CN102153088A - Method for carrying out slagging, pickling and boron removal on metal silicon - Google Patents
Method for carrying out slagging, pickling and boron removal on metal silicon Download PDFInfo
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Abstract
The invention discloses a method for carrying out slagging, pickling and boron removal on metal silicon, relates to a method for purifying polysilicon and provides the method for carrying out slagging, pickling and boron removal on the metal silicon. The method comprises the following steps of: premelting a slag forming constituent and placing the slag forming constituent into a charging bin; filling a metal silicon material into a smelting crucible; filling argon into the smelting crucible after vacuumizing; heating to melt the metal silicon material; adding the pre-molten slag forming constituent into the molten liquid metal silicon material; after a reaction is completed, pouring the liquid metal silicon material into a die and cooling the die to obtain a silicon ingot; crushing and grinding the obtained silicon ingot; sieving the obtained powder to obtain silicon powder; soaking the silicon powder in ethanol to remove oil; washing the silicon powder with water; soaking and washing the obtained powder at least once by solution of hydrochloric acid, mixed solution of sulphuric acid and nitric acid, mixed solution of hydrofluoric acid and solution of hydrochloric acid sequentially; and flushing the pickled silicon powder with clear water to obtain the metal silicon subjected to boron removal. The efficiency of removing boron is high and can reach over 96 percent. The boron content in the metal silicon is reduced to below 0.3ppmw from 8ppmw. The requirement of solar polysilicon is met.
Description
Technical field
The present invention relates to the method for purification of polysilicon, relate in particular to a kind of slag making pickling boron removal method of Pure Silicon Metal.
Background technology
Along with the development of world economy and the propelling of process of industrialization, human demand to the energy grows with each passing day.When satisfying self high speed development, humanly also be faced with the crisis that fossil energies such as coal, oil, Sweet natural gas exhaust gradually, and can't avoid the serious problem of environmental pollution.Compare with traditional energy, solar electrical energy generation has advantages such as clean environment firendly, safe and convenient, resource abundance, is reproducible green energy resource, can effectively alleviate energy shortage and environmental pollution problems.Therefore, photovoltaic energy is considered to most important new forms of energy of 21 century.
Polysilicon is the starting material of preparation silicon single crystal and solar cell, is the foundation stone of global electronic industry and photovoltaic industry.At present, the solar level silicon materials do not form independently supply system, and 90% derives from the waste material of electronic-grade silicon and the material end to end of silicon single crystal.Lack the development that solar energy polycrystalline silicon has cheaply hindered following photovoltaic industry.
The silicon purity that is generally used for solar cell is not less than 99.9999%, and boron content is not higher than 0.3ppmw.Though it is the silicon purity of Siemens Method production can satisfy the solar cell requirement, too expensive for the scale operation of solar cell.At present, there has been several method, can have produced solar energy level silicon cheaply.The technical barrier that exists is the removal, particularly boron of nonmetallic impuritys such as phosphorus, boron now, because the segregation coefficient of boron in silicon is very big and saturation steam forces down, is difficult to remove by traditional directional freeze or vacuum melting.And the content of boron impurity has very big influence to Solar cell performance, and therefore exploring various effective low-cost boron removal methods is polysilicon Study on Purification focuses.
People such as Alemany (1, Alemany C, Trassy C, Pateyron B, et al.Refiing of metallurgical grade silicon by inductive plasma[J] Solar Energy Materials﹠amp; Solar Cells, 2002,72:41-48) utilizing electromagnetic induction H
2-O
2Finding during Cement Composite Treated by Plasma silicon liquid has tangible refining effect, by calculation of thermodynamics and interpretation, confirms that the impurity element boron in the silicon is mainly removed with the form volatilization of BOH.Marvin's can wait the people (2, Wu Jijun, Ma Wenhui, Wei Kuixian, et al.Removing boron from metallurgical grade silicon by vacuum oxidation refining[C] .Proceedings of the 8
ThVacuum Metallurgy and Surface Engineering Conference.Shengyang 2007:51-55) adopts Ar-O
2Plasma body, behind the refining 10min, the boron content in the silicon drops to 2ppmw by 40ppmw in 2286～2320K scope.It is argon gas or the argon gas that adds hydrogen that Japanese Patent JP4-228414 adopts mixed gas, wherein contains water vapour, also contains the plasma body of SiO 2 powder, the surface of irradiation melted silicon, thereby the oxidation of promotion boron.Above technology has all adopted plasma body, its equipment requirements height, and the melting region of industrial silicon is narrow, and it is low to be blown into the oxidizing gas utilization ratio, and current consumption is big, and the treatment time is long, the production cost height.
