CN104724710A - Method for purifying industrial silicon by synchronously electroslag remelting and alloy liquation refining - Google Patents
Method for purifying industrial silicon by synchronously electroslag remelting and alloy liquation refining Download PDFInfo
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- CN104724710A CN104724710A CN201510118113.6A CN201510118113A CN104724710A CN 104724710 A CN104724710 A CN 104724710A CN 201510118113 A CN201510118113 A CN 201510118113A CN 104724710 A CN104724710 A CN 104724710A
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Abstract
The invention relates to an impurity removal method belonging to the field of alloy materials, particularly a method for purifying industrial silicon by synchronously electroslag remelting and alloy liquation refining. The method mainly comprises the following steps: (1) premelting industrial silicon and a metal liquation agent into an alloy, and making a consumable alloy electrode; (2) in an electroslag furnace, melting a slag melting agent into a slag basin by using an arc starting agent, overheating the slag basin, and immersing the consumable alloy electrode into the slag basin to perform electroslag remelting refining and alloy segregation refining; and (3) after finishing the refining and solidifying, obtaining a segregation alloy cast ingot, crushing and separating to obtain the purified polycrystalline silicon. Compared with the traditional metallurgical process, the method has the advantages of obviously higher impurity removal efficiency, short process and simple equipment, and is convenient to operate; and the refined material has the advantages of higher purity, fewer impurities, and uniform and compact chemical component and structure. In the electroslag remelting process, liquid slag protection always exists, thereby preventing the liquid alloy from directly contacting air, and preventing the oxidation loss of the silicon and metal liquation agent.
Description
Technical field
The present invention relates to a kind of field of alloy material and go deimpurity method, particularly the method for a kind of esr purifying industrial silicon synchronous with alloy liquation refining.
Background technology
Along with the available rate of the price of international energy continuous rise, the energy and security continuous decrease and various countries are to the raising of environmental concern degree, sun power is because it is inexhaustible, nexhaustible, safe and reliable and the feature little to environmental influence more and more receives the concern of people.In recent years, theCourse of PV Industry is rapid, sharply increases the demand of solar-grade polysilicon.But prepare solar-grade polysilicon technique due to chemical methods such as improved Siemens and have that energy consumption is high, cost is large and the problem such as environmental pollution is serious, metallurgy method prepares the focus that solar-grade polysilicon technology becomes concern.
Metallurgy method refers under the prerequisite not changing body silicon character, removing impurity in industrial silicon by directional freeze, pickling, slag refining, vacuum metling, a series of combined method such as high energy beam (electronics, ion) method, alloy liquation refining etc., is a kind of purification process step by step to impurity.Slag refining is the means effectively removing strong reducing property impurity, is one of main purification means of metallurgy method, and the removal effect of the method to nonmetallic impurity boron main in industrial silicon, phosphorus is undesirable.Boron, phosphorus affect the topmost impurity of solar cell properties, the requirement of solar-grade polysilicon to the content of B impurity is lower than 0.3 ppmw, be lower than 0.5 ppmw to the requirement of phosphorus, excessive B, P impurity can cause photo attenuation, thus affects the electricity conversion of battery.The refinery systems of traditional metallurgy method technical process also neither one complete mature, and because its long flow path, energy consumption are high and can not the problem such as continuous refining, application is industrially greatly limited.So, set up short route, high efficiency silicon materials purification process enhancement method is extremely urgent.
Esr is a kind of more special slag refinery practice, be utilize electric current by the resistance heat that produces during slag as thermal source by electrode melting, the metal dissolved pools and drips, and enters metal pool, be frozen into the method for foundry goods in water mold through slag blanket.Its method has been coupled the multiple purification effect of slag refining, wash heat and solidifying segregation, can strengthen aluminium alloy and the contact area of slag phase greatly, reach reinforcing mass transfer, improve refining efficiency, strengthen the effect of refining effect.This technique is very ripe in smelting iron and steel, and in the patent electroslag remelting slag of Baoshan Iron & Steel Co., Ltd and application (2011101247192) thereof, providing slag system proportioning is CaF230 ~ 35%; CaO 30 ~ 35%; Al
2o
325 ~ 30%; SiO
21 ~ 4%; MgO 1 ~ 5%, this method reduces hot-work die steel esr power consumption, and solves the stability problem of esr cinder high-temperature process.Meanwhile, in the refining of metal such as copper, aluminium, magnesium, technology and equipment R&D work has also been carried out both at home and abroad.Central Plains special steel bear length is poly-, the patent of Gao Hongsheng: a kind of copper electroslag remelting process (2008101404897), adopts 55-65%CaF
2, 15-25%MgF
2or NaF, 15-25%BaCl
2the slag system refining formed obtains the higher copper ingot of quality.But because the specific conductivity of silicon is less by (2.52 × 10
-4/ m Ω), electroconductibility extreme difference at normal temperatures, can not use as consumable electrode.So, there is larger bottleneck by the technology of refining by electro-slag remelting metalluragical silicon.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide the method for a kind of esr purifying industrial silicon synchronous with alloy liquation refining, solve not by the technical barrier of electroslag remelting process refining polysilicon, significantly promote refining effect.
