CN102534666A - Electrochemical double refining purification method for high purity silicon and high purity aluminum - Google Patents
Electrochemical double refining purification method for high purity silicon and high purity aluminum Download PDFInfo
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Abstract
The invention belongs to the technical field of purification of silicon and aluminum, particularly relates to an electrochemical double refining purification method for high purity silicon and high purity, which includes the following detailed steps: 1 refining and purifying alloy: mixing raw materials of metal aluminum and metallurgy silicon are smelted by adopting an alloy refining method, impurity boron in metallurgy silicon is removed, and aluminum-silicon alloy is obtained; 2 electrolytic separating: aluminum-silicon alloy serves as an anode, stainless steel serves as a cathode, low temperature fused salt serves as electrolyte, constant current electrolysis is conducted, anode mud gathered in the anode is polycrystalline silicon, and aluminum is gathered in the cathode; and 3 post-processing: the polycrystalline silicon gathered in the anode is smashed, acid pickled to remove impurities, washed by deionized water, filtered and dried to obtain low-boron polycrystalline silicon, the aluminum gathered in the cathode is washed and dried to obtain high purity aluminum. The electrochemical double refining purification method can effectively remove the impurity boron in the metallurgy silicon, is good in purification effect and high in environment-friendly benefit. Recycling rate of the aluminum is above 93%, and purity of the aluminum is above 99.999%.
Description
Technical field
The invention belongs to the technical field that silicon and aluminium are purified, particularly a kind of method of utilizing two refining purified silicons of electrochemical method and aluminium.
Background technology
Solar energy industry obtains various countries' energy strategy attention as a kind of green regenerative energy sources of high environmental protection, and especially after nuclear incident took place in Japan, solar energy industry heated up once more.Meanwhile, industry is also increasingly high for the requirement of solar cell material.At present, using the widest solar cell is silion cell.In order to guarantee its photoelectric transformation efficiency, the purity of its important composition silicon materials need reach more than the 6N.The low-cost solar battery has become one of bottleneck of heliotechnics widespread use with the preparation of polysilicon.
The working method of solar-grade polysilicon adopts Siemens Method or improvement Siemens Method more, i.e. chemical vapor deposition (CVD) method, and purifying industrial silicon obtains polysilicon.Its cardinal principle is that industrial silicon is processed into trichlorosilane (or silicon tetrachloride) with hydrochloric acid, behind the above-mentioned trichlorosilane (or silicon tetrachloride) of purifying, in siemens reactor (or fluidised form bed), obtains high purity polycrystalline silicon with High Purity Hydrogen reduction vapour deposition again.These methods mainly are to be used to produce the electronic-grade HIGH-PURITY SILICON.Be used to produce a large amount of solar-grade polysilicons and have more shortcoming.On the one hand, the technical process link is many, the time is long, and intermediate product severe toxicity, explosive is prone to lead to Serious Accident, and energy consumption is high, and is seriously polluted; On the other hand, the attaching problem of core technology and intellecture property has also seriously restricted the popularization of these technologies.
Compare with chemical method, metallurgy method purifying industrial silicon has advantages such as technical process is simple relatively, energy consumption is low, environmental pollution is little, so enjoy people to pay close attention to.Metallurgy method need combine multiple treatment technology to realize the purification of industrial silicon usually, and these technology comprise (CN 101122047A such as directional freeze, plasma melting, vacuum electron beam melting; CN87104483; CN1890177A; ZL96198989.0; ZL98105942.2; ZL98109239.3 and ZL95197920.5).Can realize the removal of most of impurity in the industrial silicon through directional solidification technique, but not obvious to the removal effect of boron impurities and phosphorus; And, can realize the removal of foreign matter of phosphor through vacuum melting because the saturated vapor pressure of phosphorus is higher.Directional freeze and vacuum melting technology are comparatively ripe purification techniquess, can be applicable to the purification of industrial silicon.Like this, the metallurgy method purifying industrial silicon key for preparing solar-grade polysilicon just is the removal of boron impurities.Slag making refining, plasma oxidation refining and alloying fractional condensation etc. are mainly adopted in the removal of boron impurities.The slag making refining, the part that can be removed boron impurities is subject to the partition ratio of boron between slag-Jin, be difficult to make the boron impurities content in the silicon up to standard, and the waste residue amount is big, and environmental problem is outstanding; Boron impurities can be effectively removed in the plasma oxidation refining, but complex equipments, service temperature are high, condition is harsh, only are confined to bench scale at present.Alloying fractional condensation method reduces and the obvious rule that descends with temperature at the partition ratio of separating out between solid silicon and melt according to boron impurities; Adopt suitable alloy metallic element and industrial silicon to carry out melting; After the cooling; Remove alloy element and impurity through steps such as pickling, reach the purpose of purified silicon.
