CN104724710B - A kind of method of electroslag remelting purifying industrial silicon synchronous with alloy liquation refining - Google Patents
A kind of method of electroslag remelting purifying industrial silicon synchronous with alloy liquation refining Download PDFInfo
- Publication number
- CN104724710B CN104724710B CN201510118113.6A CN201510118113A CN104724710B CN 104724710 B CN104724710 B CN 104724710B CN 201510118113 A CN201510118113 A CN 201510118113A CN 104724710 B CN104724710 B CN 104724710B
- Authority
- CN
- China
- Prior art keywords
- refining
- alloy
- agent
- metal
- electroslag remelting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
Deimpurity method, the method for more particularly to a kind of electroslag remelting purifying industrial silicon synchronous with alloy liquation refining are gone the present invention relates to a kind of field of alloy material.Mainly include：(1) industrial silicon and the agent of metal liquate are melt into alloy and make consumable alloy electrode in advance；(2) in electroslag furnace, slagging agent is fused into slag bath using striking agent, immerse in slag bath consumable alloy electrode after slag bath overheat, carry out electroslag remelting refining with segregation refining；(3) refining terminates with solidification, obtains segregation-alloy ingot casting, through broken apart, obtains the polysilicon of purifying.Of the invention dust removal rate is significantly improved compared with traditional metallurgy method, and flow is short, equipment is simple and convenient to operate, and the material purity after refining is higher, impurity less, chemical composition and uniform texture, densification.In esr process, there is melt cinder to protect all the time, it is to avoid the directly contact of liquid alloy and air, it is therefore prevented that the oxidational losses of silicon and metal liquate agent.
Description
Technical field
Deimpurity method is gone the present invention relates to a kind of field of alloy material, more particularly to a kind of electroslag remelting melts with alloy
The method of the synchronous purifying industrial silicon of analysis refining.
Background technology
As the price of international energy continuous rise, the availability of the energy and security continuous decrease and various countries close to environment
The raising of note degree, the characteristics of solar energy is due to its inexhaustible, nexhaustible, safe and reliable and small effect on environment increasingly
Paid close attention to by people.In recent years, theCourse of PV Industry is rapid, and the demand to solar-grade polysilicon is sharply increased.But due to
The chemical methods such as improved Siemens prepare solar-grade polysilicon technique and have that high energy consumption, cost be big and environmental pollution is serious etc. asks
Topic, metallurgy method prepares solar-grade polysilicon technology as focus of attention.
Metallurgy method refers on the premise of body silicon property is not changed, by directional solidification, pickling, slag refining, vacuum smelting
Impurity in a series of combined method removal industrial silicons such as refining, high energy beam (electronics, ion) method, alloy liquation refining, is a kind of right
The purification technique step by step of impurity.Slag refining is the means for effectively removing strong reducing property impurity, is the main purification hand of metallurgy method
One of section, the method is undesirable to the removal effect of main nonmetallic inclusion boron in industrial silicon, phosphorus.Boron, phosphorus are influence solar energy
The topmost impurity of battery performance, requirement of the solar-grade polysilicon to the content of B impurity is less than 0.3 ppmw, to phosphorus
It is required that being less than 0.5 ppmw, excessive B, P impurity can cause photo attenuation, so as to influence the electricity conversion of battery.Pass
The refinery systems of the metallurgy method technological process of system also neither one complete mature, and due to its long flow path, high energy consumption and can not
The problems such as continuous refining, application industrially is greatly limited.So, set up short route, efficient silicon materials
Purification process intensifying method is extremely urgent.
