WO2006041271A1 - Procede de production de silicium pur - Google Patents

Procede de production de silicium pur Download PDF

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Publication number
WO2006041271A1
WO2006041271A1 PCT/KZ2005/000007 KZ2005000007W WO2006041271A1 WO 2006041271 A1 WO2006041271 A1 WO 2006041271A1 KZ 2005000007 W KZ2005000007 W KZ 2005000007W WO 2006041271 A1 WO2006041271 A1 WO 2006041271A1
Authority
WO
WIPO (PCT)
Prior art keywords
silicon
slag
aluminium
present method
production
Prior art date
Application number
PCT/KZ2005/000007
Other languages
English (en)
Inventor
Marat Fatykhovich Tamendarov
Bolat Nygmetuly Mukashev
Khabibulla Abdullaevich Abdullin
Zhaksybek Abdrakhmetovich Kulekeev
Nuraly Sultanovich Bekturganov
Boris Anatolievich Beketov
Original Assignee
The Ministry Of Education And Sciences Of Republic Kazakhstan Republican State Enterprise 'center Of Chemical-Technological Researches'
'silicon Technologies', Limited Liability Partnersship
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by The Ministry Of Education And Sciences Of Republic Kazakhstan Republican State Enterprise 'center Of Chemical-Technological Researches', 'silicon Technologies', Limited Liability Partnersship filed Critical The Ministry Of Education And Sciences Of Republic Kazakhstan Republican State Enterprise 'center Of Chemical-Technological Researches'
Priority to EP05797673A priority Critical patent/EP1805106A1/fr
Priority to EA200700341A priority patent/EA009888B1/ru
Publication of WO2006041271A1 publication Critical patent/WO2006041271A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/023—Preparation by reduction of silica or free silica-containing material

