871A CN 102173421 B CN102173421 B CN 102173421B
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Abstract
The invention discloses an ore furnace low-phosphorus and low-boron 3N high-purity silicon production technique. In the invention, choose silica is taken as the silica source, petrol coke is taken as the reducing agent and wood chip or bagasse is taken as the leavening agent; the technical procedures are as follows: breaking silica into fragments and then soaking into acid, and then using deionized water to wash the silica fragments to neutral; grinding into powder with petrol coke, and soaking into acid; using deionized water to wash the petrol coke powder to neutral; drying the neutral powder and mixing the power with organic adhesives and then pressing the mixture into balls; soaking the wood chips into the soak solution and washing with deionized water to neutral, or using deionized water to wash the bagasse; mixing the silica, petrol coke and wood chips (bagasse) and putting the mixture into the ore furnace; placing silicon water into a ladle, introducing mixed gas and adding slagging constituent; placing the silicon water into the crystallizer and lowering the temperature by 15-30 DEG C /min to freeze the obtained product. The products prepared by using the technique in the invention contain the following components: Fe<=750ppmw, Al<=150ppmw, Ca<=100ppmw, P<=10ppmw and B<=2ppmw. The invention has the advantages of high-quality metal silicon, low content of impurity and low following purification cost.
Description
Technical field
The present invention relates to a kind of production technique of utilizing mineral hot furnace to produce low boron phosphorus 3N HIGH-PURITY SILICON.
Background technology
Along with the fast development of photovoltaic industry, market just increases rapidly with the speed of year 30-40% the demand of solar-grade polysilicon
,Particularly the cost performance metallurgy method solar energy polycrystalline silicon that is better than traditional Siemens Method more is subject to industry and pays close attention to.The basic ideas of metallurgy method production solar power silicon and target are to keep under the simple substance state at element silicon, remove the various impurity of mine heat furnace smelting gained Pure Silicon Metal, make the purity of silicon finally reach the requirement of sun power silicon wafer battery, and production cost will be lower than traditional Siemens Method, will accomplish simultaneously that energy consumption is low, resources conservation, environmental friendliness.It is evident that thus, the technique of the purer subsequent purification of mineral hot furnace gained silicon can simpler cost for purification can be lower.Especially original phosphorus boron content is very big to the cost impact of metallurgy method solar power silicon, because the removal of phosphorus boron is difficult in the silicon, and its processing cost can be multiplied along with the increase of original concentration.So the low-phosphorous boron high pure raw material that how to utilize mineral hot furnace to produce at low cost for metallurgy method purification production solar energy polycrystalline silicon becomes the large problem that photovoltaic industry faces in the world wide.
Its purity of Pure Silicon Metal that common mineral hot furnace is produced ≯ 99.5%.Even the silicon of top grade product, foreign matter content also are respectively Fe:1000-2500ppm, AL:800-2500ppm, Ca:200-1000ppm, P:25-60ppm, B:6-20ppm.The Pure Silicon Metal quality of existing metallic silicon smelting explained hereafter is low, and foreign matter content is high, and the later stage cost for purification is high.
Summary of the invention
The object of the invention is to for the Pure Silicon Metal quality of existing metallic silicon smelting explained hereafter lowly, foreign matter content is high, and the shortcomings such as later stage cost for purification height provide a kind of production technique of utilizing mineral hot furnace to produce low boron phosphorus 3N HIGH-PURITY SILICON.
In order to reach above-mentioned purpose, solution of the present invention is:
Utilize mineral hot furnace to produce the production technique of low boron phosphorus 3N HIGH-PURITY SILICON, concrete production craft step is as follows:
1) take silica as the silicon source, take refinery coke as reductive agent, take wood chip or bagasse as raising agent;
2) silica is broken, use acid soak 30-60 minute, extremely neutral with washed with de-ionized water;
3) with the refinery coke abrasive dust, in acid, soaked 30-60 minute, to neutral, add organic binder bond uniform stirring after drying with washed with de-ionized water, and agglomerating with the ball press extruding;
4) wood chip was soaked 30-60 minute with soak solution, extremely neutral with washed with de-ionized water; Or with the bagasse rinsed with deionized water;
5) mix silica, refinery coke and wood chip or bagasse, and drop into mine heat furnace smelting;
6) silicon water is packed into platform bag (existing equipment), logical mixed gas continuously, mixed gas is by oxygen O
2Mix with the volume ratio of air by 2:1, drop into simultaneously slag former;
7) silicon water is poured in the crystallizer, kept solidifying with 15 ℃ of-30 ℃/min speed coolings.
