EP1999286B1 - Verfahren zur elektrolytischen herstellung und zur raffination von silizium - Google Patents

Verfahren zur elektrolytischen herstellung und zur raffination von silizium Download PDF

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EP1999286B1
EP1999286B1 EP07758136.1A EP07758136A EP1999286B1 EP 1999286 B1 EP1999286 B1 EP 1999286B1 EP 07758136 A EP07758136 A EP 07758136A EP 1999286 B1 EP1999286 B1 EP 1999286B1
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alloy
silicon
electrolyte
layer
molten
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French (fr)
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EP1999286A2 (de
EP1999286A4 (de
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Sadoway Donald
Kai Johansen
Bjorn Myhre
Marianne Engvoll
Krister Engvoll
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Elkem ASA
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Elkem ASA
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/33—Silicon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
    • C25C3/28—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium of titanium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/005—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells for the electrolysis of melts

Definitions

  • the present invention relates to a method for electrolytic production and refining of metals having a high melting point at above about 1000°C, particularly silicon.
  • US patent No. 3,254,010 there is disclosed another method for refining impure silicon or germanium where a current is passed between a cathode and an anode through a molten salt electrolyte containing a fluoride, where the anode is made from impure silicon or germanium or alloys of impure silicon or germanium with more noble metals than silicon or germanium to deport on the cathode refined silicon or germanium. Also in this process solid refined silicon or solid refined germanium are deposited on the cathode.
  • the electrolyte is preferably cryolite.
  • electrolytic refining is a conventional process and is described in US patent No.1,534,318 .
  • this patent it is described a process for electrolytic refining of aluminium where there is established a lower layer of molten metal containing aluminium as an anode, an upper layer or of molten aluminium as cathode and an intermediate layer of molten electrolyte of a greater density than the molten aluminium, which electrolyte is essentially fluorides and substantially free from chloride.
  • Current is passed from the anode metal through the electrolyte to the aluminium cathode where aluminium is removed from the anode metal and deposited in the molten state at the cathode.
  • the molten electrolyte contains aluminium and sodium fluorides and between 20 and 60% of fluoride of an alkali earth metal having an atomic weight greater than 80, for example barium fluoride.
  • the present invention thus relates to an electrolytic method for production and of refining of metals having a melting point above about 1000°C, particularly silicon, said method being characterized in that it:
  • the first cell produces an alloy from the raw material and the second cell refines the alloy to produce a metal.
  • direct current passes through the anode, the first electrolyte and the cathode alloy to produce an alloy having a higher concentration of silicon in the alloy layer from the raw material.
  • direct current passes through the anode alloy, the second electrolyte and the metal to refine the alloy to the metal.
  • the two cells can also be operated independent of one another.
  • the method of the present invention can be defined as a two-step process.
  • the first step is producing an alloy from raw material in one electrolytic cell; and the second step is refining an alloy to make a metal.
  • the alloy is preferably transferred from the first electrolytic cell to the second electrolytic cell in fluid state, but the alloy may also be tapped from the first electrolytic cell, solidified and supplied to the second electrolytic cell in solid state.
  • the raw material is any conventional source of metal oxide containing silicon, or the first metal, for example, quartz for silicon.
  • the refining method of the present invention can use alloy made from a different process than the first step of the present invention.
  • the method to electrolytically refine the alloy to the metal in accordance with the present invention is characterized in that it:
  • both the alloy as well as a less pure metal of silicon can be added to the alloy layer.
  • metallurgical grade silicon can be added to the alloy layer, thereby becoming refined.
  • One of the unique aspects of the present invention is that a variety of raw material can be used in the first cell. Normal carbothermic production of metal puts constraints on the type of raw material used and introduces into the metal impurities especially through the carbon source. Any particulate form of raw material can be added to the first cell and the impurities from the carbon source are eliminated since no carbon source is necessary. This means that the alloy can be purer than conventional alloys and assists in the refining process of the present invention.
  • the alloy layer can comprise an alloy of silicon and a metal or metals more noble than silicon, called the second metal, or the second metal, alone.
  • the alloy itself will form as silicon or the first metal moves into the alloy layer.
  • the lower molten alloy layer comprising the alloy of silicon or the first metal and at least one metal more noble than silicon or the second metal must have a composition that meets the following requirements:
  • the lower molten alloy layer may for example consist of Si-Cu alloy, FeSi alloy or Cu-Fe-Si alloy. These alloys have melting points well below the melting point of silicon and accordingly also below the melting temperature of the first and second electrolyte.
  • the first oxide-based electrolyte must have a composition that meets the following requirements:
  • the second oxide-based electrolyte must have a composition that meets the requirements of the first oxide-based electrolyte, and it must have a density at the operating temperature which is greater than the density of silicon.
  • the oxide-based electrolytes further have the advantages that oxides are nontoxic and have low vapour pressures. Another advantage is that used oxide- based electrolytes are non-toxic and do not have to be deposited as special waste. The non-toxic nature of the electrolytes is true except for those which contain barium oxide, because barium oxide is considered toxic.
  • oxide based electrolytes are suitable:
  • halides particularly alkali and alkaline earth fluorides, may be added to the oxide-based electrolytes in order to modify the viscosity, density, melting point and electric conductivity of the electrolytes.
  • the amount of halides added to the oxide-based electrolytes is preferably below 20 wt % and more preferably below 7 wt %.
  • the oxide-based electrolytes should have a density above about 2.57 g/cm 3 which is the density of molten silicon at the melting point of silicon, and below about 3.37 g/cm 3 if 75% FeSi is used as alloy and below about 5.5 g/cm 3 if 50% FeSi is used as alloy.
  • the oxide-based electrolytes must have a melting point close to or below the melting point of silicon which is 1414°C.
  • a particular suitable oxide-based electrolyte for silicon is a CaO-SiO 2 electrolyte containing 40-75% SiO 2 .
  • This electrolyte has a density of between about 2.5 g/cm 3 and about 2.7 g/cm 3 and has a high solubility of Si-ions, low solubility of Si and low volatility at an operating temperature above the melting point of silicon.
  • the first and second electrolyte can have the same composition or they can be different.
  • the second electrolyte must have a density in the molten state such that it forms the intermediate molten electrolyte layer and positions itself between the upper molten metal layer and the lower molten alloy layer.
  • the first electrolyte is not so constrained.
  • the first electrolyte must have a density in the molten state such that it floats on top of the lower molten alloy layer, i.e. has a density less than the molten alloy.
  • the first electrolyte need not have a density in the molten state that is greater than metal in the molten state.
  • Either the production of the alloy or the refining method of the present invention can be performed in suitable conventional vessels that have a heat resistant refractory lining such as alumina, magnesia silicon nitride, silicon carbide or graphite.
  • a heat resistant refractory lining such as alumina, magnesia silicon nitride, silicon carbide or graphite.
  • the side walls of the vessel may favourably be provided with conventional cooling systems, such as evaporation cooled elements in order to create a freeze lining on the inside of the side walls of the vessels.
  • the method when the method entails simultaneously producing and refining where separate vessels are employed, they may be in fluid communication with each other, such as through a pipe in the side wall of both vessels.
  • the port for the pipe in both side walls must be positioned below the level of the bottom molten alloy layer, in other words, the top of the molten alloy layer should be above the level of the ports for the pipe which provides fluid communication between the vessels.
  • one vessel acts as the first electrolytic cell to produce the alloy and the other vessel acts as the second electrolytic cell for refining.
  • a single vessel is used for simultaneously making the alloy and refining the metal, wherein the vessel has been divided into the first electrolytic cell and the second electrolytic cell and the two cells are in fluid communication with each other through the alloy layer.
  • Such an arrangement 5 is shown in U.S. Patent No. 3,219,561 .
  • the two electrolytes are separate from each other and do not contaminate each other.
  • the anodes and the cathodes are connected to a direct current source in a conventional way in order to supply direct current for the method.
  • silicon in the alloy enters the second oxide-based electrolyte together with ions of any impurities in the alloy that is electrochemically less noble than silicon. Since silicon is the noblest element of the second electrolyte, silicon ions will be reduced at the cathode and will form molten pure silicon, which is collected in the molten silicon cathode. Thus impurities more noble than silicon are trapped in the alloy layer while impurities less noble than silicon are trapped in the second electrolyte.
  • the refining method of the present invention can be carried out both as a batch process and as a continuous process.
  • alloy is added to the alloy layer continuously or intermittently. Eventually the electrolytes and the alloy will become too high in impurities. The process is then stopped and the electrolytes and the remaining part of the alloy are removed form the cell. New alloy and new oxide-based electrolytes are added together with a start cathode of silicon, whereafter electric current is again passed through the electrolytic cell.