Definitions

  • the present invention relates to nonferrous metallurgy, especially to the aluminothermic method for the manufacture of pure silicon for PV industry, including solar batteries manufacture.
  • Ordinary metallurgical silicon contains amounts of metallic and nonmetallic impurities, which do not allow its use for the solar cells manufacture.
  • Nonmetallic impurities such as boron and phosphorus can be reduced mainly due to the choice of suitable raw materials used for the pure silicon production, but it is worth mentioning that Fe, Al, Mn, Cu, Ni, and other metal-containing impurities can be reduced up to the definite grades.
  • High-purified initial raw materials are expensive; therefore, it is desirable ensuring simple and inexpensive production method, which allows removing metallic impurities or reducing its concentrations up to admissible lowest degree, thus obtaining purified silicon, suitable for the use in the solar cells manufacture.
  • silicon crystallization recovers metallic impurities, which crystallize along silicon crystal boundary as intermetallic compounds or silicides. Therefore, silicon purification can be effective at the control during crystallization ensuring gathering and removing of those additives from silicon either by crucible-pulling method, or by crucible-free zone melting methods, or by dissolution of additives in mineral acids, which do not influence silicon.
  • Crucible-pulling and crucible-free zone melting methods are very expensive. Moreover, they require continuous process for the production of solar silicon.
  • quartz may be reduced by aluminum in the presence of an aluminum sulphide slag to give elemental silicon.
  • the aluminum acts simultaneously as a reducing agent for the quartz and as a solvent for the silicon that has formed, which can subsequently be crystallized out of the solution in an already very pure form, by cooling to a minimum temperature of approximately 600 0 C.
  • This process requires a lot of aluminum and, because of the odor and toxicity of the aluminum sulphide, requires additional protective measures.
  • the most closely related method which has been considered as prototype - is the method for silicon production by interaction of aluminium with siliceous slag of phosphate manufacture in a molar ratio of the slag and aluminium of 1: (0,3-0,5) at 1200 ... 1300 0 C in the presence of magnesium carbonate impurity in quantity of -20 % and cullet in quantity of 5-16% with regard to aluminium mass (see the Republic of Korea preliminary patent N° 4627, Bulletin N ⁇ , afrom Junel ⁇ , 97, C01B33/02).
  • Main disadvantages of this process concern to a certain difficulties at leaching reaction control at acid purification due to thermal emission and formation silane and gaseous hydrogen, which can lead to spontaneous ignition or explosion and to insufficient purity of recovered silicon.
  • huge amounts of calcium in silicon result in huge losses of silicon in the form of fine particles, which can be lost within washing process after the leaching.
  • the object of this innovation was therefore to provide a process which may be used on a commercial production scale, and which, starting from quartz, permits the production of pure silicon for solar cells while avoiding the expensive gas-phase deposition, and without having the disadvantages of the previously known processes.
  • the specified purpose can be achieved using the process, which is based on the following principles: the slag is load into a reactor and heated up to eutectic melting temperature. Then the melting liquid is added with aluminium in specified quantities, essential for the recovery of silica in phosphorous slag.
  • the melting liquid is added with aluminium in specified quantities, essential for the recovery of silica in phosphorous slag.
  • Favorable results may also be obtained when up to 30 mole % of alkaline earth metal fluorides or other substances that increase the solubility in the slag or the aluminum oxide that is formed are added to the slag.
  • the silicon obtained as a result of oxidation-reduction reactions in the melting liquid, can be easily separated from slag and floats to the surface, due to its lower density, comparatively to slag.
  • the present technique provides loading of new portion of slam and aluminium into the silicon melting liquid surface.
  • efficiency of the slag purification of silicon is increasing.
  • interaction of liquid silicon with slag allows decreasing the content of calcium and aluminium, which quantity at conventional aluminothermic process can reach several percents.
  • calcium and aluminium impurities can act as reducing agents for the silica in the new portion of slag.
  • the reactor is added with separate portions of the charge.
  • the process proceeds until complete sedimentation of the reacted slag and its separation with silicon, which is deposited in the top part of the reactor.
  • the silicon merges into graphite mould, separately from the slug, and slowly cooled until it is converted into frozen ingot with grain size less than lmm.
  • silicon is preliminary crushed, diffused, and released from the small particles.
  • Hydrochemical purification consists of the following two stages: First stage is characterized with application of HCl and FeC13 aqueous solution, second stage - HF and HN03 aqueous solutions. At the final stage the silicon powder is washed with deionized water and then dried.
  • Comparative analysis of the present innovation project with prototype indicates that declared method differs from well-known technique with quantitative structure of the charge, methods for the injection of the charge into the reactor in separate portions, thus enabling to control temperatures of the liquid melt and eliminate necessity in its additional intermixing, providing effective process for the silicon's slag purification.
  • the process also eliminates formation of silanes and possibility of its spontaneous ignition at acid treatment.
  • the specified differences allow producing silicon with total purity of more than 99.99 %.
  • One of the main advantages of the suggested method is that the siliceous slag simultaneously acts as a media for the silicon reducing reaction and media for extraction of impurities. Repeated passage of slag through the silicon melting liquid at its deposition in the reactor significantly strengthens silicon-fining efficiency. Insertion of charge in separate portions provides reaction completeness without mechanical mixing and allows supervising melting liquid temperature with the speed of the component addition.
  • the aluminum serving as reducing agent is advantageously used in as pure as possible a form, in order to avoid entrainment of additional impurities.
  • the use of electrolytically purified aluminum having a purity of at least 99.9% has proved particularly successful. If the impurities are substances that accumulate in particular in the slag, then lower degrees of purity of the aluminum may be tolerated. On the other hand, as regards impurities that dissolve only slightly in the slag, such as iron or phosphorus for example, care must be taken from the start that the aluminum is as pure as possible.
  • the process of the present invention can be fully described in the following example:
  • Open graphite crucible was filled with 4000 g of slag.
  • the slag was heated in the induction furnace at the melting temperature of (1300-1350 0 C).
  • the amount of 000 g of granulated aluminium with total purity of at least 99,6 % was introduced into the siliceous slag liquid melt in the reaction chamber. Because of the exothermic nature of the reduction reaction of the phosphorous slag with aluminum, the molten temperature rises up to 1420-1600 C. In this temperature interval, the silicon in the molten state can be easily separated from the slag.
  • Obtained silicon should be discharged into the mould. This allows keeping rather slow speed of cooling for the grain pattern formation, where silicon crystallites are separated from each other with boundaries, which in turn provide effective segregation of metallic impurities. Phases of silicon crushing and dissemination are necessary for the removal of small particles, less than 0,060 mm. As silicon is characterized with higher degree of hardness, its crushing firstly provides destruction of the material on the crystal boundaries, thus removing significant quantities of impurity atoms at the mechanical effect stage.
  • the second state of the leaching process should be carried out within 30 minutes at the room temperature and includes treatment of powder with hydrofluoric acid and nitric acid aqueous solutions, diluted with, for example 1-2 % HF, 4-5 % HNO 3 . Application of solutions with higher concentrations will result in huge losses of silicon at its dissolution with impurities.
  • the second stage can be characterized with dissolution of oxide film on the silicon crystals surfaces and with partial pickling of the silicon coating surface. Silicon oxide film and coating surfaces are contaminated with impurities, contained in silicon in insignificant quantities, which however, concentrate on the Si/SiO 2 phase boundary, and absorbed with crystal cavities and oxide film.
  • the silicon, purified at the second stage of the leaching process should be washed with water and dried.
  • the product is sifted on 1 mm crushing unit, and then washed with distilled water or with water, purified in ion-exchange filter. Decantation allows removing small particles with sizes lesser than 0,050-mm during all washing stages. '
  • Such silicon represents initial material, used for the "solar silicon' ingots growth by various methods of crucible pulling, or by crucible-free zone melting.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)

