CN102259859B - Production technology for metallurgical silicon with low boron content and low phosphorus content - Google Patents
Production technology for metallurgical silicon with low boron content and low phosphorus content Download PDFInfo
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- CN102259859B CN102259859B CN 201110146268 CN201110146268A CN102259859B CN 102259859 B CN102259859 B CN 102259859B CN 201110146268 CN201110146268 CN 201110146268 CN 201110146268 A CN201110146268 A CN 201110146268A CN 102259859 B CN102259859 B CN 102259859B
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Abstract
The invention relates to a production technology for metallurgical silicon with low boron (B) content and low phosphorus (P) content. The technical scheme comprises the following steps of: selecting silica with silicon dioxide (SiO2) of over 99 percent, B of less than 10ppmw and P of less than 5ppmw and cracking the silica until the particle size of the silica ranges from 50 to 120 millimeters; cleaning the silica by using water and drying the cleaned silica in the air as raw silicon; selecting petroleum coke as a reducing agent; uniformly mixing the following compound additives in percentage by weight: 60 to 65 percent of CaF, 22 to 26 percent of CaO and 7 to 11 percent of Na2SiO3; weighing according to the weight ratio of the compound additives to the reducing agent to the silica of 1 to 4 to 10 respectively and mixing the compound additives, the reducing agent and the silica, feeding the mixture into an ore furnace and smelting at temperature of 2,000 to 2,400 DEG C for 4 to 5.5 hours, stopping heating for every 1.5 to 2 hours and ramming the furnace for three times; simultaneously discharging non-silicon substances and smelted metallurgical silicon liquid in the ore furnace, injecting the non-silicon substances and the smelted metallurgical silicon liquid into a silicon water bag and performing oxygen blowing to slowly increase air pressure until the liquid silicon mixtureis in a boiling state and keeping the boiling state for 35 to 50 minutes; and removing slag and directionally solidifying to obtain the high-quality metallurgical silicon.
Description
Technical field
The present invention relates to the metalluragical silicon production technical field, particularly relate to the production technique of the low-phosphorous metalluragical silicon of a kind of low boron.
Background technology
The purposes of metalluragical silicon very extensively is mainly used in and produces organosilicon, produces highly purified semiconductor material, solar cell material, and preparation has alloy of special purpose or the like.
At present, the metalluragical silicon product all adopts the smelting production method preparation, is about to natural mineral products silica through fragmentation, mixes with carbonaceous reducing agents such as charcoal, bituminous coal, refinery cokes, and send into according to a certain ratio and carry out melting in the hot stove in ore deposit: its melting chemical equation is SiO
2+ C=Si+CO
2↑, silica is reduced into silicon, regularly come out of the stove, carry out external refining after, obtain the metalluragical silicon product.Flourish along with the photovoltaic industry proposes higher requirement to the production of metalluragical silicon, and the high-quality low-phosphorous metalluragical silicon of low boron enjoys people to pay close attention to.
Produce high-quality metalluragical silicon, at first should set about, natural silicon ore SiO from the raw material selection
2Get final product according to qualifications, but the selection of reductive agent is comparatively difficult.After last century the mid-1960s, China begins to mix with charcoal, bituminous coal and refinery coke and makes reductive agent, and wherein the phosphorus content of charcoal ash oontent high, bituminous coal is big, is inappropriate for and produces high-quality metalluragical silicon; And the boron of refinery coke, phosphorus and other foreign matter content are optimal selection less.But use full refinery coke in smelting process, the response capacity and the ventilation property of refinery coke are relatively poor, are prone to produce heavy silit, have nature sorting depositional phenomenon, make furnace bottom rising, have a strong impact on ordinary production.
How to overcome the furnace bottom rising that full petroleum coke as reducing agent brings, and in smelting process, add which kind of auxiliary material, how to carry out problems such as external refining, in the prior art, also solved effectively.
Summary of the invention
The objective of the invention is to the weak point of producing high-quality metalluragical silicon at present.Providing a kind of provides a kind of employing full petroleum coke as reducing agent, cooperates the method for composite additive production metallurgy silicon, and it is many that it has solved existing metalluragical silicon foreign matter content, and the technical problem of furnace bottom rising, and can smelt high-quality metalluragical silicon.