At present, research at most, the best alloy system of refining effect is the aluminum silicon alloy system.And the shortcoming of this method is that the alloy usage quantity is big, and reagent consumption is big, and material circulation, energy consumption problem are given prominence to.Especially aluminium is as a kind of important light metal, and it reclaims the cost for purification that price is seriously limiting polysilicon.
Summary of the invention
The objective of the invention is to overcome above-mentioned not enough problem; The method of the two refinings purifications of electrochemistry of a kind of HIGH-PURITY SILICON and rafifinal is provided; Adopt the two purified means of electrochemistry, effectively aluminium in the silumin behind the refining and modifying and silicon are separated, both reclaimed and obtained rafifinal efficiently; Also effectively remove the boron impurities in the polysilicon, had higher environmental benefit and economic benefit.
The present invention for realizing the technical scheme that above-mentioned purpose adopted is: the method that the two refinings of the electrochemistry of a kind of HIGH-PURITY SILICON and rafifinal are purified; Concrete steps are following: (1) refining and modifying is purified: employing refining and modifying method is carried out melting to the mixing raw material of metallic aluminium and metalluragical silicon; Remove the boron impurities in the metalluragical silicon, thereby obtain aluminum silicon alloy; (2) electrolytic separation: aluminum silicon alloy is as anode, and stainless steel is as negative electrode, and low-temperature molten salt carries out constant-current electrolysis as electrolytic solution, and the anode sludge of anode enrichment is polysilicon, the negative electrode enriched in aluminum; (3) aftertreatment: the polysilicon of anode enrichment is carried out fragmentation, pickling impurity removal, washed with de-ionized water, filtration and drying, obtains the polysilicon of low boron, with the aluminium of negative electrode enrichment clean, the dry rafifinal that obtains.
The purity of metallic aluminium was massfraction 90%-99% during said (1) refining and modifying was purified, and the purity of metalluragical silicon is massfraction 98%-99%.
The concrete processing parameter that said (1) refining and modifying is purified is: smelting temperature is 700-1400 ℃, and soaking time is 0.5-4h, and cooling rate is 0.1-20 ℃/min.
During said (1) refining and modifying is purified in the aluminum silicon alloy massfraction of metallic aluminium be 20%-80%.
Low-temperature molten salt in said (2) electrolytic separation is NaCl-AlCl
3Or NaCl-AlCl
3-KCl, wherein AlCl
3X be 30%-65%.
The concrete processing parameter of said (2) electrolytic separation is: current density 10-200 mA/cm
2, electrolysis temperature 60-300 ℃, electrolysis time 0.5-6h.
The sour reagent of pickling impurity removal is one or more in hydrochloric acid, hydrofluoric acid, nitric acid, sulfuric acid and the chloroazotic acid in said (3) aftertreatment, and acid concentration is 1.0 ~ 6.0mol/L.
Unusual effect of the present invention is:
1, use metallic aluminium and metalluragical silicon to be raw material, adopt the refining and modifying method that metalluragical silicon is purified, can effectively remove the boron impurities in the metalluragical silicon, its refining effect is good, and environmental benefit is high.
2, adopt electrochemical techniques to realize separation, the recovery of aluminium and the output of rafifinal of aluminium silicon for the Si-Al alloy after solidifying.The recovery utilization rate of aluminium reaches more than 93%, and purity reaches more than 99.999%.
Description of drawings
Accompanying drawing 1 is a process flow sheet of the present invention.
Embodiment
Specify the present invention below in conjunction with specific embodiment and accompanying drawing, but the present invention is not limited to specific embodiment.
Implement row 1
The method that the two refinings of the electrochemistry of a kind of HIGH-PURITY SILICON and rafifinal are purified follows these steps to carry out operations such as silicon, alloy refining, electrolytic separation and relevant aftertreatment:
(1) refining and modifying is purified: the segregation coefficient of impurity reduces along with the reduction of temperature.Adopt the refining and modifying method of purification that silicon and aluminium are configured to alloy and can effectively reduce the liquidus temperature of alloy melt, thereby impurity such as boron are suppressed in the melt, and silicon is improved as its purity of primary phase.Adopting the refining and modifying method is that metallic aluminium and the purity of massfraction 90.0% is that massfraction 98.0%, boron content are that the mixing raw material of the metalluragical silicon of 14ppmw carries out the boron impurities in the melting removal metalluragical silicon to purity, thereby obtains aluminum silicon alloy.The concrete processing parameter that refining and modifying is purified is: smelting temperature is 700 ℃, and soaking time is 0.5h, and cooling rate is 0.1 ℃/min, and the massfraction of metallic aluminium is 80% in the aluminum silicon alloy.