Si system alloy can reduce impurity segregation coefficient in the silicon greatly, becomes the research focus of smelting method purifying polycrystalline silicon in recent years.People (3 such as Kazuki Morita, T.Yoshikawa and K.Morita, Removal of B from Si by solidification refining with Si-Al metals[J], Metall.Mater.Trans., 2005,36B:731-736.) silumin has been carried out going deep into systematic research except that boron, utilize the temperature gradient zone melting method to obtain the separation factor of boron under differing temps, boron is more much smaller than the separation factor between solid Si and the liquid phase Si at the separation factor between solid Si and the Si-Al alloy melt, and reduction (fusing point that will be higher than the Si-Al alloy) along with temperature, separation factor can be more and more littler, and the boron impurities clearance can reach more than 98% in the final silicon.U.S. Pat 2010/0254879A1 has mentioned and has a kind ofly fed Cl from the Si-Al alloy melt
2Or N
2Gas, boron can be reduced to 0.1ppmw from 30ppmw.Though with Al is that the good results are evident for the removal of impurities of solvent metal purified silicon, and self is with low cost, but the avidity between Al and Si is bigger, and density is close, thereby increased the difficulty that HIGH-PURITY SILICON is peeled off out from the Si-Al alloy, so generally will utilize the mode of repeatedly pickling it could be removed, and this has increased cost to a certain extent.
At present, slag practice is a boron impurity most effectual way in the low-cost silica removal.U.S. Pat 5788945 discloses a kind of 60%CaO～40%SiO that continuously adds in melting silicon
2The method of slag former, it is convection current in a container by slag and silicon that slag is handled, or by two or two convection current that realize melting slag and melt silicon with upper container, the boron content in the raw silicon can be reduced to 1ppmw from 40ppmw.It is SiO that U.S. Pat 2008/0241045A1 adopts slag former
2-Na
2CO
3, temperature is under 1600 ℃, and boron is reduced to 0.16ppmw in the silicon, wherein the slag former reusable edible.
Slag practice research is with a long history, still has following problem in industrial application at present: at first, and the still difficult requirement that reaches solar-grade polysilicon of the removal effect of boron.Secondly, help the consumption of slag agent too high relatively in the slagging process, limited scale operation, also can produce certain pollution silicon.
Hydrometallurgy route purification metallurgical grade silicon is the process that the silica flour that is crushed to certain particle diameter is leached by leaching agent (generally being acid).Chinese patent 200610170726.5 discloses the acid washing method of a kind of Pure Silicon Metal through nitric acid, hydrochloric acid and hydrofluoric acid and hydrogen peroxide solution, and the purity of the silicon that obtains is greater than 99.97%.Chinese patent 200810011266.0 has adopted a kind of method with chemical means purified silicons such as acid, alkali, earlier industrial silicon is crushed to suitable degree, soak with sodium hydroxide solution, use hydrochloric acid, chloroazotic acid and hydrofluoric acid acidleach then respectively again, obtain purity and be 99.99% silicon.Above technology can be carried out at normal temperatures, running cost is low, equipment is simple, treatment capacity is big, shortcoming be can only by with other metallurgy method in conjunction with just producing qualified solar level silicon materials, particularly nonmetallic impuritys such as boron, phosphorus are not had removal effect basically.
Summary of the invention
The objective of the invention is to the problem that exists in the Pure Silicon Metal boron removal method in the prior art, a kind of slag making pickling boron removal method of easy and simple to handle, environmental pollution is little, production cost is low Pure Silicon Metal is provided.