In step 1), the mass percent of silica chemical composition requires: SiO
2〉=99%, Fe
2O
3≤ 0.08%, Al
2O
3≤ 0.06%, CaO≤0.05%, P≤3ppm, B≤2ppm; Petroleum coking is learned composition quality per-cent and is required: fixed carbon 〉=83%, fugitive constituent=14%-16%, ash content≤0.3%, P≤6ppm, B≤2ppm; The wood chip chemical composition requires: P≤140ppm, B=3-5ppm.
In step 2) in, silica particle size after cracking≤80mm, acid is HCl:HF:HNO in mass ratio
3The mixing acid of=3:1:2 proportioning, soak solution acid total content (various acid solution total mass percentage concentration) is 5%-15%, and is extremely neutral with washed with de-ionized water.
In step 3), the refinery coke grinding particle size is the 20-200 order, and acid is HCl:HF:H in mass ratio
2SO
4The mixing acid of=3:1:1 proportioning, various acid solution total mass percentage concentrations are 5%-15%, and are extremely neutral with washed with de-ionized water, tackiness agent is rice paste, coal-tar pitch or starch, puddled time 30-45 minute, balling-up granularity requirements 25-50mm needs after the balling-up to dry 30-50 minute in 105-120 ℃ of environment.
In step 4), the chip dimensions size is: length * wide * height=100 * 50 * 5-150 * 80 * 10(does not have dimensional requirement to bagasse), soak solution is sodium hydroxide (NaOH), mass percentage concentration is 5%-20%.
In step 5), silica, refinery coke and wood chip or bagasse mass mixing ratio are about 8:4:1, adopt to be different from traditional new flushing and casting method: smoldering is until integral body is grilled thoroughly, and boiler face integral body is forced jetsam, and reinforced one piece is finished.
In step 6), the slag former composition is by mass percentage: CeO (rare earth) accounts for 40%-60%, and BaO accounts for 25%-35%, Na
2O accounts for 5%-35%; Its add-on is the 2%-10% of silicon water by mass percentage.
In step 7), the low-phosphorous boron 3N HIGH-PURITY SILICON product that can obtain requiring is broken to≤80-100mm pack in silicon ingot cooling in the device to be crystallized into pieces.
In step 7), crystallizer adopts the graphite lining to do inner bag, is castable around the inner bag, and the bottom of inner bag is the composite structure of refractory brick and asbestos plate, and Buffer Unit is installed in the periphery of castable.Graphite lining, castable, Buffer Unit, refractory brick, asbestos plate and box hat play insulation jointly as the member of integral heat insulation system in the crystallizer, slow down the solid speed of silicon water-setting, fully realize the effect that the slag gold separates.
After adopting such scheme, the present invention utilizes mineral hot furnace stably to smelt low-phosphorous boron 3N HIGH-PURITY SILICON by starting material such as selected and processing silica, refinery coke, wood chips, Fe≤750ppmw wherein, AL≤150ppmw, Ca≤100ppmw, P≤10ppmw, B≤2ppmw.The Pure Silicon Metal quality that smelting technology of the present invention is produced is high, and foreign matter content is low, and the later stage cost for purification is low.
Description of drawings
Fig. 1 is the structural representation of the used crystallizer of the present invention.
Embodiment
Silica is crushed to granularity≤80mm, is HCl:HF:HNO at mass ratio
3=3:1:2, various sour total mass percentage concentrations are to soak 40 minutes in 10% the mixing acid, then with washed with de-ionized water to neutral.It is the 20-200 order that petroleum coke powder is broken to granularity, is HCl:HF:H at mass ratio
2SO
4=3:1:1, various sour total mass percentage concentrations are to soak 40 minutes in 10% the mixing acid, then with washed with de-ionized water to neutral; Be a meter paste in mass ratio: refinery coke=5:100 adds rice and sticks with paste as tackiness agent, stirs balling-up after 35 minutes, dries 30 minutes under 120 ℃ of environment after the balling-up.Be to soak 50 minutes in 15% the NaOH soak solution wood chip in mass percentage concentration, then with washed with de-ionized water to neutral.
Silica, refinery coke and the wood chip of handling well is about 8:4:1 in mass ratio mixes, drop into mine heat furnace smelting.The platform bag of after having smelted silicon water being packed into drops into slag former, and slag former be 5% of silicon water by mass percentage, and the slag former composition is by mass percentage: CeO (rare earth) accounts for 50%, BaO and accounts for 30%, Na
2O accounts for 20%, passes into simultaneously by oxygen O
2Press the gas mixture 30 minutes that the volume ratio of 2:1 forms with air.After complete silicon water is poured in the crystallizer, kept solidifying with the cooling of 20 ℃/min speed.Silicon ingot cooling in the device to be crystallized is broken into pieces to≤80-100mm pack.