Abstract

Procédé de production de silicium pur par réduction aluminothermique de dioxyde de silicium dans des scories phosphorées contenant du silicium pour l'industrie photovoltaïque et la fabrication de batteries solaires. Les scories phosphorées sont introduites dans un creuset en graphite ouvert, puis chauffées dans un four à induction à la température de fonte eutectique, après quoi de l'aluminium est ajouté. Le silicium obtenu séparé des scories émerge à la surface desdites scories. On ajoute alors une nouvelle quantité de scories et d'aluminium. Ce processus est répété plusieurs fois, jusqu'à une sédimentation complète des scories mises en réaction et leur séparation du silicium qui apparaît dans la partie supérieure du réacteur. Le silicium obtenu est introduit dans un moule en graphite et refroidi jusqu'à la formation de grains à taille moyenne des cristaux inférieure à 1 mm. Le silicium est alors broyé et passé au tamis en vue de l'élimination de petites particules et soumis à un traitement hydrochimique avec des solutions aqueuses d'acides minéraux en deux étapes. Ledit procédé permet d'obtenir de la poudre de silicium d'une pureté globale de 99,99 %. Des résultats favorables peuvent également être obtenus lorsque jusqu'à 30 % en moles de fluorures de métaux alcalino-terreux ou d'autres substances qui augmentent la solubilité dans les scories ou l'oxyde d'aluminium qui est formé sont ajoutés aux scories.
PCT/KZ2005/000007 2004-10-12 2005-10-12 Procede de production de silicium pur WO2006041271A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP05797673A EP1805106A1 (fr) 2004-10-12 2005-10-12 Procede de production de silicium pur
EA200700341A EA009888B1 (ru) 2004-10-12 2005-10-12 Способ получения чистого кремния

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KZ2004/1443.1 2004-10-12
KZ20041443 2004-10-12

Publications (1)

Publication Number Publication Date
WO2006041271A1 true WO2006041271A1 (fr) 2006-04-20

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Application Number Title Priority Date Filing Date
PCT/KZ2005/000007 WO2006041271A1 (fr) 2004-10-12 2005-10-12 Procede de production de silicium pur

Country Status (3)