  • the refining method of the present invention is carried out as a continuous process, there are arranged means for continuous or intermittent supply of alloy, means for continuous or intermittent removal of oxide-based electrolytes and means for continuous or intermittent supply of fresh oxide-based electrolytes. Finally there are arranged means for continuous or intermittent lapping of refined metal from the upper molten metal layer.
  • the reason for removal of alloy is that the alloy will, during electrolysis get an increased content of impurity elements more noble than silicon. Also, during electrolysis the electrolytes will get an increased content of elements less noble than silicon, and to reduce this content of impurity elements, part of the electrolytes are removed and may after purification be returned to the electrolyte layers in the cell or be deposited.
  • the method for both making the alloy and refining the metal can be carried out as either a batch or a continuous process.
  • the present invention it is thus provided a simple cost effective method for obtaining a pure form of metals, especially, silicon.
  • Low cost alloys of silicon and a metal more noble than silicon can be used as the alloy.
  • silicon alloys such as FeSi alloys and Cu-Si alloys can be used as alloy.
  • Such alloys can be produced in accordance with the present invention or in any conventional manner using any conventional means.
  • FIG 1 there it is shown a schematic view of an electrolytic cell for carrying out the method of the present invention for refining of silicon.
  • the electrolytic 5 cell comprises a vessel 1 having a refractory layer 2.
  • a lower layer 3 of an alloy of silicon and a metal more noble than silicon such as a Cu-Si alloy that acts as an anode in the electrolytic cell.
  • an oxide-based electrolyte 4 having a density lower than the density of the anode alloy 3 and a higher density than molten silicon.
  • a suitable electrolyte 4 is a mixture of 50 % by weight of CaO and 50 % by weight of SiO 2 .
  • the electrolyte layer 4 On the top of the electrolyte layer 4 there is a layer 5 of pure silicon metal acting as a cathode.
  • the anode 4 and the cathode 5 are, via contacts 6 and 7 respectively, connected to a direct current source (not shown) for conducting current to the electrolytic cell.
  • a direct current source not shown
  • silicon in the anode alloy 3 enters the oxide-based electrolyte 4 together with ions of any impurities in the anode alloy 3 that is electrochemically less noble than silicon. Since silicon is the noblest element of the electrolyte 4 silicon ions will be reduced at the cathode 5 and will form molten pure silicon, which is collected in the molten 20 silicon cathode 5.
  • impurities more noble than silicon are trapped in the anode layer 3 while impurities less noble than silicon are trapped in the electrolyte 4.
  • Pure refined silicon is from time to time tapped from the molten cathode layer 5.
  • Additional solid or molten anode alloy or solid or molten unrefined grade of silicon is continuously or intermittently 25 supplied to the molten anode layer 3 through an anode alloy supply channel 8.
  • the anode layer will have an increased content of impurities of metals more noble than silicon and the electrolyte will get an increased content of elements less noble than silicon.
  • the electrolytic cell must therefore be stopped and restarted with pure anode alloy and new uncontaminated electrolyte.
  • vessel 10 has refractory layer 11.
  • Alloy layer 12 comprises the alloy and electrolyte layers 13 contains the second electrolyte and electrolyte layer 14 contains the first electrolyte.
  • Layer 15 is pure metal and acts as cathode.
  • Anode 16 and cathode 17 via conventional contacts are connected 5 to a direct current source, not shown.
  • Wall 18 separates the two cells, the first electrolyte cell 19 and the second electrolytic cell 20. Alloy layer 12 flows between the two cells under wall 18.
  • raw material e.g.
  • quartz, SiO 2 is reduced electrolytically to metallic state such as silicon to increase the concentration of silicon in alloy layer 12 and then in the second electrolytic cell 20, silicon alloy is moved from the anode layer through the second electrolyte layer 13 to the pure metal layer 15.
  • the alloy layer 12 fills the cells to a level above the lower edge of wall 18 and thereby separates the two electrolytes of the two cells.
  • the anode 16 is immersed in electrolyte layer 14 and cathode 17 is immersed in metal layer 15, but neither is in direct contact with alloy layer 12.
  • the alloy layer 12 acts as a common electrode.
  • Silicon and elements more noble than silicon that are in the first electrolyte of electrolyte layer 14 precipitate at, and alloy with, the molten alloy.
  • Anode 16 can be either inert or consumable, such as, baked carbon or graphite.
  • electrolyte layer 31 had a composition of 55 wt. % CaO and 45 wt. % SiO 2 .
  • Raw material of SiO 2 quartz, was added frequently to layer 31 to maintain the electrolyte composition and to provide a source of raw material to the process.
  • a voltage of 4.5 V was applied between graphite anode 32 and cathode 33, to give a cathode current density of approximately 1 A/cm 2 .
  • the cell temperature was held constant at 1650°C.
  • the cell started with a liquid cathode 34 made of copper.
  • the first metal is silicon and the second metal is copper in this cell.
  • the copper cathode contained about 20 wt. % Si, giving a current efficiency of about 40%.
  • the alloy was produced of SiCu.
  • this cell started with pure second metal in the alloy layer and through the operation of the cell the alloy is formed in the alloy layer.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Silicon Compounds (AREA)

