CN103058201A - Method for removing impurity boron in metallurgical silicon by utilizing composite refining agent - Google Patents
Method for removing impurity boron in metallurgical silicon by utilizing composite refining agent Download PDFInfo
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- CN103058201A CN103058201A CN2013100591971A CN201310059197A CN103058201A CN 103058201 A CN103058201 A CN 103058201A CN 2013100591971 A CN2013100591971 A CN 2013100591971A CN 201310059197 A CN201310059197 A CN 201310059197A CN 103058201 A CN103058201 A CN 103058201A
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 81
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 78
- 239000010703 silicon Substances 0.000 title claims abstract description 78
- 238000007670 refining Methods 0.000 title claims abstract description 52
- 239000012535 impurity Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 25
- 229910052786 argon Inorganic materials 0.000 claims abstract description 20
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 235000013312 flour Nutrition 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 101100008044 Caenorhabditis elegans cut-1 gene Proteins 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 71
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 15
- 239000010439 graphite Substances 0.000 abstract description 15
- 230000006698 induction Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 1
- 229910002804 graphite Inorganic materials 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 239000011863 silicon-based powder Substances 0.000 abstract 1
- 239000002893 slag Substances 0.000 description 17
- 241000209456 Plumbago Species 0.000 description 14
- 238000005520 cutting process Methods 0.000 description 7
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920005591 polysilicon Polymers 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000007664 blowing Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 150000001639 boron compounds Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- XUKUURHRXDUEBC-SXOMAYOGSA-N (3s,5r)-7-[2-(4-fluorophenyl)-3-phenyl-4-(phenylcarbamoyl)-5-propan-2-ylpyrrol-1-yl]-3,5-dihydroxyheptanoic acid Chemical compound C=1C=CC=CC=1C1=C(C=2C=CC(F)=CC=2)N(CC[C@@H](O)C[C@H](O)CC(O)=O)C(C(C)C)=C1C(=O)NC1=CC=CC=C1 XUKUURHRXDUEBC-SXOMAYOGSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241001584775 Tunga penetrans Species 0.000 description 1
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- -1 boron oxide compound Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000013083 solar photovoltaic technology Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
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Abstract
The invention provides a method for removing impurity boron in metallurgical silicon by utilizing a composite refining agent. The method comprises the following steps of: crushing and grinding metallurgical silicon used as a raw material until the grain size is 150-200 meshes, fully mixing the prepared refining agent and silicon powder at a the mass ratio of (1:1):(3-1); preparing a cylindrical shape in a tablet press, and packaging into a graphite crucible, refining in a high-frequency induction furnace with 10-20L/min of argon, slowly cooling after carrying out heat preservation for 0.5-4 hours within the temperature range of 1420-1650 DEG C to obtain the refined silicon sample. By adopting the method, the oxidability of SiO2 is utilized; meanwhile, gaseous boride is generated from FeC12 and impurity boron; the FeCl12 and SiO2 in the refining agent play a role in boron removal at the same time; the removal efficiency of boron in the metallurgical silicon is improved to over 97%, and the boron content in the metallurgical silicon is obviously reduced. The method is simple to operate and strong in practicability.
Description
Technical field
The present invention relates to the method for purification of metallurgy-prepared polysilicon, especially relate to the method that a kind of composite refiner is removed boron impurities in the metallurgical grade silicon, belong to the solar-photovoltaic technology field.