The structure of crystallizer adopts graphite lining 1 to do inner bag as shown in Figure 1, is castable 2 around the inner bag, and the bottom of inner bag is the composite structure of refractory brick 3 and asbestos plate 4, and Buffer Unit 5 and box hat 6 are installed in the periphery of castable 2.
Show Fe=323ppmw in the Pure Silicon Metal of gained, AL=46ppmw, Ca=73ppmw, P=7.4ppmw, B=1.7ppmw with the detection of ICP-OES method.
Silica is crushed to granularity≤80mm, is HCl:HF:HNO at mass ratio
3=3:1:2, various sour total mass percentage concentrations are to soak 60 minutes in 15% the mixing acid, then with washed with de-ionized water to neutral.It is the 20-200 order that petroleum coke powder is broken to granularity, is HCl:HF:H at mass ratio
2SO
4=3:1:1, various sour total mass percentage concentrations are to soak 60 minutes in 15% the mixing acid, then with washed with de-ionized water to neutral; Be starch in mass ratio: refinery coke=10:100 adds starch as tackiness agent, stirs balling-up after 40 minutes, dries 40 minutes under 110 ℃ of environment after the balling-up.Be to soak 60 minutes in 20% the NaOH soak solution wood chip in mass percentage concentration, then with washed with de-ionized water to neutral.
Silica, refinery coke and the wood chip of handling well is about 8:4:1 in mass ratio mixes, drop into mine heat furnace smelting.The platform bag of after having smelted silicon water being packed into drops into slag former, and slag former be 5% of silicon water by mass percentage, and the slag former composition is by mass percentage: CeO (rare earth) accounts for 40%, BaO and accounts for 35%, Na
2O accounts for 25%, passes into simultaneously by oxygen O
2Press the gas mixture 30 minutes that the volume ratio of 2:1 forms with air.After complete silicon water is poured in the crystallizer (structure is with embodiment 1), kept solidifying with the cooling of 15 ℃/min speed.Silicon ingot cooling in the device to be crystallized is broken into pieces to≤80-100mm pack.
Show Fe=271ppmw in the Pure Silicon Metal of gained, AL=42ppmw, Ca=68ppmw, P=6.8ppmw, B=1.5ppmw with the detection of ICP-OES method.
Silica is crushed to granularity≤80mm, is HCl:HF:HNO at mass ratio
3=3:1:2, various sour total mass percentage concentrations are to soak 50 minutes in 6% the mixing acid, then with washed with de-ionized water to neutral.It is the 20-200 order that petroleum coke powder is broken to granularity, is HCl:HF:H at mass ratio
2SO
4=3:1:1, various sour total mass percentage concentrations are to soak 50 minutes in 6% the mixing acid, then with washed with de-ionized water to neutral; Be coal-tar pitch in mass ratio: refinery coke=10:100 adds starch as tackiness agent, stirs balling-up after 45 minutes, dries 50 minutes under 105 ℃ of environment after the balling-up.Bagasse is used rinsed with deionized water 60 minutes.
Silica, refinery coke and the bagasse of handling well is about 8:4:1 in mass ratio mixes, drop into mine heat furnace smelting.The platform bag of after having smelted silicon water being packed into drops into slag former, and slag former be 5% of silicon water by mass percentage, and the slag former composition is by mass percentage: CeO (rare earth) accounts for 55%, BaO and accounts for 25%, Na
2O accounts for 20%, passes into simultaneously by oxygen O
2Press the gas mixture 30 minutes that the volume ratio of 2:1 forms with air.After complete silicon water is poured in the crystallizer (structure is with embodiment 1), kept solidifying with the cooling of 25 ℃/min speed.Silicon ingot cooling in the device to be crystallized is broken into pieces to≤80-100mm pack.
Show Fe=423ppmw in the Pure Silicon Metal of gained, AL=57ppmw, Ca=75ppmw, P=7.8ppmw, B=1.8ppmw with the detection of ICP-OES method.
Advantage of the present invention is to adopt the wet purification technology, the raw material that metal smelting silicon is used (silica, refinery coke, wood chip or bagasse) carries out purification processes, to remove partial impurities in the raw material, part B, P have particularly been removed, then adopt new flushing and casting method, and in conjunction with slag making and crystallization technique, just can go out low-phosphorous boron 3N HIGH-PURITY SILICON with our traditional mine heat furnace smelting, produce solar energy polycrystalline silicon for follow-up metallurgy method purification low-phosphorous boron high pure raw material is provided, greatly simplify subsequent purification technique, saved cost.