(2) electrolytic separation: in the various metallic elements of anode aluminum silicon alloy, have only aluminium on anode, to dissolve, and silicon, the inactive metallic element of copper geometric ratio aluminium do not dissolve, and still stay in the alloy, therefore, be dissolved in the electrolytic solution Al
3+Preferentially on negative electrode, deposit, and silicon precipitates as the anode sludge.Adopt aluminum silicon alloy as anode, stainless steel is as negative electrode, and low-temperature molten salt carries out constant-current electrolysis as electrolytic solution, and the anode sludge of anode enrichment is polysilicon, the negative electrode enriched in aluminum.Low-temperature molten salt in the electrolytic separation is NaCl-AlCl
3, AlCl wherein
3X be 30%, the concrete processing parameter of electrolytic separation is: current density 200 mA/cm
2, 300 ℃ of electrolysis temperatures, electrolysis time 6h.
(3) aftertreatment: the polysilicon of anode enrichment is carried out fragmentation, pickling impurity removal, washed with de-ionized water, filtration and drying; Obtain the polysilicon of low boron; With the aluminium of negative electrode enrichment clean, the dry rafifinal that obtains; The sour reagent that the polysilicon of anode enrichment is carried out pickling impurity removal is hydrochloric acid, and acid concentration is 6.0mol/L.
The polysilicon of the low boron of gained and the purity check detected result of rafifinal are: the purity of the polysilicon of low boron is massfraction 99.95%, and boron impurities content is 0.56 ppmw, and the purity of rafifinal is massfraction 99.9993%, and the recovery is 93.6%.
Implement row 2
The method that the two refinings of the electrochemistry of a kind of HIGH-PURITY SILICON and rafifinal are purified follows these steps to carry out operations such as silicon, alloy refining, electrolytic separation and relevant aftertreatment:
(1) refining and modifying is purified: adopting the refining and modifying method is that metallic aluminium and the purity of massfraction 99.0% is that massfraction 99.0%, boron content are that the mixing raw material of the metalluragical silicon of 11ppmw carries out the boron impurities in the melting removal metalluragical silicon to purity; Thereby obtain aluminum silicon alloy; The concrete processing parameter that refining and modifying is purified is: smelting temperature is 1400 ℃; Soaking time is 4h, and cooling rate is 20 ℃/min, and the massfraction of metallic aluminium is 20% in the aluminum silicon alloy.
(2) electrolytic separation: adopt aluminum silicon alloy as anode, stainless steel is as negative electrode, and low-temperature molten salt carries out constant-current electrolysis as electrolytic solution, and the anode sludge of anode enrichment is polysilicon, the negative electrode enriched in aluminum, and the low-temperature molten salt in the electrolytic separation is NaCl-AlCl
3-KCl, wherein AlCl
3X be 65%, the concrete processing parameter of electrolytic separation is: current density 10mA/cm
2, 60 ℃ of electrolysis temperatures, electrolysis time 0.5h.
(3) aftertreatment: the polysilicon of anode enrichment is carried out fragmentation, pickling impurity removal, washed with de-ionized water, filtration and drying; Obtain the polysilicon of low boron; With the aluminium of negative electrode enrichment clean, the dry rafifinal that obtains; The sour reagent that the polysilicon of anode enrichment is carried out pickling impurity removal is hydrochloric acid, and acid concentration is 1.0mol/L.
The polysilicon of the low boron of gained and the purity check detected result of rafifinal are: the purity of the polysilicon of low boron is massfraction 99.91%, and boron impurities content is 0.67 ppmw, and the purity of rafifinal is massfraction 99.9992%, and the recovery is 95.4%.
Implement row 3
The method that the two refinings of the electrochemistry of a kind of HIGH-PURITY SILICON and rafifinal are purified follows these steps to carry out operations such as silicon, alloy refining, electrolytic separation and relevant aftertreatment:
(1) refining and modifying is purified: adopting the refining and modifying method is that metallic aluminium and the purity of massfraction 95.5% is that massfraction 98.2%, boron content are that the mixing raw material of the metalluragical silicon of 15ppmw carries out the boron impurities in the melting removal metalluragical silicon to purity; Thereby obtain aluminum silicon alloy; The concrete processing parameter that refining and modifying is purified is: smelting temperature is 1200 ℃; Soaking time is 1h, and cooling rate is 1.5 ℃/min, and the massfraction of metallic aluminium is 40% in the aluminum silicon alloy.