Electroslag remelting is a kind of special slag refinery practice of comparing, the resistance heat produced when being and utilizing electric current by slag
As thermal source by electrode melting, the metal for dissolving pools drop, metal bath is entered through slag blanket, is solidified in water mold
Into the method for casting.Its method has coupled many repurifieds effect of slag refining, wash heat and solidifying segregation, can greatly strengthen
Aluminium alloy and the contact area of slag phase, reach reinforcing mass transfer, improve refining efficiency, strengthen the effect of refining effect.This technique
It is extremely ripe in terms of smelting iron and steel, the patent electroslag remelting slag of Baoshan Iron ＆ Steel Co., Ltd and its application
(2011101247192) in, it is CaF230~35% to provide slag system proportioning；CaO 30~35%；Al2O325~30%；SiO21
~4%；MgO 1~5%, this method reduce hot die steel electroslag remelting power consumption, and solve electroslag remelting cinder high-temperature
The stability problem of process.Meanwhile, technology and equipment research and development work have been also carried out in terms of the refining of metal such as copper, aluminium, magnesium both at home and abroad
Make.The Central Plains special steel bear poly-, patent of Gao Hongsheng long：A kind of copper electroslag remelting process (2008101404897), using 55-65%
CaF2, 15-25%MgF2Or NaF, 15-25%BaCl2The slag system refining for being constituted obtains quality copper ingot higher.But due to silicon
Electrical conductivity it is smaller by (2.52 × 10-4/ m Ω), electric conductivity extreme difference at normal temperatures, it is impossible to used as consutrode.So, lead to
There is larger bottleneck in the technology for crossing refining by electro-slag remelting metalluragical silicon.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of electroslag remelting is same with alloy liquation refining
The method for walking purifying industrial silicon, solves the technical barrier that polysilicon can not be refined by electroslag remelting process, and essence is substantially improved
Refining effect.
The production method principle of electroslag remelting of the invention purifying polycrystalline silicon synchronous with alloy liquation refining is：First by work
Industry silicon is melt into alloy and as consutrode in advance with metal liquate agent high temperature, slag is melted slagging by the effect of striking agent
Pond, immerses in slag bath consutrode after slag bath overheat, carries out electroslag remelting refining with segregation refining.
Implement step as follows：
1) industrial silicon and the agent of metal liquate are melt into alloy and make consutrode in advance；
2) metal oxide or metal fused salt are mixed, fritting prepares slag forming agent；
3) in electroslag furnace, slag is made to be fused into slag bath using striking agent, by the immersion of consumable alloy electrode after slag bath overheat
In slag bath, electroslag remelting refining is carried out with segregation refining；
4) refining terminates with solidification, obtains segregation-alloy ingot casting, through broken apart, obtains 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 alloying
Compound；
Step 1) described in metal liquate agent purity be 99%~99.999%；
Step 2) described in metal oxide be CaO, SiO2、Al2O3、MgO、Na2O、Fe2O3, two kinds in MnO, BaO
Or two or more mixtures；Described metal fused salt is CaCl2、KCl、NaCl、CaF2、Na2CO3、Na2SiO3、Na3AlF6In
Two or more mixture；
Step 2) described in the chemical constituent of slag agent be by weight percentage：
Present invention advantage compared with prior art is：It is of the invention compared with traditional metallurgy method, refining effect has pole
It is big to improve.The method can make in silicon that typical nonmetallic inclusion B, P are minimum to reach following content：B：0.3ppmw；P：0.5ppmw.
And flow is short, equipment is simple and convenient to operate, the material purity after refining is higher, impurity less, chemical composition and institutional framework are equal
Even, densification.In esr process, there is melt cinder to protect all the time, it is to avoid the directly contact of liquid alloy and air, it is therefore prevented that silicon
With the oxidation of metal liquate agent.
Brief description of the drawings
Fig. 1 is technical schematic diagram of the invention.
Specific embodiment
Embodiment 1
3kg silicon materials and 3kg metallic tins (purity is 99.99%) are melt into tin silicon alloy and are made 40 × 800mm of Φ in advance
Consutrode.By 30kg CaO, SiO2、Al2O3、CaF2According to mass ratio 3:3:2:2 ratio is melt into CaO-SiO in advance2-Al2O3-
CaF2Slag, slag chemical constituent is CaO/SiO2=1, SiO2/Al2O3=1.5,18kg is taken out as slag agent.In electroslag furnace,
Slag is fused into slag bath using striking agent, immerse in slag bath consumable alloy electrode after slag bath overheat, carry out electroslag remelting essence
Refining and segregation refining.Refining terminates with solidification, obtains segregation-alloy ingot casting, through broken apart, obtains the polysilicon of purifying.
Purification the results are shown in Table 1.