The slag making pickling boron removal method of described Pure Silicon Metal may further comprise the steps:
1) with the slag former fritting and pack into and add in the feed bin, the Pure Silicon Metal material is packed in the smelting pot, be evacuated to applying argon gas to 9000～11000Pa behind 200～600Pa;
2) heating and melting Pure Silicon Metal material in the liquid metal silicon material after the slag former adding thawing of step 1) fritting, is warming up to 1600～1800 ℃, feeds argon gas again, after the reaction liquid metal silicon material is poured in the mould, and cooling promptly gets silicon ingot;
3) with the fragmentation of gained silicon ingot, grinding, sieving obtains 60～100 purpose silica flours, and the gained silica flour deoils with alcohol immersion, and water cleans up again;
4) step 3) gained silica flour is used successively hydrochloric acid soln, sulfuric acid and nitric acid mixed solution, hydrofluoric acid mixed solution, hydrochloric acid soln washing by soaking at least 1 time, the silica flour after the pickling is clean with flushing with clean water again, promptly gets the Pure Silicon Metal that removes behind the boron.
In step 1), described slag former can be Al
2O
3-MnO-SiO
2-CaF
2Slag former etc., described Al
2O
3-MnO-SiO
2-CaF
2The composition of slag former can be by mass percentage: Al
2O
3Be 10%～30%, MnO is 5%～10%, CaF
2Be 5%～15%, surplus is SiO
2The mass ratio of described Pure Silicon Metal material and slag former can be 1: (0.05～1); Described smelting furnace can adopt the vacuum melting ingot furnaces of using more; Described Pure Silicon Metal material can be reguline metal silicon material or granulated metal silicon material.
In step 2) in, the speed of described feeding argon gas can be 1.5～5L/min, and the time of described reaction can be 2～5h.
In step 4), the temperature of described washing by soaking can be 50～60 ℃; Described hydrochloric acid soln mass concentration can be 20%～40%, and the time of hydrochloric acid soln washing by soaking can be 5～8h; Both volume ratios can be 1: 1 in described sulfuric acid and the nitric acid mixed solution, and the time of sulfuric acid and the washing of nitric acid mixed liquid dipping can be 10～12h; The prescription of hydrofluoric acid mixed solution can be: press mass ratio, hydrofluoric acid is 10%～40%, tensio-active agent alpha-olefin sodium sulfonate (AOS) or linear alkylbenzene sulphonic acid (LAS) are 2%～5%, hydrogen peroxide is 4%～8%, ammonium persulphate is 5%～10%, and the time of hydrofluoric acid mixed solution washing by soaking is 16～18h.
Compared with prior art, the present invention has following advantage:
1) according to phase diagram theory, boron oxidation products BO
1.5Combine with MnO easily, this means Al
2O
3-MnO-SiO
2-CaF
2This slag system has very strong oxygenizement at boron, has strong sorption simultaneously, to boron removal effect highly significant in the silicon.
2) hydrofluoric acid has weak acid and strong complexing dual function, can corrode silicon, produces small pore space structure at silicon face, and fluorion can form the title complex ion with boric acid under acidic conditions simultaneously
, impurity is dissolved out from silicon face absorption.Can reduce under the situation of silicon powder surface activation energy adding tensio-active agent, the impurity element of silica flour inside, particularly boron, to surface transport, and hydrogen peroxide and ammonium persulphate boron oxide cause the content of boron further to reduce from silica flour inside.
3) the present invention removes boron efficient height, can be up to more than 96%.Boron content in the Pure Silicon Metal is reduced to below the 0.3ppmw from 8ppmw, satisfies the requirement of solar-grade polysilicon.
Embodiment
Embodiment 1
1) with the slag former Al of 2.5kg
2O
3(20%wt)-MnO (5%wt)-SiO
2(70%wt)-CaF
2(5%wt) carry out fritting, the gained slag equivalent feed bin that adds in the feeding device of packing into.
2) go in the smelting pot the 50kg Pure Silicon Metal is packaged, open mechanical pump, when being evacuated to 500Pa, closed vacuum valve cuts out mechanical pump, and applying argon gas is to 10000Pa.
3) start heating in medium frequency the silicon material melted, treat that the silicon material melts fully after, rotation adds feed bin, adds the slag former of fritting in silicon liquid, utilizes two colorimetric-infrared thermometers to make temperature of reaction be controlled at 1700 ℃.
4) venting pin is reduced to silicon liquid surface preheating 10min, slowly insert then apart from crucible bottom 10mm place, the beginning aeration-agitation, the pilot-gas flow is 3L/min, behind the ventilation 3h, the upper strata silicon liquid in the smelting pot is all poured into accepted in the graphite crucible mold again, reduce the temperature to 800 ℃, insulation 1h with postcooling, takes out silicon ingot.