The production method principle of esr of the present invention purifying polycrystalline silicon synchronous with alloy liquation refining is: first industrial silicon and metal liquate agent High Temperature Pre are melt into alloy and as consumable electrode, slag is made to be fused into slag bath by the effect of striking agent, after slag bath is overheated, consumable electrode is immersed in slag bath, carry out esr refining and segregation refining.
Specific implementation step is as follows:
1) industrial silicon and the agent of metal liquate are melt into alloy in advance and make consumable electrode;
2) by metal oxide or metal fused salt all mixed, slag forming agent is prepared in fritting;
3) in electroslag furnace, utilize striking agent to make slag be fused into slag bath, after slag bath is overheated, consumable alloy electrode is immersed in slag bath, carry out esr refining and segregation refining;
4) refining with solidify end, obtain segregation-alloy ingot casting, through broken apart, obtain the polysilicon of purifying.
Step 1) described in the agent of metal liquate be Sn, Al, Cu, Fe, Ni, Zn, or its two or more alloy cpd;
Step 1) described in the purity of metal liquate agent be 99% ~ 99.999%;
Step 2) described in metal oxide be CaO, SiO
2, Al
2o
3, MgO, Na
2o, Fe
2o
3, two or more mixture in MnO, BaO; Described metal fused salt is CaCl
2, KCl, NaCl, CaF
2, Na
2cO
3, Na
2siO
3, Na
3alF
6in two or more mixture;
Step 2) described in the chemical composition of slag agent be by weight percentage:
The present invention's advantage is compared with prior art: the present invention is compared with traditional metallurgy method, and refining effect has very big raising.The method can to make in silicon that typical nonmetallic impurity B, P are minimum reaches following content: B:0.3ppmw; P:0.5ppmw.And flow process is short, equipment is simple, easy to operate, the material purity after refining is higher, impurity is less, chemical composition and uniform texture, densification.In esr process, there is melt cinder to protect all the time, avoid liquid alloy and contact with the direct of air, prevent the oxidation of silicon and the agent of metal liquate.
Accompanying drawing explanation
Fig. 1 is technical schematic diagram of the present invention.
Embodiment
Embodiment 1
3kg silicon material and 3kg metallic tin (purity is 99.99%) are melt into tin silicon alloy in advance and make the consumable electrode of Φ 40 × 800mm.By 30kg CaO, SiO
2, Al
2o
3, CaF
2caO-SiO is melt in advance according to the ratio of mass ratio 3:3:2:2
2-Al
2o
3-CaF
2slag, slag chemical composition is CaO/SiO
2=1, SiO
2/ Al
2o
3=1.5, take out 18kg as slag agent.In electroslag furnace, utilize striking agent to make slag be fused into slag bath, after slag bath is overheated, consumable alloy electrode is immersed in slag bath, carry out esr refining and segregation refining.Refining with solidify end, obtain segregation-alloy ingot casting, through broken apart, obtain the polysilicon of purifying.
Purification the results are shown in Table 1.
Table 1
Unit: ppmw
Embodiment 2
1kg silicon material and 1k g metallic copper (purity is 99.9%) are melt into cupro silicon in advance and make the consumable electrode of Φ 40 × 1000mm.By CaO, SiO
2, Al
2o
3, CaF
2, MgO is melt into CaO-SiO in advance according to the ratio of mass ratio 2:3:3:2:1
2-Al
2o
3-NaCl-MgO slag, slag chemical composition is CaO/SiO
2=0.67, SiO
2/ Al
2o
3=1, take out 1kg as slag agent.In electroslag furnace, utilize striking agent to make slag be fused into slag bath, after slag bath is overheated, consumable alloy electrode is immersed in slag bath, carry out esr refining and segregation refining.Refining with solidify end, obtain segregation-alloy ingot casting, through broken apart, obtain the polysilicon of purifying.Purification the results are shown in Table 2.
Table 2
Unit: ppmw
Embodiment 3
50g silicon material and 100g metallic copper (purity is 99.999%), 30g metallic aluminium are melt into copper aluminum silicon alloy in advance and make the consumable electrode of Φ 40 × 1000mm.By CaO, SiO
2, CaCl
2, Na
3alF
6, BaO is melt into CaO-SiO in advance according to the ratio of mass ratio 4:5:1:2:1
2-CaCl
2-Na
3alF
6-BaO slag, slag chemical composition is CaO/SiO
2=0.8, take out 500g as slag agent.In electroslag furnace, utilize striking agent to make slag be fused into slag bath, after slag bath is overheated, consumable alloy electrode is immersed in slag bath, carry out esr refining and segregation refining.Refining with solidify end, obtain segregation-alloy ingot casting, through broken apart, obtain the polysilicon of purifying.Purification the results are shown in Table 3.