Table 1
Unit：ppmw
Embodiment 2
1kg silicon materials and 1k g metallic coppers (purity is 99.9%) are melt into cupro silicon and are made 40 × 1000mm of Φ in advance
Consutrode.By CaO, SiO2、Al2O3、CaF2, MgO is according to mass ratio 2:3:3:2:1 ratio is melt into CaO-SiO in advance2-
Al2O3- NaCl-MgO slags, slag chemical constituent is CaO/SiO2=0.67, SiO2/Al2O3=1,1kg is taken out as slag agent.
In electroslag furnace, slag is fused into slag bath using striking agent, immerse in slag bath consumable alloy electrode after slag bath overheat, carry out
Electroslag remelting is refined and segregation refining.Refining terminates with solidification, obtains segregation-alloy ingot casting, through broken apart, obtains pure
The polysilicon of change.Purification the results are shown in Table 2.
Table 2
Unit：ppmw
Embodiment 3
50g silicon materials are melt into copper alusil alloy and be made in advance with 100g metallic coppers (purity is 99.999%), 30g metallic aluminiums
The consutrode of 40 × 1000mm of Φ.By CaO, SiO2、CaCl2、Na3AlF6, BaO is according to mass ratio 4:5:1:2:1 ratio is pre-
It is melt into CaO-SiO2-CaCl2-Na3AlF6- BaO slags, slag chemical constituent is CaO/SiO2=0.8,500g is taken out as slag
Agent.In electroslag furnace, slag is fused into slag bath using striking agent, immerse in slag bath consumable alloy electrode after slag bath overheat,
Electroslag remelting refining is carried out with segregation refining.Refining terminates with solidification, obtains segregation-alloy ingot casting, through broken apart, obtains
The polysilicon that must be purified.Purification the results are shown in Table 3.
Table 3
Unit：ppmw
In a word, industrial silicon and metal liquate agent Sn, Al, Cu, Fe, Ni, Zn etc. are made consumable alloy electrode by the present invention, are made
It constitutes loop in electroslag refining with slag, solves the technical barrier that polysilicon can not be refined by electroslag remelting process,
Impurity element distribution coefficient is small in solving slag refining process, the slow technical barrier of mass transfer rate, and alloy is greatly improved
The isolation of purified effect of middle impurity.
And the present invention overcomes the shortcomings of metallurgy method process efficiency is low, power consumption is high, product is unstable, can effectively remove
Boron, phosphorus and metal impurities.
Above example is provided just for the sake of the description purpose of the present invention, and is not intended to limit the scope of the present invention.This
The scope of invention is defined by the following claims.The various equivalents that do not depart from spirit and principles of the present invention and make and repair
Change, all should cover within the scope of the present invention.
Claims (3)
1. the method for a kind of electroslag remelting purifying industrial silicon synchronous with alloy liquation refining, it is characterised in that comprise the following steps：
(1) industrial silicon and the agent of metal liquate are melt into alloy and are made consumable alloy electrode in advance；Two or more metals is aoxidized
Thing or metal fused salt are mixed even, and fritting is prepared into slagging agent；
(2) in electroslag furnace, slagging agent is fused into slag bath using striking agent, consumable alloy electrode is immersed into slag after slag bath overheat
Chi Zhong, carries out electroslag remelting refining with segregation refining；
(3) refining terminates with solidification, obtains segregation-alloy ingot casting, through broken apart, obtains the polysilicon of purifying；
Metal oxide described in the step (1) and metal fused salt are selected from by CaO, SiO2、Al2O3、MgO、Na2O、Fe2O3、
MnO、BaO、CaCl2、KCl、NaCl、CaF2、Na2CO3、Na2SiO3、Na3AlF6The two or more composition for being constituted；
The chemical constituent of the metal oxide and metal fused salt is by weight percentage：
2. the method for electroslag remelting purifying industrial silicon synchronous with alloy liquation refining according to claim 1, it is characterised 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 electroslag remelting purifying industrial silicon synchronous with alloy liquation refining according to claim 1, it is characterised in that：