5) with the fragmentation of step 4) gained silicon ingot, grinding, sieving obtains 60～100 purpose silica flours, and silica flour is by the alcohol immersion processing of deoiling, and is clean with the deionized water bath.
6) silica flour after the step 5) processing is joined in the hydrochloric acid soln of 20% concentration, under the condition of magnetic agitation, liquid-solid ratio is 1: 3, and temperature is to soak 8h in 50～60 ℃ of solution, uses deionized water rinsing 3 times.
7) silica flour after the step 6) pickling is added in the mixed solution of 1: 1 vitriol oil of volume ratio and concentrated nitric acid, under the condition of magnetic agitation, liquid-solid ratio is 1: 3, and temperature is to soak 12h in 50～60 ℃ of solution, usefulness deionized water rinsing 5 times.
8) silica flour after the step 7) pickling is added in the mixed solution of ammonium persulphate of the hydrogen peroxide of the tensio-active agent alpha-olefin sodium sulfonate (AOS) of hydrofluoric acid, 5% concentration of 40% concentration or linear alkylbenzene sulphonic acid (LAS), 5% concentration and 10% concentration, under the condition of magnetic agitation, liquid-solid ratio is 1: 3, temperature is to soak 18h in 50～60 ℃ of solution, uses deionized water rinsing 5 times.
9) silica flour after the step 8) processing is joined in the hydrochloric acid soln of 40% concentration, under the condition of magnetic agitation, liquid-solid ratio is 1: 3, temperature is to soak 5h in 50～60 ℃ of solution, with deionized water rinsing repeatedly, is 6 until the pH of water value, oven dry promptly gets the silicon material of removing boron.
The boron content that records in the silicon by plasma inductance coupling mass spectrograph (ICP-MS) only is 0.21ppmw.
Embodiment 2
Technical process is with embodiment 1.Slag former is the Al of 5kg
2O
3(20%wt)-MnO (10%wt)-SiO
2(65%wt)-CaF
2(5%wt).The weight ratio of slag former and silicon material is 1: 10 (slag silicon ratio is 0.1).After treating that the silicon material melts fully, rotation adds feed bin, adds the slag former of fritting in silicon liquid, utilizes two colorimetric-infrared thermometers to make temperature of reaction be controlled at 1700 ℃.Venting pin is reduced to silicon liquid surface preheating 10min, slowly insert then apart from crucible bottom 20mm place, the pilot-gas flow is 3L/min, behind the ventilation 4h, again the upper strata silicon liquid in the smelting pot is all poured into and accepted in the graphite crucible mold, reduce the temperature to 800 ℃, insulation 1h, with postcooling, take out silicon ingot.The fragmentation of silicon ingot silicon ingot, grinding, sieving obtains 60～100 purpose silica flours, and silica flour is by the alcohol immersion processing of deoiling, and is clean with the deionized water bath.
Acid cleaning process is identical with embodiment 1.
The boron content that records in the silicon by plasma inductance coupling mass spectrograph (ICP-MS) is 0.18ppmw.
Embodiment 3
Technical process is with embodiment 1.Slag former is the Al of 7.5kg
2O
3(30%wt)-MnO (5%wt)-SiO
2(55%wt)-CaF
2(10%wt).The weight ratio of slag former and silicon material is 1: 5 (slag silicon ratio is 02).After treating that the silicon material melts fully, rotation adds feed bin, adds the slag former of fritting in silicon liquid, utilizes two colorimetric-infrared thermometers to make temperature of reaction be controlled at 1600 ℃.Venting pin is reduced to silicon liquid surface preheating 10min, slowly insert then apart from crucible bottom 20mm place, the pilot-gas flow is 2L/min, behind the ventilation 3h, again the upper strata silicon liquid in the smelting pot is all poured into and accepted in the graphite crucible mold, reduce the temperature to 800 ℃, insulation 1h, with postcooling, take out silicon ingot.The fragmentation of silicon ingot silicon ingot, grinding, sieving obtains 60～100 purpose silica flours, and silica flour is by the alcohol immersion processing of deoiling, and is clean with the deionized water bath.
Acid cleaning process is with embodiment 1.The boron content that records in the silicon by plasma inductance coupling mass spectrograph (ICP-MS) is 0.17ppmw.