Technical solution of the present invention is: the operation of this technology divides following step to carry out:
A. prepare raw material, select SiO
2＞99%, the silica of B＜10ppmw, P＜5ppmw, particle size after cracking to 50～120mm, clean through washing, dry as raw silicon; The Powdered refinery coke of selecting quality 2B is as reductive agent; The self-control composite additive, composite additive is by weight percentage: CaF
260～65%: CaO22～26%: Na
2SiO
37～11%, mix;
B. reduction reaction, according to composite additive: reductive agent: the weight ratio of silica=1: 4: 10 is weighed respectively, mixes, and drops in the hot stove in ore deposit, and 2000 ℃～2400 ℃ following meltings 4～5.5 hours, middle every stopping at a distance from 1.5～2 hours heated, and smashes stove 3 times;
C. oxygen blast refining is together discharged non-silicon matter in the hot stove in ore deposit and fused metalluragical silicon liquid, injects in the silicon water bag, carries out the oxygen blast operation, slowly increases air pressure, makes the liquid-state silicon mixture reach boiling state and gets final product, and continues 35～50 minutes;
D. slagging-off stops oxygen blast, leaves standstill silicon water bag 2～5 minutes, and tipping silicon water bag is clean with silicon liquid surface slag removal;
E. directional freeze: molten silicon liquid is poured in the coagulator, built the insulation loam cake, cooling is solidified naturally;
F. take out silicon ingot, broken, sub-elect that surface texturisation is closely knit, the silico briquette of bright in color, no slag inclusion thing, obtain high-quality metalluragical silicon.
The present invention compared with prior art has the following advantages:
1, it is few to bring foreign matter content into.The present invention only adopts refinery coke as reductive agent; Silica is removed because of adherent surface dirt in mining, transportation, storage, the shattering process through washing; Composite additive also is the few product of preferred foreign matter content; Thereby reduced the introducing of the introducing of impurity, particularly phosphorus impurities, created good condition for producing the low-phosphorous metalluragical silicon of low boron.
2, solve because of full petroleum coke as reducing agent furnace bottom rising problem.The Calcium Fluoride (Fluorspan) CaF that adopts in the composite additive of the present invention
2Can soften the non-silicon matters such as SiC that are deposited in furnace bottom that metalluragical silicon produces in smelting, need not the blowing out scarfing cinder in the production process, when silicon liquid was discharged the hot stove in ore deposit, slag liquid was non-rising and together discharge, and furnace bottom does not have slag liquid to accumulate phenomenon to take place.
3, good except that the boron phosphor-removing effect.Adopt quicklime CaO, water glass Na2SiO3 in the composite additive of the present invention, with silica SiO
2What form optimal components ratio removes boron dephosphorization slag, in the oxygen blast refining process, and the further oxidation come-up of slag; Boron, the phosphorus impurities dispersion coefficient in slag is high; And slag has stronger dispersivity, handles through scarfing cinder again, and is very obvious to the boron phosphorus effect of removing in the silicon.
4, melting reaction speed is fast, energy efficient.2000 ℃～2400 ℃ of smelting temperatures of the present invention, just high about 200～400 ℃ than normal smelting temperature, (too greatly then reduction reaction is poor for granularity to select the preferable granularity of silica simultaneously; The too little then ventilation property of granularity is poor); Guaranteed the fast speed that melting reaction is required, reacted more abundant, greying has taken place form the minimizing of SiC condition; Can accomplish reaction within a short period of time, cut down the consumption of energy.
5, the insulation directional freeze utilizes the impurity segregation principle to make impurity enriched; During sorting, be prone to distinguish quality from silico briquette surface texturisation degree of compactness and color and luster, sorting according to qualifications after the silicon ingot fragmentation; Further improve product quality, the metallic impurity total content is effectively reduced in the metalluragical silicon.
Embodiment
Embodiment of the present invention is following:
Step 1: prepare raw material, select SiO
2＞99%, the silica of B＜10ppmw, P＜5ppmw, particle size after cracking to 50～120mm, clean through washing, dry as the silicon source; The Powdered refinery coke of selecting quality 2B is as reductive agent; Be by weight percentage: CaF
265%: CaO 25%: Na
2SiO
310% self-control composite additive, thorough mixing is even;
Step 2: reduction reaction, according to composite additive: reductive agent: the weight ratio of silica=1: 4: 10 is weighed respectively, mixes, and drops in the hot stove in ore deposit, and 2000 ℃～2400 ℃ following meltings 5 hours, middle every stopping at a distance from 1.5 hours heated, and smashes stove 3 times;
Step 3: the oxygen blast refining, non-silicon matter in the hot stove in ore deposit and fused metalluragical silicon liquid are together discharged, inject in the silicon water bag, carry out the oxygen blast operation, slowly increase air pressure, make the liquid-state silicon mixture reach boiling state and get final product, continue 50 minutes;
Step 4: slagging-off, stop oxygen blast, left standstill silicon water bag 4 minutes, tipping silicon water bag is clean with silicon liquid surface slag removal;
Step 5: directional freeze: molten silicon liquid is poured in the directional freeze device, built the insulation loam cake, cooling is solidified naturally.
Step 6: take out silicon ingot, broken, sub-elect that surface texturisation is closely knit, the silico briquette of bright in color, no slag inclusion thing, obtain high-quality metalluragical silicon.