Background technology
Because solar electrical energy generation has the relative popularity of absolute security, resource and the advantage that other conventional energy resourcess such as abundance, long lifetime and non-maintaining property do not possess, under energy shortage and environmental protection pressure continues to increase and national governments are positive support on policy, the photovoltaic industry development is very swift and violent.Global energy total amount statistics shows that sun power has accounted for 0.24% in the global energy total amount, and the proportion in renewable energy source then reaches 4.67%.Sun power is inexhaustible renewable and clean energy resource, and succeeding in developing first turnover ratio since U.S.'s Bell Laboratory in 1954 is 4.5% monocrystalline silicon battery, the photovoltaic power generation technology that from then on has been born and has converted solar energy into electrical energy.1990～2011 years global solar battery production obtain the growth of explosive type, since calendar year 2001, the annual average rate of increase of photovoltaic module has reached more than 30%, world's photovoltaic in 2005 is 1787MW, 2007 is 4000MW, global solar battery production in 2008 is 6850MW, rises to 9340MW in 2009, reaches 21GWp in 2010.Sun power is in Germany, Spain, and the developed countries such as Japan obtain positive promotion and application.Under the support of world market and country policy, China becomes the production capacity big country of global solar battery, output occupy the whole world half.Since two thousand eight global economy enters the downturn period, Germany in 2011, and the photovoltaics such as Italy are installed big country and are in succession reduced the photovoltaic subsidy, so that rely on the photovoltaic industry of government subsidy to be inflicted heavy losses on.Therefore, reducing the photovoltaic generation cost, realize the par online, is the significant problem that the photovoltaic industry faces.
At present, crystalline silicon is the topmost base mateiral of solar cell, in occupation of most of cost of solar cell.Improved Siemens is the main method of producing solar-grade polysilicon, but the method is difficult to satisfy the requirement of low-cost solar level polysilicon owing to shortcomings such as investment are larger, and production cost is higher.It is less that metallurgy method has investment, the advantages such as production cost is lower are favored gradually, its technical process and method are as raw material take metallurgical grade silicon, combine by purifying techniques such as hydrometallurgy, directional freeze, vacuum melting, slag refining and electron beam melting purifications, the purity of silicon product is reached or near 6N(99.9999%), to satisfy the requirement of solar-grade polysilicon.Boron is one of impurity element of most critical in the solar-grade polysilicon, its too high levels can reduce minority carrier life time and the optoelectronic transformation efficiency of solar cell material greatly, research finds that also the Fe-B complex body that forms between the boron in the silicon and the iron is the major cause that forms optical attenuation in the solar cell.
The method of removing boron impurities in the metallurgical grade silicon mainly contains blowing refining, plasma body refining and slag refining, because the slag refining method is simple, cost is low and become the topmost external refining mode of present metallurgical grade silicon.At present, choosing of refining agent is mainly with CaO-SiO
2Binary is the oxide compound slag on basis, its principle is to add the oxide compound that oxygenant is oxidized to boron impurities boron in metallurgical grade silicon, because it is acid that the oxide compound of boron is, will with slag in basic oxide be combined into stable borate, absorbed by slag after the boron oxidation in the silicon and remove thereby make.The people such as Luo Dawei " Trans. Nonferrous Met. Soc. China " (2011, deliver " Boron removal from metallurgical silicon using CaO-SiO on 21:1178-1184)
2-CaF
2", studied under the 1823K and utilized CaO-SiO
2-Al
2O
3Slag is down to 2ppmw with impurity B content by original 15ppmw, and Al, the Ca in the metallurgical grade silicon and the clearance of Mg also reach respectively 85.0%, 50.2% and 66.7% simultaneously.The people such as Cai Jing " material Leader " (2009, deliver " high-purity metalluragical silicon is except the progress of boron " on 23:81-84), under 1973 K with CaO-SiO
2-Na
2The O pre-melted slag is added in the fusion metallurgy level silicon that boron impurities content is 10ppmw by certain time interval, and passes into 99.5%Ar+0.5%H with the 18L/min flow velocity in silicon liquid
2O90 min, after the refining in the silicon boron content to 0.23ppmw.