Claims (14)

  1. Verfahren zum Herstellen und Reinigen eines Metalls in einem elektrolytischen Verfahren, gekennzeichnet durch:
    Versorgen einer ersten elektrolytischen Zelle mit einer oberen geschmolzenen Elektrolytschicht, welche einen ersten auf Oxid basierenden Elektrolyten umfasst, welcher Siliciumoxid enthält, wobei sich der erste Elektrolyt in einem geschmolzenen Zustand befindet und einen Schmelzpunkt unterhalb der Betriebstemperatur des Prozesses hat, einer Anode, positioniert in der oberen geschmolzenen elektrolytischen Schicht, und einer unteren geschmolzenen Legierungsschicht, umfassend eine Legierung aus Silicium und mindestens einem edleren Metall als Silicium, wobei besagte Legierung eine Kathode in der ersten elektrolytischen Zelle bildet, wobei besagter erster Elektrolyt eine Dichte geringer als die Dichte der Legierung hat;
    Zugeben eines Rohmaterials zu besagter oberer geschmolzener Elektrolytsicht, wobei das Rohmaterial ein Metalloxid des Siliciums umfasst;
    Leiten eines Gleichstroms durch die Anode zur Kathode zum Verringern des Metalloxids, um eine Legierung mit einer höheren Konzentration des Siliciums herzustellen;
    Übertragen der Legierung der unteren geschmolzenen Legierungsschicht der ersten elektrolytischen Zelle in eine zweite elektrolytische Zelle, um so eine untere geschmolzene Legierungsschicht vorzusehen, welche die Legierung der zweiten elektrolytischen Zelle umfasst, wobei besagte Legierung eine Anode in der zweiten elektrolytischen Zelle bildet;
    Versorgen der zweiten elektrolytischen Zelle mit einer oberen geschmolzenen Metallschicht aus Silicium, wobei besagte obere geschmolzene Metallschicht eine Kathode bildet, und einer geschmolzenen Elektrolyt-Zwischenschicht, welche einen zweiten auf Oxid basierenden Elektrolyten umfasst, welcher ein Oxid von Silicium enthält, wobei sich der zweite Elektrolyt in einem geschmolzenen Zustand befindet und einen Schmelzpunkt unterhalb der Betriebstemperatur des Prozesses hat, wobei besagter zweiter Elektrolyt eine Dichte zwischen der Dichte der oberen geschmolzenen Siliciumschicht und der unteren geschmolzenen Legierungsschicht hat; und
    Leiten eines elektrischen Gleichstroms durch die Anode zur Kathode der zweiten elektrolytischen Zelle, wodurch sich Silicium aus der Anodenlegierung zur oberen geschmolzenen Siliciumschicht bewegt.
  2. Verfahren nach Anspruch 1, worin die erste Zelle und die zweite Zelle getrennte Gefäße sind, die sich durch ein Rohr in flüssiger Kommunikation befinden.
  3. Verfahren nach Anspruch 1, worin sich die erste Zelle und die zweite Zelle im gleichen Gefäß befinden und durch eine Wand getrennt sind und sich durch einen Raum unter der Wand in flüssiger Kommunikation befinden.
  4. Verfahren nach Anspruch 1, worin der erste und zweite Elektrolyt gleich sind.
  5. Verfahren nach Anspruch 1, worin das Metall, welches edler als das zu reinigende Metall ist, Kupfer, Eisen oder Silber ist.
  6. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass die untere geschmolzene Legierungsschicht eine Legierung aus Silicium und mindestens einem edleren Metall als Silicium umfasst, einen Schmelzpunkt unter dem Schmelzpunkt von Silicium hat.
  7. Verfahren gemäß Anspruch 4, dadurch gekennzeichnet, dass der auf Oxid basierende Elektrolyt bis zu 20 Gew.-% eines Halogenids enthält.
  8. Verfahren gemäß Anspruch 7, dadurch gekennzeichnet, dass der auf Oxid basierende Elektrolyt bis zu 7 Gew.-% eines Halogenids enthält.
  9. Verfahren gemäß Anspruch 4 zum Reinigen von Silicium, dadurch gekennzeichnet, dass der auf Oxid basierende Elektrolyt das CaO-SiO2 ist.
  10. Verfahren gemäß Anspruch 9, dadurch gekennzeichnet, dass die auf Oxid basierenden Elektrolyte 40-75 Gew.-% SiO2 enthalten.
  11. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass der auf Oxid basierende Elektrolyt ausgewählt ist unter CaO-Al2O3-SiO2, enthaltend bis zu 50 Gew.-% Al2O3, BaO-SiO2, BaO-TiO2-SiO2, CaO-TiO2-SiO2, MgO-TiO2-SiO2, Al2O3-CaO-MgO-SiO2, Al2O3-CaO-SiO2-TiO2 und CaO-MgO-SiO2, welches bis zu 40 Gew.-% MgO enthält.
  12. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass die Anodenlegierung eine Cu-Si-Legierung ist.
  13. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass die Anodenlegierung eine Ferrosiliciumlegierung ist.
  14. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass die Anodenlegierung eine Cu-Fe-Si-Legierung ist.
EP07758136.1A 2006-03-10 2007-03-08 Verfahren zur elektrolytischen herstellung und zur raffination von silizium Active EP1999286B1 (de)