Embodiment 4
Technological process is with embodiment 1.Slag former is the Al of 10kg
2O
3(10%wt)-MnO (10%wt)-SiO
2(70%wt)-CaF
2(10%wt).The weight ratio of slag former and silicon material is 3: 10 (slag silicon ratio is 0.3).After treating that the silicon material melts fully, rotation adds feed bin, adds the slag former of fritting in silicon liquid, utilizes two colorimetric-infrared thermometers to make temperature of reaction be controlled at 1800 ℃.Venting pin is reduced to silicon liquid surface preheating 10min, slowly insert then apart from crucible bottom 10mm place, the pilot-gas flow is 5L/min, behind the ventilation 4h, again the upper strata silicon liquid in the smelting pot is all poured into and accepted in the graphite crucible mold, reduce the temperature to 800 ℃, insulation 1h, with postcooling, take out silicon ingot.The fragmentation of silicon ingot silicon ingot, grinding, sieving obtains 60～100 purpose silica flours, and silica flour is by the alcohol immersion processing of deoiling, and is clean with the deionized water bath.
Acid cleaning process is with embodiment 1.The boron content that records in the silicon by plasma inductance coupling mass spectrograph (ICP-MS) is 0.14ppmw.
Embodiment 5
Technological process is with embodiment 1.Slag former is the Al of 15kg
2O
3(30%wt)-MnO (10%wt)-SiO
2(45%wt)-CaF
2(15%wt).The weight ratio of slag former and silicon material is 1: 2 (slag silicon ratio is 0.5).After treating that the silicon material melts fully, rotation adds feed bin, adds the slag former of fritting in silicon liquid, utilizes two colorimetric-infrared thermometers to make temperature of reaction be controlled at 1600 ℃.Venting pin is reduced to silicon liquid surface preheating 10min, slowly insert then apart from crucible bottom 10mm place, the pilot-gas flow is 2L/min, behind the ventilation 2h, again the upper strata silicon liquid in the smelting pot is all poured into and accepted in the graphite crucible mold, reduce the temperature to 800 ℃, insulation 1h, with postcooling, take out silicon ingot.The fragmentation of silicon ingot silicon ingot, grinding, sieving obtains 60～100 purpose silica flours, and silica flour is by the alcohol immersion processing of deoiling, and is clean with the deionized water bath.
Acid cleaning process is with embodiment 1.The boron content that records in the silicon by plasma inductance coupling mass spectrograph (ICP-MS) is 0.14ppmw.
Embodiment 6
Technological process is with embodiment 1.Slag former is the Al of 25kg
2O
3(10%wt)-MnO (5%wt)-SiO
2(70%wt)-CaF
2(15%wt).The weight ratio of slag former and silicon material is 1: 1 (slag silicon ratio is 1).After treating that the silicon material melts fully, rotation adds feed bin, adds the slag former of fritting in silicon liquid, utilizes two colorimetric-infrared thermometers to make temperature of reaction be controlled at 1800 ℃.Venting pin is reduced to silicon liquid surface preheating 10min, slowly insert then apart from crucible bottom 20mm place, the pilot-gas flow is 5L/min, behind the ventilation 5h, again the upper strata silicon liquid in the smelting pot is all poured into and accepted in the graphite crucible mold, reduce the temperature to 800 ℃, insulation 1h, with postcooling, take out silicon ingot.The fragmentation of silicon ingot silicon ingot, grinding, sieving obtains 60～100 purpose silica flours, and silica flour is by the alcohol immersion processing of deoiling, and is clean with the deionized water bath.
Acid cleaning process is with embodiment 1.The boron content that records in the silicon by plasma inductance coupling mass spectrograph (ICP-MS) is 0.11ppmw.