Norway Elkem company has invented a kind of to silicon liquid interpolation 60%CaO-40%SiO
2The method of slag former (US5788945), the B content in the silicon can be reduced to 1ppmw from 40ppmw.Japanese Patent (NO.066523) proposes, SiO
2Content is better above 45% slag system boron removal effect, utilizes 65%SiO
2-35%CaO slag is down to 1.6ppmw with the boron content in the raw silicon from 7ppmw.Zhao Youwen etc. disclose " a kind of metallurgical silicon purification method and a kind of online slagging boron removal method " (CN 101671027), and oxygen blast is combined with slagging boron removal, add SiO
2, NaCl, Na
2O and MgO make the boron content in the silicon be reduced to 12ppmw from 28ppmw.Chinese patent " a kind of polycrystalline silicon purifying boron removal method " (CN101671023A), adds Na in silicon melt
2CO
3, SiO
2With slag formers such as basic metal, through slag refining repeatedly, the boron content in the silicon melt can be reduced to 0.18ppmw from 15ppmw.
More than these refinings except in the method for boron, when using the method for slag refining separately, be difficult to be reduced to below the 1.0ppmw boron content is disposable, reach this requirement, must use together or repeatedly repeat slag refining in conjunction with the air blowing oxidation refining, obviously, this will inevitably improve refining except the cost of boron.The present invention adopts a kind of method of composite refiner, through initial refining, can be with the boron content in the metallurgical grade silicon to 0.58ppmw, and clearance reaches more than 97%.
Summary of the invention
The object of the present invention is to provide a kind of composite refiner to remove the method for boron impurities in the metallurgical grade silicon, realize by following technical proposal.
Boron impurities in a kind of composite refiner removal metallurgical grade silicon (boron-containing quantity of metallurgical grade silicon is 10～30ppmw) method, following each step of process:
(1) with boron content be the block metallurgical grade silicon of 10～30ppmw to be crushed to granularity be 150～200 purpose powder, again that refining agent and metallurgical grade silica flour is full and uniform in the ratio of 1:1～3:1, and mixed material is pressed into the cylinder sheet;
(2) step (1) gained cylinder sheet is passed into the argon shield that flow is 10～20L/min, and after adopting 50 ℃/min to be warmed up to 1420～1650 ℃, behind insulation 0.5～4h, be cooled to room temperature with 20 ℃/min again, then close argon gas, take out sample;
(3) remove end to end impurity enriched part, namely obtain removing the silicon of boron impurities.
Boron content in the middle of gained silicon recycling ion jigger coupling mass spectrograph (ICP-MS) test sample.
The refining agent of described step (1) is the FeCl of mass content 35%～75%
2With 65%～25% SiO
2Mixture.
Described SiO
2And FeCl
2Be the analytical pure anhydrous powder, its purity is more than 99.8%.
The pressure that described step (1) is pressed into the cylinder sheet is 15MPa.
The removal of described step (3) end to end impurity enriched partly is that sample is respectively cut 1/10 of sample length end to end.
Remove the method for boron impurities with existing metallurgical grade silicon and compare, the present invention has the following advantages:
The present invention had both utilized SiO
2Oxygenant is oxidized to solid-state boron oxide compound with boron impurities in the silicon and removes, and makes again boron impurities and FeCl in the silicon simultaneously
2Reaction generates the form volatilization of gaseous boron compound, from thermodynamics of reactions, and FeCl
2Be most effective except boron in the molten chloride commonly used, this has improved the boron rate of removing of refining agent greatly, and boron is removed reaction can be expressed as respectively formula (1) and (2):
（2）
Boron removal method blowing refining, plasma body refining and slag refining that metallurgical grade silicon is traditional, present method do not need complicated air blowing or plasma body a refining unit, can finish in induction furnace, equipment is simple, less investment, production cost is low, can reach higher except boron efficient.The method has broken through and has adopted oxide compound to remove technique and the thinking of boron fully at present, has improved the removal efficient of boron in the silicon.Innovative point of the present invention is to make the boron impurities in the silicon not only to remove with the form of solid-oxide but also with the form volatilization of gaseous boron compound, and method is simple to operate, practical, after the refining in the metallurgical grade silicon removal efficient of boron reach more than 97%, basically can satisfy solar-grade polysilicon to the requirement of impurity element boron content.