The purity of metal liquate agent described in step (1) is 99%~99.999%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510118113.6A CN104724710B (en) | 2015-03-18 | 2015-03-18 | A kind of method of electroslag remelting purifying industrial silicon synchronous with alloy liquation refining |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510118113.6A CN104724710B (en) | 2015-03-18 | 2015-03-18 | A kind of method of electroslag remelting purifying industrial silicon synchronous with alloy liquation refining |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104724710A CN104724710A (en) | 2015-06-24 |
| CN104724710B true CN104724710B (en) | 2017-06-13 |
Family
ID=53449215
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510118113.6A Active CN104724710B (en) | 2015-03-18 | 2015-03-18 | A kind of method of electroslag remelting purifying industrial silicon synchronous with alloy liquation refining |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104724710B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112938983B (en) * | 2021-01-27 | 2023-01-24 | 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103011169A (en) * | 2012-12-14 | 2013-04-03 | 厦门大学 | Preparation method for sheet silicon |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120164054A1 (en) * | 2009-01-08 | 2012-06-28 | Bp Corporation North America Inc. | Impurity Reducing Process and Purified Material |
-
2015
- 2015-03-18 CN CN201510118113.6A patent/CN104724710B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103011169A (en) * | 2012-12-14 | 2013-04-03 | 厦门大学 | Preparation method for sheet silicon |
Non-Patent Citations (2)
| Title |
|---|
| Electrically Enhanced Boron Removal from Silicon Using Slag;M.S. ISLAM et al.;《METALLURGICAL AND MATERIALS TRANSACTIONS B》;20131109;第45卷(第1期);第2页右栏第3段至第3页右栏第1段、图2 * |
| Removal of Boron from Silicon-Tin Solvent by Slag Treatment;XIAODONG MA et al.;《METALLURGICAL AND MATERIALS TRANSACTIONS B》;20130226;第44卷(第3期);第528页右栏倒数第1段至第531页右栏倒数第1段、表2、图4 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104724710A (en) | 2015-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102965529B (en) | Preparation method of short-process titanium alloy Ti-Ni-Nb | |
| CN111378848B (en) | Pre-melted slag for electroslag remelting for improving purity of GH4169 alloy return and preparation method thereof | |
| CN103146943B (en) | Red impure copper refining agent and preparation method thereof | |
| CN101855391A (en) | Method for processing silicon powder to obtain silicon crystals | |
| CN102229430B (en) | Technical method for preparing solar energy polycrystalline silicon by using metallurgical method | |
| CN103318894B (en) | Remove the method for boron in polysilicon | |
| CN104724710B (en) | A kind of method of electroslag remelting purifying industrial silicon synchronous with alloy liquation refining | |
| CN105274365A (en) | Titanium alloy preparation technology | |
| CN102534666B (en) | Electrochemical double refining purification method for high purity silicon and high purity aluminum | |
| CN102153088B (en) | Method for carrying out slagging, pickling and boron removal on metal silicon | |
| CN108048676A (en) | The method that thermit reduction prepares aluminium lanthanum intermediate alloy | |
| CN101712474B (en) | Method for preparing solar-grade high-purity silicon by dilution purifying technology | |
| CN102874816B (en) | Method and device for preparing polysilicon by electromagnetically separating aluminum-silicon alloy solution | |
| He et al. | A review of the process on the purification of metallurgical grade silicon by solvent refining | |
| CN1081245C (en) | Preparation of boronic aluminium alloy with high conductivity | |
| CN101775650B (en) | Preparation method of solar polycrystalline silicon cast ingot and device thereof | |
| CN104711440A (en) | Preparation technique of aluminum-strontium alloy modifier | |
| CN101603129B (en) | Method for removing iron impurity from aluminium alloy | |
| CN106636668B (en) | A kind of waste and old electromagnetic wire copper refining agent and its preparation method and application | |
| CN101928983B (en) | Method for producing polycrystalline silicon and polycrystalline silicon membrane by accelerant process | |
| CN104726750A (en) | Preparation process of aluminum-strontium alloy modifier applied to casting of aluminum-silicon alloy | |
| CN108149025A (en) | A kind of preparation method of high-performance oxygen-free copper bar | |
| CN110616338B (en) | Impurity removal method for copper melt and preparation method for high-purity high-conductivity copper | |
| CN101863476B (en) | Method for removing boron element from silicon | |
| CN104762537A (en) | Preparation technique of aluminum-strontium alloy modifier for casting aluminum-silicon alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |