CN102557039A - Refining agent for boron removal of slagging and refining industrial silicon melt - Google Patents
Refining agent for boron removal of slagging and refining industrial silicon melt Download PDFInfo
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- CN102557039A CN102557039A CN2012100573790A CN201210057379A CN102557039A CN 102557039 A CN102557039 A CN 102557039A CN 2012100573790 A CN2012100573790 A CN 2012100573790A CN 201210057379 A CN201210057379 A CN 201210057379A CN 102557039 A CN102557039 A CN 102557039A
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- 229910052796 boron Inorganic materials 0.000 title claims abstract description 106
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 98
- 239000010703 silicon Substances 0.000 title claims abstract description 98
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000007670 refining Methods 0.000 title claims abstract description 79
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 51
- 239000002893 slag Substances 0.000 claims abstract description 86
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000012535 impurity Substances 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000009877 rendering Methods 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 239000000155 melt Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000007789 gas Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 238000011112 process operation Methods 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 238000005272 metallurgy Methods 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 8
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920005591 polysilicon Polymers 0.000 description 3
- 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 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010669 acid-base reaction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Silicon Compounds (AREA)
Abstract
The invention provides a refining agent for the boron removal of a slagging and refining industrial silicon melt. The refining agent comprises the following ingredients in mass percent: 1-99% of Li2O, 1-99% of SiO2 and 0-98% of basic oxides. A using method of the refining agent comprises the following steps: industrial silicon with the boron content of 1-500 ppmw is taken as a raw material and is mixed with the refining agent for the boron removal of the slagging and refining industrial silicon melt according to a mass ratio of 10:1 to 1:10, the slagging and refining is carried out at the temperature of 1450-1850 DEG C, then, the cooling is carried out, and finally, the slag-silicon separation is carried out, so that the impurity, i.e. boron is removed along with slag. The refining agent has a remarkable effect in boron removal, and the using method of the refining agent has the advantages that: the boron content of industrial silicon can be lowered to be less than 1 ppmw, the slag-silicon separation is easy, the process operation is simple, the requirements on equipment are low, the cost is low, the energy consumption is low, the pollution is little, no harmful gases are generated, the waste slag can be recycled and reutilized, and the method is environment-friendly.
Description
Technical field
The present invention relates to a kind of refining agent of removing boron impurity in the industrial silicon melt, belong to the technical field of metallurgy method purifying industrial silicon.
Background technology
Because energy dilemma and traditional energy are to the pollution of environment, polysilicon solar cell becomes the focus that the whole world is paid close attention to.At present, the kiloton production of polysilicon mainly still adopts the improvement Siemens Method, and gordian technique is still grasped by minority developed countries such as the U.S., Germany, Japan and Norway, forms blockade on new techniques and corner on the market.Solve the situation of China's solar cell and the main dependence on import of material thereof, let solar cell get in the general population's the productive life, must explore novel method and the new way that solar energy level silicon is produced.
Metallurgy method prepares solar-grade polysilicon and is meant with metallurgical grade silicon (purity 98.5~99.5%) to be that raw material directly makes the method for purity at the polycrystalline silicon raw material that is used to produce solar cell more than 99.9999% through metallurgy purification.Metallurgy method is in 1996 the earliest by Kawasaki Steel (Kawasaki Steel Corp.); The method by industrial silicon production solar energy level silicon of exploitation mainly comprises: methods such as blowing refining method, electron-beam process beam-plasma smelting process, directional freeze, slag practice, vacuum melting method, high temperature fused salt electrolysis method, high pure raw material carbothermic method under the support of NEDO.For chemistry routes such as improvement Siemens Method; Metallurgy method has great importance; Because the rapid growth of photovoltaic industry is directly related with renewable energy producing method with cleaning, because the metallurgy method less investment, the construction period is short; Production energy consumption is low, is considered to direct and the most most economical method.