(2) electrolytic separation: adopt aluminum silicon alloy as anode, stainless steel is as negative electrode, and low-temperature molten salt carries out constant-current electrolysis as electrolytic solution, and the anode sludge of anode enrichment is polysilicon, the negative electrode enriched in aluminum, and the low-temperature molten salt in the electrolytic separation is NaCl-AlCl
3-KCl, wherein AlCl
3X be 50%, the concrete processing parameter of electrolytic separation is: current density 50mA/cm
2, 100 ℃ of electrolysis temperatures, electrolysis time 3h.
(3) aftertreatment: the polysilicon of anode enrichment is carried out fragmentation, pickling impurity removal, washed with de-ionized water, filtration and drying; Obtain the polysilicon of low boron; With the aluminium of negative electrode enrichment clean, the dry rafifinal that obtains; The sour reagent that the polysilicon of anode enrichment is carried out pickling impurity removal is nitric acid, and acid concentration is 2.0mol/L.
The polysilicon of the low boron of gained and the purity check detected result of rafifinal are: the purity of the polysilicon of low boron is massfraction 99.94%, and boron impurities content is 0.45 ppmw, and the purity of rafifinal is massfraction 99.9996%, and the recovery is 98.8%.
Implement row 4
Follow these steps to carry out operations such as silicon, alloy refining, electrolytic separation and relevant aftertreatment:
(1) refining and modifying is purified: adopting the refining and modifying method is that metallic aluminium and the purity of massfraction 96.8% is that massfraction 98.8%, boron content are that the mixing raw material of the metalluragical silicon of 12ppmw carries out the boron impurities in the melting removal metalluragical silicon to purity; Thereby obtain aluminum silicon alloy; The concrete processing parameter that refining and modifying is purified is: smelting temperature is 1000 ℃; Soaking time is 3h, and cooling rate is 10 ℃/min, and the massfraction of metallic aluminium is 60% in the aluminum silicon alloy.
(2) electrolytic separation: adopt aluminum silicon alloy as anode, stainless steel is as negative electrode, and low-temperature molten salt carries out constant-current electrolysis as electrolytic solution, and the anode sludge of anode enrichment is polysilicon, the negative electrode enriched in aluminum, and the low-temperature molten salt in the electrolytic separation is NaCl-AlCl
3, AlCl wherein
3X be 40%, the concrete processing parameter of electrolytic separation is: current density 100mA/cm
2, 200 ℃ of electrolysis temperatures, electrolysis time 4h.
(3) aftertreatment: the polysilicon of anode enrichment is carried out fragmentation, pickling impurity removal, washed with de-ionized water, filtration and drying; Obtain the polysilicon of low boron; With the aluminium of negative electrode enrichment clean, the dry rafifinal that obtains; The sour reagent that the polysilicon of anode enrichment is carried out pickling impurity removal is sulfuric acid, and acid concentration is 3.0mol/L.
The polysilicon of the low boron of gained and the purity check detected result of rafifinal are: the purity of the polysilicon of low boron is massfraction 99.96%, and boron impurities content is 0.42 ppmw, and the purity of rafifinal is massfraction 99.9998%, and the recovery is 94.9%.
Claims (7)
1. the two refinings of the electrochemistry of HIGH-PURITY SILICON and the rafifinal method of purifying; It is characterized in that; Concrete steps are following: (1) refining and modifying is purified: employing refining and modifying method is carried out melting to the mixing raw material of metallic aluminium and metalluragical silicon, removes the boron impurities in the metalluragical silicon, thereby obtains aluminum silicon alloy; (2) electrolytic separation: aluminum silicon alloy is as anode, and stainless steel is as negative electrode, and low-temperature molten salt carries out constant-current electrolysis as electrolytic solution, and the anode sludge of anode enrichment is polysilicon, the negative electrode enriched in aluminum; (3) aftertreatment: the polysilicon of anode enrichment is carried out fragmentation, pickling impurity removal, washed with de-ionized water, filtration and drying, obtains the polysilicon of low boron, with the aluminium of negative electrode enrichment clean, the dry rafifinal that obtains.
2. the method that the two refinings of the electrochemistry of a kind of HIGH-PURITY SILICON according to claim 1 and rafifinal are purified; It is characterized in that: the purity of metallic aluminium was massfraction 90%-99% during said (1) refining and modifying was purified, and the purity of metalluragical silicon is massfraction 98%-99%.