Compare except boron with the oxide compound slag system of present research, present method has not only been utilized SiO
2Oxidisability, simultaneously, FeCl
2Generate gaseous boron compound, the FeCl in the refining agent with boron impurities
2And SiO
2Played simultaneously the effect except boron, the removal efficient of boron in the metallurgical grade silicon is brought up to more than 97%, reduced significantly the boron content in the metallurgical grade silicon, present method is simple to operate, and is practical.
Description of drawings
Fig. 1 is the process flow diagram of the inventive method.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail, but protection domain of the present invention is not limited to described content.
Embodiment 1
(1) with boron content be the block metallurgical grade silicon of 22ppmw to be crushed to granularity be 150～200 purpose powder 30g, again that refining agent and metallurgical grade silica flour is full and uniform in the ratio of 1:1, refining agent is the analytical pure FeCl of 10.5g
2Analytical pure SiO with 19.5g
2Mixture, and mixed material is pressed into the cylinder sheet take pressure as 15MPa;
(2) step (1) gained cylinder sheet is packed in the middle of the plumbago crucible, and plumbago crucible is put into the silica tube of high frequency furnace, pass into the argon shield that flow is 10L/min in the silica tube, and after adopting 50 ℃/min to be warmed up to 1420 ℃, behind the insulation 0.5h, be cooled to room temperature with 20 ℃/min again, silicon melt is fully separated with refining agent, then close argon gas, take out sample;
(3) use wire cutting machine to remove impurity enriched part end to end (sample respectively cut end to end sample length 1/10), namely obtain removing the silicon of boron impurities, the boron content that utilizes ICP-MS to detect in the silicon sample is 5.0ppmw, and clearance reaches 77%.
Embodiment 2
(1) with boron content be the block metallurgical grade silicon of 28ppmw to be crushed to granularity be 150～200 purpose powder 15g, again that refining agent and metallurgical grade silica flour is full and uniform in the ratio of 2:1, refining agent is the analytical pure FeCl of 10.5g
2Analytical pure SiO with 19.5g
2Mixture, and mixed material is pressed into the cylinder sheet;
(2) step (1) gained cylinder sheet is packed in the middle of the plumbago crucible, and plumbago crucible is put into the silica tube of high frequency furnace, pass into the argon shield that flow is 15L/min in the silica tube, and after adopting 50 ℃/min to be warmed up to 1550 ℃, behind the insulation 2h, be cooled to room temperature with 20 ℃/min again, silicon melt is fully separated with refining agent, then close argon gas, take out sample;
(3) use wire cutting machine to remove end to end impurity enriched part, namely obtain removing the silicon of boron impurities, utilize the boron content in the ICP-MS detection silicon sample, clearance reaches 88%.
Embodiment 3
(1) with boron content be the block metallurgical grade silicon of 22ppmw to be crushed to granularity be 150～200 purpose powder 10g, again that refining agent and metallurgical grade silica flour is full and uniform in the ratio of 3:1, refining agent is the analytical pure FeCl of 13.5g
2Analytical pure SiO with 16.5g
2Mixture, and mixed material is pressed into the cylinder sheet take pressure as 15MPa;
(2) step (1) gained cylinder sheet is packed in the middle of the plumbago crucible, and plumbago crucible is put into the silica tube of high frequency furnace, pass into the argon shield that flow is 15L/min in the silica tube, and after adopting 50 ℃/min to be warmed up to 1550 ℃, behind the insulation 4h, be cooled to room temperature with 20 ℃/min again, silicon melt is fully separated with refining agent, then close argon gas, take out sample;
(3) use wire cutting machine to remove impurity enriched part end to end (sample respectively cut end to end sample length 1/10), namely obtain removing the silicon of boron impurities, the boron content that utilizes ICP-MS to detect in the silicon sample is 0.58ppmw, and clearance reaches 97%.