Table 3
Unit: ppmw
In a word, industrial silicon and the agent of metal liquate Sn, Al, Cu, Fe, Ni, Zn etc. are made consumable alloy electrode by the present invention, make it in electroslag refining, form loop with slag, solve not by the technical barrier of electroslag remelting process refining polysilicon, solve impurity element partition ratio in slag refining process little, the technical barrier that rate of mass transfer is slow, has increased substantially the isolation of purified effect of impurity in alloy.
And the present invention overcomes, and metallurgy method process efficiency is low, consume energy high, the shortcoming such as product is unstable, can effectively remove boron, phosphorus and metallic impurity.
There is provided above embodiment to be only used to describe object of the present invention, and do not really want to limit the scope of the invention.Scope of the present invention is defined by the following claims.Do not depart from spirit of the present invention and principle and the various equivalent substitutions and modifications made, all should contain within the scope of the present invention.
Claims (5)
1. a method for esr purifying industrial silicon synchronous with alloy liquation refining, its feature comprises the following steps:
(1) industrial silicon and the agent of metal liquate are melt into alloy in advance and make consumable alloy electrode; Two or more metal oxide or metal fused salt are mixed, fritting is prepared into slagging agent;
(2) in electroslag furnace, utilize striking agent to make slagging agent be fused into slag bath, after slag bath is overheated, consumable alloy electrode is immersed in slag bath, carry out esr refining and segregation refining;
(3) refining with solidify end, obtain segregation-alloy ingot casting, through broken apart, obtain the polysilicon of purifying.
2. the method for esr purifying industrial silicon synchronous with alloy liquation refining according to claim 1, it is characterized in that: metal liquate agent described in step (1) is Sn, Al, Cu, Fe, Ni, Zn, or its two or more alloy cpd.
3. the method for esr purifying industrial silicon synchronous with alloy liquation refining according to claim 1, is characterized in that: described in step (1), the purity of metal liquate agent is 99% ~ 99.999%.
4. the method for esr purifying industrial silicon synchronous with alloy liquation refining according to claim 1, is characterized in that: described in step (2), metal oxide and metal fused salt are selected from by CaO, SiO
2, Al
2o
3, MgO, Na
2o, Fe
2o
3, MnO, BaO, CaCl
2, KCl, NaCl, CaF
2, Na
2cO
3, Na
2siO
3, Na
3alF
6two or more the composition formed.
5. the method for esr purifying industrial silicon synchronous with alloy liquation refining according to claim 4, is characterized in that: the chemical composition of described metal oxide and metal fused salt is by weight percentage:
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111926146A (en) * | 2020-09-16 | 2020-11-13 | 攀钢集团研究院有限公司 | Method for reducing consumption of refractory material of electric furnace |
| CN112938983A (en) * | 2021-01-27 | 2021-06-11 | 中国科学院过程工程研究所 | Regenerated silicon prepared based on crystalline silicon cutting waste and preparation method thereof |
| CN115707786A (en) * | 2021-08-18 | 2023-02-21 | 中国科学院过程工程研究所 | Device and method for regenerating metal by vacuum electroslag-rotary segregation |
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| WO2009078467A1 (en) * | 2007-12-18 | 2009-06-25 | The Japan Steel Works, Ltd. | Slag for electroslag remelting of coppoer alloys and process for manufacturing copper alloy products |
| US20120164054A1 (en) * | 2009-01-08 | 2012-06-28 | Bp Corporation North America Inc. | Impurity Reducing Process and Purified Material |
| CN103011169A (en) * | 2012-12-14 | 2013-04-03 | 厦门大学 | Preparation method for sheet silicon |
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2015
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| WO2009078467A1 (en) * | 2007-12-18 | 2009-06-25 | The Japan Steel Works, Ltd. | Slag for electroslag remelting of coppoer alloys and process for manufacturing copper alloy products |
| CN101903544A (en) * | 2007-12-18 | 2010-12-01 | 株式会社日本制钢所 | Slag for electroslag remelting of coppoer alloys and process for manufacturing copper alloy products |
| US20120164054A1 (en) * | 2009-01-08 | 2012-06-28 | Bp Corporation North America Inc. | Impurity Reducing Process and Purified Material |
| CN103011169A (en) * | 2012-12-14 | 2013-04-03 | 厦门大学 | Preparation method for sheet silicon |
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|---|
| M.S. ISLAM ET AL.: "Electrically Enhanced Boron Removal from Silicon Using Slag", 《METALLURGICAL AND MATERIALS TRANSACTIONS B》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111926146A (en) * | 2020-09-16 | 2020-11-13 | 攀钢集团研究院有限公司 | Method for reducing consumption of refractory material of electric furnace |
| CN112938983A (en) * | 2021-01-27 | 2021-06-11 | 中国科学院过程工程研究所 | Regenerated silicon prepared based on crystalline silicon cutting waste and preparation method thereof |
| CN115707786A (en) * | 2021-08-18 | 2023-02-21 | 中国科学院过程工程研究所 | Device and method for regenerating metal by vacuum electroslag-rotary segregation |
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