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US37287506A 2006-03-10 2006-03-10
US80740006P 2006-07-14 2006-07-14
PCT/US2007/063555 WO2007106709A2 (en) 2006-03-10 2007-03-08 Method for electrolytic production and refining of metals

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JP (1) JP5183498B2 (de)
AU (1) AU2007226754B2 (de)
BR (1) BRPI0708603B1 (de)
CA (1) CA2645161C (de)
ES (1) ES2633113T3 (de)
NO (1) NO344829B1 (de)
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JP7373361B2 (ja) * 2019-11-07 2023-11-02 三菱重工業株式会社 電解製錬炉及び電解製錬方法
KR102498338B1 (ko) * 2020-03-17 2023-02-10 서울대학교산학협력단 과산화수소 제조용 전기분해장치 및 이를 이용한 과산화수소의 제조 방법
KR102380607B1 (ko) * 2020-07-06 2022-03-31 한국원자력연구원 폐 실리콘 처리 장치 및 이를 이용한 폐 실리콘 처리 방법
CN115012003B (zh) * 2022-06-20 2024-02-06 中南大学 一种硫化锑矿熔盐电解连续化生产的方法及装置

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JP2005510630A (ja) * 2001-11-22 2005-04-21 キューアイティー−フェル エ チタン インク． 液体状態の化合物を含む酸化チタンからチタン金属又は合金を電解採取する方法

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BRPI0708603B1 (pt) 2016-05-17
WO2007106709A9 (en) 2008-01-03
BRPI0708603A2 (pt) 2011-06-07
JP5183498B2 (ja) 2013-04-17
CA2645161C (en) 2011-11-22
CA2645161A1 (en) 2007-09-20
EP1999286A2 (de) 2008-12-10
ES2633113T3 (es) 2017-09-19
AU2007226754A1 (en) 2007-09-20
WO2007106709A2 (en) 2007-09-20
AU2007226754B2 (en) 2011-01-20
NO20083970L (no) 2008-09-17
EP1999286A4 (de) 2011-09-07
JP2009529607A (ja) 2009-08-20
WO2007106709A3 (en) 2007-11-29
NO344829B1 (no) 2020-05-18

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