Embodiment 4
(1) with boron content be the block metallurgical grade silicon of 30ppmw to be crushed to granularity be 150～200 purpose powder 10g, again that refining agent and metallurgical grade silica flour is full and uniform in the ratio of 3:1, refining agent is the analytical pure FeCl of 13.5g
2Analytical pure SiO with 16.5g
2Mixture, and mixed material is pressed into the cylinder sheet take pressure as 15MPa;
(2) step (1) gained cylinder sheet is packed in the middle of the plumbago crucible, and plumbago crucible is put into the silica tube of high frequency furnace, pass into the argon shield that flow is 20L/min in the silica tube, and after adopting 50 ℃/min to be warmed up to 1650 ℃, behind the insulation 3h, be cooled to room temperature with 20 ℃/min again, silicon melt is fully separated with refining agent, then close argon gas, take out sample;
(3) use wire cutting machine to remove impurity enriched part end to end (sample respectively cut end to end sample length 1/10), namely obtain removing the silicon of boron impurities, utilize ICP-MS to detect boron content in the silicon sample, clearance reaches 96%.
Embodiment 5
(1) with boron content be the block metallurgical grade silicon of 10ppmw to be crushed to granularity be 150～200 purpose powder 30g, again that refining agent and metallurgical grade silica flour is full and uniform in the ratio of 1:1, refining agent is the analytical pure FeCl of 22.5g
2Analytical pure SiO with 7.5g
2Mixture, and mixed material is pressed into the cylinder sheet;
(2) step (1) gained cylinder sheet is packed in the middle of the plumbago crucible, and plumbago crucible is put into the silica tube of high frequency furnace, pass into the argon shield that flow is 20L/min in the silica tube, and after adopting 50 ℃/min to be warmed up to 1500 ℃, behind the insulation 2h, be cooled to room temperature with 20 ℃/min again, silicon melt is fully separated with refining agent, then close argon gas, take out sample;
(3) use wire cutting machine to remove impurity enriched part end to end (sample respectively cut end to end sample length 1/10), namely obtain removing the silicon of boron impurities, utilize ICP-MS to detect boron content in the silicon sample, clearance reaches 94%.
Embodiment 6
(1) with boron content be the block metallurgical grade silicon of 15ppmw to be crushed to granularity be 150～200 purpose powder 10g, again that refining agent and metallurgical grade silica flour is full and uniform in the ratio of 3:1, refining agent is the analytical pure FeCl of 10.5g
2Analytical pure SiO with 19.5g
2Mixture, and mixed material is pressed into the cylinder sheet take pressure as 15MPa;
(2) step (1) gained cylinder sheet is packed in the middle of the plumbago crucible, and plumbago crucible is put into the silica tube of high frequency furnace, pass into the argon shield that flow is 20L/min in the silica tube, and after adopting 50 ℃/min to be warmed up to 1500 ℃, behind the insulation 4h, be cooled to room temperature with 20 ℃/min again, silicon melt is fully separated with refining agent, then close argon gas, take out sample;
(3) use wire cutting machine to remove impurity enriched part end to end (sample respectively cut end to end sample length 1/10), namely obtain removing the silicon of boron impurities, utilize ICP-MS to detect boron content in the silicon sample, clearance reaches 86%.