3. the method that the two refinings of the electrochemistry of a kind of HIGH-PURITY SILICON according to claim 1 and rafifinal are purified; It is characterized in that: the concrete processing parameter that said (1) refining and modifying is purified is: smelting temperature is 700-1400 ℃; Soaking time is 0.5-4h, and cooling rate is 0.1-20 ℃/min.
4. the method that the two refinings of the electrochemistry of a kind of HIGH-PURITY SILICON according to claim 1 and rafifinal are purified is characterized in that: during said (1) refining and modifying is purified in the aluminum silicon alloy massfraction of metallic aluminium be 20%-80%.
5. the method that the two refinings of the electrochemistry of a kind of HIGH-PURITY SILICON according to claim 1 and rafifinal are purified, it is characterized in that: the low-temperature molten salt in said (2) electrolytic separation is NaCl-AlCl
3Or NaCl-AlCl
3-KCl, wherein AlCl
3X be 30%-65%.
6. the method that the two refinings of the electrochemistry of a kind of HIGH-PURITY SILICON according to claim 1 and rafifinal are purified, it is characterized in that: the concrete processing parameter of said (2) electrolytic separation is: current density 10-200 mA/cm
2, electrolysis temperature 60-300 ℃, electrolysis time 0.5-6h.
7. the method that the two refinings of the electrochemistry of a kind of HIGH-PURITY SILICON according to claim 1 and rafifinal are purified; It is characterized in that: the sour reagent of pickling impurity removal is one or more in hydrochloric acid, hydrofluoric acid, nitric acid, sulfuric acid and the chloroazotic acid in said (3) aftertreatment, and acid concentration is 1.0 ~ 6.0mol/L.
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Cited By (7)
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| CN103173780A (en) * | 2013-03-01 | 2013-06-26 | 中南大学 | Method and device for preparing solar polycrystalline silicon material by semi-continuous molten salt electrolysis |
| CN104372380A (en) * | 2014-11-18 | 2015-02-25 | 辽宁石化职业技术学院 | Low-temperature fused salt method for preparing high-purity chromium |
| CN104846402A (en) * | 2015-04-17 | 2015-08-19 | 内蒙古机电职业技术学院 | Apparatus and method for low temperature electrolysis separation of silicon-aluminum alloy |
| CN105063660A (en) * | 2015-08-03 | 2015-11-18 | 中南大学 | Method for directly preparing nanometer silicon powder in electrolytic refining process |
| CN109252045A (en) * | 2018-10-31 | 2019-01-22 | 东北大学 | A method of extracting metallic aluminium and Antaciron from aluminum-containing mineral |
| CN111748828A (en) * | 2020-06-05 | 2020-10-09 | 北京科技大学 | Method for recycling copper, silver, selenium and tellurium through molten salt electrolysis of copper anode slime |
| WO2022237490A1 (en) * | 2021-05-08 | 2022-11-17 | 郑州大学 | Method for producing metal aluminum and polysilicon by using high silicon aluminum-containing resource |
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| CN103173780A (en) * | 2013-03-01 | 2013-06-26 | 中南大学 | Method and device for preparing solar polycrystalline silicon material by semi-continuous molten salt electrolysis |
| CN103173780B (en) * | 2013-03-01 | 2015-06-03 | 中南大学 | Method and device for preparing solar polycrystalline silicon material by semi-continuous molten salt electrolysis |
| CN104372380A (en) * | 2014-11-18 | 2015-02-25 | 辽宁石化职业技术学院 | Low-temperature fused salt method for preparing high-purity chromium |
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| CN104846402A (en) * | 2015-04-17 | 2015-08-19 | 内蒙古机电职业技术学院 | Apparatus and method for low temperature electrolysis separation of silicon-aluminum alloy |
| CN105063660A (en) * | 2015-08-03 | 2015-11-18 | 中南大学 | Method for directly preparing nanometer silicon powder in electrolytic refining process |
| CN109252045A (en) * | 2018-10-31 | 2019-01-22 | 东北大学 | A method of extracting metallic aluminium and Antaciron from aluminum-containing mineral |
| CN111748828A (en) * | 2020-06-05 | 2020-10-09 | 北京科技大学 | Method for recycling copper, silver, selenium and tellurium through molten salt electrolysis of copper anode slime |
| WO2022237490A1 (en) * | 2021-05-08 | 2022-11-17 | 郑州大学 | Method for producing metal aluminum and polysilicon by using high silicon aluminum-containing resource |
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