Claims (10)
1. the slag making pickling boron removal method of a Pure Silicon Metal is characterized in that may further comprise the steps:
1) with the slag former fritting and pack into and add in the feed bin, the Pure Silicon Metal material is packed in the smelting pot, be evacuated to applying argon gas to 9000～11000Pa behind 200～600Pa;
2) heating and melting Pure Silicon Metal material in the liquid metal silicon material after the slag former adding thawing of step 1) fritting, is warming up to 1600～1800 ℃, feeds argon gas again, after the reaction liquid metal silicon material is poured in the mould, and cooling promptly gets silicon ingot;
3) with the fragmentation of gained silicon ingot, grinding, sieving obtains 60～100 purpose silica flours, and the gained silica flour deoils with alcohol immersion, and water cleans up again;
4) step 3) gained silica flour is used successively hydrochloric acid soln, sulfuric acid and nitric acid mixed solution, hydrofluoric acid mixed solution, hydrochloric acid soln washing by soaking at least 1 time, the silica flour after the pickling is clean with flushing with clean water again, promptly gets the Pure Silicon Metal that removes behind the boron.
2. the slag making pickling boron removal method of a kind of Pure Silicon Metal as claimed in claim 1 is characterized in that in step 1), and described slag former is Al
2O
3-MnO-SiO
2-CaF
2Slag former, its composition is by mass percentage: Al
2O
3Be 10%～30%, MnO is 5%～10%, CaF
2Be 5%-15%, surplus is SiO
2
3. the slag making pickling boron removal method of a kind of Pure Silicon Metal as claimed in claim 1 is characterized in that the mass ratio at material of Pure Silicon Metal described in the step 1) and slag former is 1: (0.05～1).
4. the slag making pickling boron removal method of a kind of Pure Silicon Metal as claimed in claim 1 is characterized in that adopting the vacuum melting ingot furnaces of using at smelting furnace described in the step 1) more; Described Pure Silicon Metal material is reguline metal silicon material or granulated metal silicon material.
5. the slag making pickling boron removal method of a kind of Pure Silicon Metal as claimed in claim 1 is characterized in that in step 2) in, the speed of described feeding argon gas is 1.5～5L/min.
6. the slag making pickling boron removal method of a kind of Pure Silicon Metal as claimed in claim 1 is characterized in that in step 2) in, the time of described reaction is 2～5h.
7. the slag making pickling boron removal method of a kind of Pure Silicon Metal as claimed in claim 1 is characterized in that in step 4), and the temperature of described washing by soaking is 50～60 ℃.
8. the slag making pickling boron removal method of a kind of Pure Silicon Metal as claimed in claim 1 is characterized in that in step 4), and described hydrochloric acid soln mass concentration is 20%～40%, and the time of hydrochloric acid soln washing by soaking is 5～8h.
9. the slag making pickling boron removal method of a kind of Pure Silicon Metal as claimed in claim 1 is characterized in that in step 4), and both volume ratios are 1: 1 in sulfuric acid and the nitric acid mixed solution, and the time of sulfuric acid and the washing of nitric acid mixed liquid dipping is 10～12.
10. the slag making pickling boron removal method of a kind of Pure Silicon Metal as claimed in claim 1, it is characterized in that in step 4), the prescription of hydrofluoric acid mixed solution is: press mass ratio, hydrofluoric acid is 10%～40%, tensio-active agent alpha-olefin sodium sulfonate or linear alkylbenzene sulphonic acid are 2%～5%, hydrogen peroxide is 4%～8%, and ammonium persulphate is 5%～10%, and the time of hydrofluoric acid mixed solution washing by soaking is 16～18h.
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| CN104058405B (en) * | 2013-05-10 | 2016-08-24 | 福建兴朝阳硅材料股份有限公司 | A kind of remove foreign matter of phosphor and the method for boron in metallic silicon |
| CN110194456A (en) * | 2019-06-14 | 2019-09-03 | 宝兴易达光伏刃料有限公司 | A method of utilizing discarded silicon mud metal smelting silicon |
| CN110194456B (en) * | 2019-06-14 | 2022-10-21 | 宝兴易达光伏刃料有限公司 | Method for smelting metal silicon by using waste silicon sludge |
| CN111157672A (en) * | 2020-01-07 | 2020-05-15 | 武钢集团昆明钢铁股份有限公司 | Method for rapidly measuring content of calcium fluoride in slag of steelmaking refining furnace |
| CN115353110A (en) * | 2022-07-28 | 2022-11-18 | 商南中剑实业有限责任公司 | Method for removing boron impurities in industrial silicon by silicomanganese slagging and refining |
| CN115353110B (en) * | 2022-07-28 | 2023-11-21 | 商南中剑实业有限责任公司 | Method for removing boron impurities in industrial silicon by silicomanganese slagging refining |
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