Embodiment 7
(1) with boron content be the block metallurgical grade silicon of 22ppmw to be crushed to granularity be 150～200 purpose powder 15g, again that refining agent and metallurgical grade silica flour is full and uniform in the ratio of 2:1, refining agent is the analytical pure FeCl of 22.5g
2Analytical pure SiO with 7.5g
2Mixture, and mixed material is pressed into the cylinder sheet take pressure as 15MPa;
(2) step (1) gained cylinder sheet is packed in the middle of the plumbago crucible, and plumbago crucible is put into the silica tube of high frequency furnace, pass into the argon shield that flow is 10L/min in the silica tube, and after adopting 50 ℃/min to be warmed up to 1450 ℃, behind the insulation 1h, be cooled to room temperature with 20 ℃/min again, silicon melt is fully separated with refining agent, then close argon gas, take out sample;
(3) use wire cutting machine to remove impurity enriched part end to end (sample respectively cut end to end sample length 1/10), namely obtain removing the silicon of boron impurities, the boron content that utilizes ICP-MS to detect in the silicon sample is 3.85ppmw, and clearance reaches 82.5%.
Claims (5)
1. a composite refiner is removed the method for boron impurities in the metallurgical grade silicon, it is characterized in that through following each step:
(1) with boron content be the block metallurgical grade silicon of 10～30ppmw to be crushed to granularity be 150～200 purpose powder, again that refining agent and metallurgical grade silica flour is full and uniform in the ratio of 1:1～3:1, and mixed material is pressed into the cylinder sheet;
(2) step (1) gained cylinder sheet is passed into the argon shield that flow is 10～20L/min, and after adopting 50 ℃/min to be warmed up to 1420～1650 ℃, behind insulation 0.5～4h, be cooled to room temperature with 20 ℃/min again, then close argon gas, take out sample;
(3) remove end to end impurity enriched part, namely obtain removing the silicon of boron impurities.
2. composite refiner according to claim 1 is removed the method for boron impurities in the metallurgical grade silicon, and it is characterized in that: the refining agent of described step (1) is the FeCl of mass content 35%～75%
2With 65%～25% SiO
2Mixture.
3. composite refiner according to claim 1 is removed the method for boron impurities in the metallurgical grade silicon, and it is characterized in that: the pressure that described step (1) is pressed into the cylinder sheet is 15MPa.
4. composite refiner according to claim 1 is removed the method for boron impurities in the metallurgical grade silicon, and it is characterized in that: the removal of described step (3) end to end impurity enriched partly is that sample is respectively cut 1/10 of sample length end to end.
5. composite refiner according to claim 2 is removed the method for boron impurities in the metallurgical grade silicon, it is characterized in that: described SiO
2And FeCl
2Be the analytical pure anhydrous powder, its purity is more than 99.8%.
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|---|---|---|---|---|
| CN105329901A (en) * | 2015-10-22 | 2016-02-17 | 昆明理工大学 | Method for removing impurity boron in industrial silicon by adding zinc compound into calcium silicate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4457902A (en) * | 1980-10-24 | 1984-07-03 | Watson Keith R | High efficiency hydrocarbon reduction of silica |
| CN101565186A (en) * | 2009-05-26 | 2009-10-28 | 昆明理工大学 | Method for removing boron impurities in silicon |
| CN102515168A (en) * | 2011-12-12 | 2012-06-27 | 昆明理工大学 | Method for removing boron impurity in industrial silicon |
-
2013
- 2013-02-26 CN CN201310059197.1A patent/CN103058201B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4457902A (en) * | 1980-10-24 | 1984-07-03 | Watson Keith R | High efficiency hydrocarbon reduction of silica |
| CN101565186A (en) * | 2009-05-26 | 2009-10-28 | 昆明理工大学 | Method for removing boron impurities in silicon |
| CN102515168A (en) * | 2011-12-12 | 2012-06-27 | 昆明理工大学 | Method for removing boron impurity in industrial silicon |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105329901A (en) * | 2015-10-22 | 2016-02-17 | 昆明理工大学 | Method for removing impurity boron in industrial silicon by adding zinc compound into calcium silicate |
| CN105329901B (en) * | 2015-10-22 | 2017-10-27 | 昆明理工大学 | It is a kind of that the method that zinc compound removes boron impurity in industrial silicon is added into calcium silicates |
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