Claims (4)
1. utilize mineral hot furnace to produce the production technique of low boron phosphorus 3N HIGH-PURITY SILICON, it is characterized in that production craft step is as follows:
1) take silica as the silicon source, take refinery coke as reductive agent, take wood chip or bagasse as raising agent, wherein, the mass percent of silica chemical composition requires: SiO
2〉=99%, Fe
2O
3≤ 0.08%, Al
2O
3≤ 0.06%, CaO≤0.05%, P≤3ppm, B≤2ppm; Petroleum coking is learned composition quality per-cent and is required: fixed carbon 〉=83%, fugitive constituent=14%-16%, ash content≤0.3%, P≤6ppm, B≤2ppm; The wood chip chemical composition requires: P≤140ppm, B=3-5ppm;
2) silica is broken, use acid soak 30-60 minute, extremely neutral with washed with de-ionized water;
3) with the refinery coke abrasive dust, in acid, soaked 30-60 minute,, add organic binder bond after drying and stir to neutral with washed with de-ionized water, and agglomerating with the ball press extruding, wherein, tackiness agent is rice paste, coal-tar pitch or starch;
4) wood chip was soaked 30-60 minute with soak solution, extremely neutral with washed with de-ionized water; Or with the bagasse rinsed with deionized water;
5) mix silica, refinery coke and wood chip or bagasse, and drop into mine heat furnace smelting, wherein, silica, refinery coke and wood chip or bagasse mass mixing ratio are 8:4:1, adopt the flushing and casting method: smoldering is until integral body is grilled thoroughly, and boiler face integral body is forced jetsam, and reinforced one piece is finished;
6) silicon water is packed into platform bag, logical mixed gas, mixed gas is by oxygen O
2Mix with the volume ratio of air by 2:1, drop into simultaneously slag former, wherein, the slag former composition is by mass percentage: CeO accounts for 40%-60%, and BaO accounts for 25%-35%, Na
2O accounts for 5%-35%; Its add-on is the 2%-10% of silicon water by mass percentage;
7) silicon water is poured in the crystallizer, kept solidifying with 15 ℃ of-30 ℃/min speed coolings; The low-phosphorous boron 3N HIGH-PURITY SILICON product that can obtain requiring is broken to≤80-100mm pack in silicon ingot cooling in the device to be crystallized into pieces.
2. the production technique of utilizing mineral hot furnace to produce low boron phosphorus 3N HIGH-PURITY SILICON as claimed in claim 1 is characterized in that: in step 2) in, silica particle size after cracking≤80mm, acid is HCl:HF:HNO in mass ratio
3The mixing acid of=3:1:2 proportioning, soak solution acid total content is that various acid solution total mass percentage concentrations are 5%-15%, and is extremely neutral with washed with de-ionized water.
3. the production technique of utilizing mineral hot furnace to produce low boron phosphorus 3N HIGH-PURITY SILICON as claimed in claim 1, it is characterized in that: in step 3), the refinery coke grinding particle size is the 20-200 order, acid is HCl:HF:H in mass ratio
2SO
4The mixing acid of=3:1:1 proportioning, various acid solution total mass percentage concentrations are 5%-15%,, puddle time 30-45 minute to neutral with washed with de-ionized water, balling-up granularity requirements 25-50mm needs after the balling-up to dry 30-50 minute in 105-120 ℃ of environment.
4. the mineral hot furnace of utilizing as claimed in claim 1 is produced the production technique of hanging down boron phosphorus 3N HIGH-PURITY SILICON, it is characterized in that: in step 7), crystallizer adopts the graphite lining to do inner bag, be castable around the inner bag, the bottom of inner bag is the composite structure of refractory brick and asbestos plate, and Buffer Unit and box hat are installed in the periphery of castable.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2060936C1 (en) * | 1993-01-06 | 1996-05-27 | Сибирский металлургический институт им.Серго Орджоникидзе | Method for production of crystalline silicium |
| CN1472137A (en) * | 2002-07-29 | 2004-02-04 | 王清东 | Method for preparing silicon metal |
| CN101230434A (en) * | 2008-02-18 | 2008-07-30 | 张国辉 | Method for producing high-activity granular carbon reductant |
| CN101724902A (en) * | 2009-12-16 | 2010-06-09 | 东北大学 | Process for preparing solar-grade polysilicon by adopting high-temperature metallurgy method |
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2011
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2060936C1 (en) * | 1993-01-06 | 1996-05-27 | Сибирский металлургический институт им.Серго Орджоникидзе | Method for production of crystalline silicium |
| CN1472137A (en) * | 2002-07-29 | 2004-02-04 | 王清东 | Method for preparing silicon metal |
| CN101230434A (en) * | 2008-02-18 | 2008-07-30 | 张国辉 | Method for producing high-activity granular carbon reductant |
| CN101724902A (en) * | 2009-12-16 | 2010-06-09 | 东北大学 | Process for preparing solar-grade polysilicon by adopting high-temperature metallurgy method |
Non-Patent Citations (1)
| Title |
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| 杨华.工业硅生产三要素.《铁合金》.2003,(第6期),11-17. * |
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