The metalluragical silicon foreign matter content that adopts inductively-coupled plasma spectrometer (ICP-OES) test production technique of the present invention to produce is following:
B≤3ppmw、P≤6ppmw。
Fe≤1200ppmw、Al≤350ppmw、Ca≤800ppmw、Cu≤50ppmw、Mn≤60ppmw、Cr≤20ppmw。
Silicone content Si >=99.7%.
Can know by These parameters; The production technique of the low-phosphorous metalluragical silicon of the low boron of this kind is good; The general metalluragical silicon of the content of impurity B, P, Fe, Al, Ca, Cu, Mn, Cr has obvious reduction, particularly B, P index extremely low in the metalluragical silicon of producing, and is the low low-phosphorous metalluragical silicon of boron.
Claims (2)
1. the production technique of the low-phosphorous metalluragical silicon of low boron is characterized in that the operation of this technology is divided following step:
A. prepare raw material, select SiO
2＞99%, the silica of B＜10ppmw, P＜5ppmw, particle size after cracking to 50～120mm, clean through washing, dry as raw silicon; The Powdered refinery coke of selecting quality 2B is as reductive agent; The self-control composite additive, composite additive is by weight percentage: CaF
260～65%: CaO22～26%: Na
2SiO
37～11%, mix;
B. reduction reaction, according to composite additive: reductive agent: the weight ratio of silica=1: 4: 10 is weighed respectively, mixes, and drops in the hot stove in ore deposit, and 2000 ℃～2400 ℃ following meltings 5 hours, middle every stopping at a distance from 1.5～2 hours heated, and smashes stove 3 times;
C. oxygen blast refining is together discharged non-silicon matter in the hot stove in ore deposit and fused metalluragical silicon liquid, injects in the silicon water bag, carries out the oxygen blast operation, slowly increases air pressure, makes the liquid-state silicon mixture reach boiling state and gets final product, and continues 35～50 minutes;
D. slagging-off stops oxygen blast, leaves standstill silicon water bag 4～6 minutes, and tipping silicon water bag is clean with silicon liquid surface slag removal;
E. directional freeze: molten silicon liquid is poured in the directional freeze device, built the insulation loam cake, cooling is solidified naturally;
F. take out silicon ingot, broken, sub-elect that surface texturisation is closely knit, the silico briquette of bright in color, no slag inclusion thing, obtain metalluragical silicon.
2. the production technique of the low-phosphorous metalluragical silicon of a kind of low boron according to claim 1; It is characterized in that the directional freeze device adopts the high-performance lagging material to process; Silicon liquid temp cooling rate is slowed down, utilize the impurity segregation principle, impurity enriched is solidified place or crystal grain boundary place to the end; After fragmentation, sorting, obtain high-quality metalluragical silicon.
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| CN107311180B (en) * | 2017-05-25 | 2019-06-28 | 宁夏东梦能源股份有限公司 | The method for preparing low borosilicate using mineral hot furnace |
| US20220212937A1 (en) * | 2019-04-30 | 2022-07-07 | Wacker Chemie Ag | Method for refining crude silicon melts using a particulate mediator |
| CN110156023B (en) * | 2019-06-14 | 2022-10-21 | 宝兴易达光伏刃料有限公司 | Environment-friendly method for smelting high-purity silicon |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1543435A (en) * | 2001-07-23 | 2004-11-03 | Medium purity of silicon metallurgy and preparing process thereof | |
| US7682585B2 (en) * | 2006-04-25 | 2010-03-23 | The Arizona Board Of Regents On Behalf Of The University Of Arizona | Silicon refining process |
| CN102066250A (en) * | 2008-06-16 | 2011-05-18 | N.E.D.硅股份公司 | Method for preparing high-purity metallurgical-grade silicon |
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| JP4835867B2 (en) * | 2007-04-20 | 2011-12-14 | 信越化学工業株式会社 | Silicon purification method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1543435A (en) * | 2001-07-23 | 2004-11-03 | Medium purity of silicon metallurgy and preparing process thereof | |
| US7682585B2 (en) * | 2006-04-25 | 2010-03-23 | The Arizona Board Of Regents On Behalf Of The University Of Arizona | Silicon refining process |
| CN102066250A (en) * | 2008-06-16 | 2011-05-18 | N.E.D.硅股份公司 | Method for preparing high-purity metallurgical-grade silicon |
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| JP特开2008-266075A 2008.11.06 |
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Effective date of registration: 20190329 Address after: 751100 Jinji Industrial Park, Wuzhong City, Ningxia Hui Autonomous Region, south of Jinwei Third Road Patentee after: Ningxia High Energy Technology Co., Ltd. Address before: 751100 Friendship East Road, Litong District, Wuzhong City, Ningxia Hui Autonomous Region Patentee before: Ningxia Yinxing Polycrystalline Silicon Co., Ltd. |
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