Because the specific physical character of some impurity element, the refining effect of some metallurgy method is very poor.Like boron, show that impurity element boron has relatively large separation factor, be 0.9, far above metallic impurity, even through twice directional freeze process, the purity of boron does not still reach the requirement of solar energy level silicon; And during 1823K, the saturated vapor pressure of boron is 6.78 * 10
-7Pa be far smaller than the vp 0.40Pa of silicon at this moment, so the method for vacuum melting also can't effectively be removed boron.And the boron impurities element is stayed the easy defective that forms in the material, and the compound minority carrier of defective can reduce battery conversion efficiency.Electron beam and beam-plasma smelting process can be removed the boron in the silicon effectively, but because the costliness of refining unit and the mistake high energy consumption in the refining process have determined electron-beam process and the limitation of beam-plasma smelting process on suitability for industrialized production.Therefore, the effective way of exploring various removal boron has become one of main research focus of metallurgy method purifying polycrystalline silicon.
The M. Tanahashi of Japan Nagoya university is at paper " Distribution behavior of boron between SiO
2-saturated NaO
0.5-CaO-SiO
2Flux-molten silicon " (J. Min. Mater. Process Ins. Jpn., 2002, calculate basic oxide Na in 118:497-505)
2The interpolation of O can be increased to 3.5 with the partition ratio of B in slag and silicon.Based on this, the Cai Jing of Xiamen University the paper progress of boron " high-purity metalluragical silicon remove " (the material Leader, 2009,12 (23): 81-84) with 55%CaO-30%SiO
2-15%Na
2The fritting of O slag is added in the fusion metallurgy level silicon that boron impurities content is 10ppm by certain time interval, under 1973K, in melt, feeds 99.5%Ar+0.5%H with the 18L/min flow velocity
2O, slag making blowing refining 90min can reduce to 0.23ppm with the boron content in the metallurgical grade silicon.People such as the L.A.V. Teixeira of Tokyo Univ Japan are at paper " Removal of Boron from Molten Silicon Using CaO-SiO
2Based Slags " (ISIJ Int., 2009, studied CaO-SiO respectively in 49:783-787)
2-0%Na
2O, CaO-SiO
2-7%Na
2O and CaO-SiO
2-10%Na
2Three kinds of different slag systems of O remove effect of boron, experimental result shows, to CaO-SiO
2The binary slag system adds Na
2O can obviously increase L
B, and L
BBe along with Na
2The increase of O content increases.
Summary of the invention
The objective of the invention is to realize that the boron impurities in the industrial silicon melt is removed efficiently in the slag making refining process, a kind of Li is provided
2O is an industrial silicon melt slagging boron removal refining agent, realizes through following technical proposal.
OnePlant the refining agent of slag making rendering industry silicon melt, comprise the following component of mass percent: Li except that boron
2O is 1~99%, SiO
2Be 1~99%, basic oxide are 0~98%.
Said Li
2O generates Li by under refining temperature, decomposing
2The compound of O substitutes, like Li
2CO
3Deng.
Said refining agent also comprises other compounds, like Al
2O
3, CaF
2Deng.
Said basic oxide are like CaO, MgO, BaO, Na
2O, K
2O etc.
The refining agent that said slag making rendering industry silicon melt removes boron in use; Be to be that the industrial silicon of 1~500ppmw is that 10 ︰, 1~1 ︰ 10 mixes as the refining agent that raw material and slag making rendering industry silicon melt remove boron by mass ratio with boron-containing quantity; Under 1450~1850 ℃, carry out slag making refining 0.5~15h, the boron impurities element in the silicon, the refining agent chemisorption that pure boron or the boron-oxygen that after oxidation, generates all can be added into; And its reacting generating compound is stayed in the slag; Cooling is then carried out slag silicon at last and is separated, and boron impurities is accompanied by slag and obtains removing.
The addition sequence that said slag making rendering industry silicon melt removes the refining agent of boron be prior to the industrial silicon raw material or melt adds or during refining time sharing segment add, or with each component in the refining agent add respectively, or with adding together after each component is mixed in the refining agent etc., but be not limited to above-mentioned addition sequence.
The adding method that said slag making rendering industry silicon melt removes the refining agent of boron be directly from fire door, or directly from breather line add, or from modes such as fire door and breather line add simultaneously, but be not limited to above-mentioned adding mode.
Said slag making rendering industry silicon melt removes the refining agent and the conventional refining gas while or the use that intersects of boron.
Said conventional refining gas be in air, oxygen-rich air, oxygen, water vapour, argon gas, the nitrogen any one or multiple, but be not limited to above-mentioned gas.
In the slag making refining process, the impurity B element oxidation in the industrial silicon generates gaseous state B
x O
y, part is removed with the gaseous form volatilization, and part is still with acidic oxide B
x O
yRemain in the melt silicon.Under the high temperature fused state, Li
2B in O and the silicon
x O
yAcid-base reaction takes place generate Li
xB
yO
zCompound is stayed it in slag; Simultaneously, add a small amount of alkaline Li
2O can obviously improve slag basicity, and slag basicity raises, with the B in the absorption melt silicon
x O
yAnd generate compound with its generation acid-base reaction and stay in the slag.The slag making refining finishes the back when carrying out the separation of slag silicon, and the boron impurities element is accompanied by slag and obtains removing, and makes the boron content in the industrial silicon be reduced to < 1ppmw.Through facts have proved on a large scale, use this refining agent slag making rendering industry silicon melt, in the boron impurity, other common impurity (like Al, Ca, P etc.) has also obtained removal in various degree in the silicon in removing silicon.
After the invention provides refining agent that a kind of slag making rendering industry silicon melt removes boron and industrial silicon mixing, carry out slag making refining purifying industrial silicon, the refining agent that is added can with the impurity B element of remnants among the chemisorption Si, and with its reaction enrichment and slag in.Utilize the characteristic of refining agent; Remove impurity (Al, Ca, P, B) in the silicon through slag making; Especially to the most difficult boron of removing one of impurity in the silicon, effect is obvious, is used to produce the high-quality industrial silicon product of ultralow boron content; Compare with existing used refining agent, the present invention has following advantage:
(1) effect is remarkable, and this method can be reduced to the boron content in the industrial silicon that < 1ppmw can be used for producing the high-quality industrial silicon of ultralow boron content;
(2) main compound Li
2O density is little, so slag system density is bigger with melt silicon difference much smaller than other existing slag systems, is easy to the separation of slag silicon;
(3) technological operation is simple, and is low for equipment requirements, with low cost;
(4) energy consumption is low, pollutes for a short time, and this process does not produce that obnoxious flavour, waste residue are capable of circulation to be utilized again, and is environmentally friendly.
This method can combine with the existing production process of industrial silicon, directly toward filling an amount of refining agent of the middle adding of two-maing ladle of industrial silicon melt, controls suitable refinery practice and parameter; Can reach refining effect; Realize effective utilization of industrial silicon melt heat, pollution-free, less investment; Easy handling and industrial applications meet the industry policy of energy-saving and emission-reduction.
Embodiment
Below in conjunction with embodiment the present invention is done further elaboration.
Embodiment 1
Take by weighing analytical pure Li
2O is 1.75g, SiO
2For 18.29g, CaO are 14.96g grinds 5min and mixes in agate mortar after, make the refining agent that slag making rendering industry silicon melt removes boron.
The industrial silicon 35g that with boron-containing quantity is 15ppmw is that 1 ︰ 1 mixes with the refining agent that slag making rendering industry silicon melt removes boron by mass ratio as raw material, and feeding argon gas in the stove carries out slag making refining 1.5h under 1550 ℃; Boron impurities element in the silicon; The refining agent chemisorption that pure boron or the boron-oxygen that after oxidation, generates all can be added into, and its reacting generating compound is stayed in the slag cooling then; Carry out slag silicon at last and separate, boron impurities is accompanied by slag and obtains removing.Use ICPMS to measure boron content and be 0.44ppmw, the boron clearance is 97.07%.
Embodiment 2
Take by weighing analytical pure Li
2O is 7g, SiO
2For 15.4g, CaO are 12.6g grinds 8min and mixes in agate mortar after, make the refining agent that slag making rendering industry silicon melt removes boron.
The industrial silicon 35g that with boron-containing quantity is 15ppmw is that 1 ︰ 1 mixes with the refining agent that slag making rendering industry silicon melt removes boron by mass ratio as raw material, and feeding argon gas in the stove carries out slag making refining 3h under 1650 ℃; Boron impurities element in the silicon; The refining agent chemisorption that pure boron or the boron-oxygen that after oxidation, generates all can be added into, and its reacting generating compound is stayed in the slag cooling then; Carry out slag silicon at last and separate, boron impurities is accompanied by slag and obtains removing.Use ICPMS to measure boron content and be 0.43ppmw, the boron clearance is 97.13%.
Embodiment 3
Take by weighing analytical pure Li
2O is 14g, SiO
2For 11.55g, CaO are 9.45g grinds 4min and mixes in agate mortar after, make the refining agent that slag making rendering industry silicon melt removes boron.
The industrial silicon 35g that with boron-containing quantity is 15ppmw is that 1 ︰ 1 mix with the refining agent that slag making rendering industry silicon melt removes boron by mass ratio as raw material; Under 1800 ℃, carry out slag making refining 6h, the boron impurities element in the silicon, the refining agent chemisorption that pure boron or the boron-oxygen that after oxidation, generates all can be added into; And its reacting generating compound is stayed in the slag; Cooling is then carried out slag silicon at last and is separated, and boron impurities is accompanied by slag and obtains removing.Use ICPMS to measure boron content and be 0.46ppmw, the boron clearance is 96.93%.
Embodiment 4
Take by weighing analytical pure Li
2CO
3Be 315g, SiO
2For 17.5g, BaO are 8.75g, Al
2O
3Be 8.75g, make the refining agent that slag making rendering industry silicon melt removes boron.
The industrial silicon 35g that with boron-containing quantity is 500ppmw is that 1 ︰ 10 mix with the refining agent that slag making rendering industry silicon melt removes boron by mass ratio as raw material; Under 1850 ℃, carry out slag making refining 0.5h, the boron impurities element in the silicon, the refining agent chemisorption that pure boron or the boron-oxygen that after oxidation, generates all can be added into; And its reacting generating compound is stayed in the slag; Cooling is then carried out slag silicon at last and is separated, and boron impurities is accompanied by slag and obtains removing.Use ICPMS to measure boron content and be 15ppmw, the boron clearance is 97%.
Embodiment 5
Take by weighing analytical pure Li
2O is 3.465g, SiO
2Be 0.035g, mix promptly making the refining agent that slag making rendering industry silicon melt removes boron.
The industrial silicon 35g that with boron-containing quantity is 1ppmw is that 10 ︰s 1 mix with the refining agent that slag making rendering industry silicon melt removes boron by mass ratio as raw material; Under 1450 ℃, carry out slag making refining 15h, the boron impurities element in the silicon, the refining agent chemisorption that pure boron or the boron-oxygen that after oxidation, generates all can be added into; And its reacting generating compound is stayed in the slag; Cooling is then carried out slag silicon at last and is separated, and boron impurities is accompanied by slag and obtains removing.Use ICPMS to measure boron content and be 0.04ppmw, the boron clearance is 96%.
Embodiment 6
Take by weighing analytical pure Li
2O is 0.035g, SiO
2For 3.465g grinds 4min and mix in agate mortar after, make the refining agent that slag making rendering industry silicon melt removes boron.
The industrial silicon 35g that with boron-containing quantity is 100ppmw is that 10 ︰s 1 mix with the refining agent that slag making rendering industry silicon melt removes boron by mass ratio as raw material; Under 1600 ℃, carry out slag making refining 6h, the boron impurities element in the silicon, the refining agent chemisorption that pure boron or the boron-oxygen that after oxidation, generates all can be added into; And its reacting generating compound is stayed in the slag; Cooling is then carried out slag silicon at last and is separated, and boron impurities is accompanied by slag and obtains removing.Use ICPMS to measure boron content and be 2.88ppmw, the boron clearance is 97.12%.
Embodiment 7
Take by weighing analytical pure Li
2O is 0.35g, SiO
2For 0.35g, MgO are 34.3g grinds 2min and mixes in agate mortar after, make the refining agent that slag making rendering industry silicon melt removes boron.
The industrial silicon 35g that with boron-containing quantity is 15ppmw is that 1 ︰ 1 mix with the refining agent that slag making rendering industry silicon melt removes boron by mass ratio as raw material; Under 1500 ℃, carry out slag making refining 10h, the boron impurities element in the silicon, the refining agent chemisorption that pure boron or the boron-oxygen that after oxidation, generates all can be added into; And its reacting generating compound is stayed in the slag; Cooling is then carried out slag silicon at last and is separated, and boron impurities is accompanied by slag and obtains removing.Use ICPMS to measure boron content and be 0.51ppmw, the boron clearance is 96.6%.
Claims (3)
1. a slag making rendering industry silicon melt removes the refining agent of boron, it is characterized in that: the following component that comprises mass percent: Li
2O is 1~99%, SiO
2Be 1~99%, basic oxide are 0~98%.
2. remove the refining agent of boron according to the said slag making rendering industry of claim 1 silicon melt, it is characterized in that: said Li
2O generates Li by under refining temperature, decomposing
2The compound of O substitutes.
3. claim 1 or 2 said slag making rendering industry silicon melts remove the method for use of the refining agent of boron; It is characterized in that through the following step: the industrial silicon that with boron-containing quantity is 1~500ppmw is that 10 ︰s 1~1 ︰ 10 mix with the refining agent that slag making rendering industry silicon melt removes boron by mass ratio as raw material; Under 1450~1850 ℃, carry out slag making refining 0.5~15h; Cooling is then carried out slag silicon at last and is separated, and boron impurities is accompanied by slag and obtains removing.
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CN103073001A (en) * | 2013-02-26 | 2013-05-01 | 昆明理工大学 | Method for removing impurity boron of metallurgical silicon by high-basicity refining agent |
CN103276446A (en) * | 2013-06-06 | 2013-09-04 | 青岛隆盛晶硅科技有限公司 | Method for reutilization of slag agent after medium smelting |
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Cited By (6)
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CN103073001A (en) * | 2013-02-26 | 2013-05-01 | 昆明理工大学 | Method for removing impurity boron of metallurgical silicon by high-basicity refining agent |
CN103073001B (en) * | 2013-02-26 | 2015-12-02 | 昆明理工大学 | A kind of method adopting high alkalinity refining agent to remove boron impurities in metallurgical grade silicon |
CN103276446A (en) * | 2013-06-06 | 2013-09-04 | 青岛隆盛晶硅科技有限公司 | Method for reutilization of slag agent after medium smelting |
CN103276446B (en) * | 2013-06-06 | 2015-09-09 | 青岛隆盛晶硅科技有限公司 | A kind of method of slag agent recycling after medium melting |
CN114349009A (en) * | 2022-01-21 | 2022-04-15 | 贵州理工学院 | Slag agent for refining and deferrization of iron and titanium outside industrial silicon furnace |
CN115852193A (en) * | 2022-12-26 | 2023-03-28 | 山东创新金属科技有限公司 | Aluminum alloy smelting refining agent and preparation method thereof |
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