Country Link
EP (1) EP1805106A1 (fr)
EA (1) EA009888B1 (fr)
WO (1) WO2006041271A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7964172B2 (en) 2009-10-13 2011-06-21 Alexander Mukasyan Method of manufacturing high-surface-area silicon
WO2012000428A1 (fr) * 2010-06-29 2012-01-05 Byd Company Limited Procédé de préparation d'un silicium de pureté élevée
WO2013078220A1 (fr) * 2011-11-22 2013-05-30 Dow Corning Corporation Procédé de production de silicium pour applications solaires à partir de dioxyde de silicium
KR101306688B1 (ko) 2012-04-17 2013-09-17 연세대학교 산학협력단 슬래그로부터 실리콘을 회수하는 방법 및 장치
KR20150099660A (ko) * 2014-02-21 2015-09-01 재단법인영월청정소재산업진흥원 고순도 메탈실리콘 제조를 위한 실리카의 물리적 및 화학적 처리방법
RU2648436C2 (ru) * 2016-01-25 2018-03-26 Общество с Ограниченной Ответственностью Научно-Производственное Предприятие "КЛИН" Способ получения порошка кремния высокой чистоты из смеси диоксида кремния и алюминия
WO2018114861A1 (fr) * 2016-12-19 2018-06-28 Norwegian University Of Science And Technology (Ntnu) Procédé de production de silicium de qualité commerciale
RU2764670C9 (ru) * 2016-12-19 2022-07-28 Норведжиан Юниверсити Оф Сайенс Энд Текнолоджи (Нтну) Способ получения технического кремния (варианты)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EA029631B1 (ru) * 2016-09-15 2018-04-30 Геннадий Николаевич Чумиков Способ получения металлургического кремния повышенной чистоты из кремнийсодержащих полупродуктов (кварцевая мелочь, пыль кремниевого производства (микрокремнезем)) методом алюминотермии

Citations (2)

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US4457903A (en) * 1982-03-11 1984-07-03 Heliotronic Forshungs Und Entwicklungsgesellschaft Fur Solarzellen Grundstoffe Mbh Semicontinuous process for the production of pure silicon
US4539194A (en) * 1983-02-07 1985-09-03 Elkem A/S Method for production of pure silicon

Patent Citations (2)

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US4457903A (en) * 1982-03-11 1984-07-03 Heliotronic Forshungs Und Entwicklungsgesellschaft Fur Solarzellen Grundstoffe Mbh Semicontinuous process for the production of pure silicon
US4539194A (en) * 1983-02-07 1985-09-03 Elkem A/S Method for production of pure silicon

Non-Patent Citations (3)

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MUKASHEV B N ET AL: "Development of a technology of silicon production by recycling phosphorous industry wastes", SOLAR ENERGY MATERIALS AND SOLAR CELLS, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM, NL, vol. 72, no. 1-4, April 2002 (2002-04-01), pages 605 - 611, XP004339810, ISSN: 0927-0248 *
MUKASHEV, B. N. ET AL: "A novel low cost process for the production of semiconductor polycrystalline silicon from recycled industrial waste", NATO SCIENCE SERIES, 3: HIGH TECHNOLOGY , 73(PERSPECTIVES, SCIENCE AND TECHNOLOGIES FOR NOVEL SILICON ON INSULATOR DEVICES), 75-84 CODEN: NSSTFF; ISSN: 1388-6576, 2000, XP008060568 *
TAMENDAROV M F ET AL COMMISSION OF THE EUROPEAN COMMUNITIES: "TECHNOLOGY AND THERMODYNAMIC MODELLING FOR SEMICOMDUCTOR SILICON PRODUCTION BY RECYCLING INDUSTRIAL WASTES", 16TH. E.C. PHOTOVOLTAIC SOLAR ENERGY CONFERENCE. GLASCOW, UNITED KINGDOM, MAY 1 - 5, 2000, PROCEEDINGS OF THE INTERNATIONAL PHOTOVOLTAIC SOLAR ENERGY CONFERENCE, LONDON : JAMES & JAMES LTD, GB, vol. VOL. 2 OF 3. CONF. 16, 1 May 2000 (2000-05-01), pages 1631 - 1633, XP001138965, ISBN: 1-902916-18-2 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7964172B2 (en) 2009-10-13 2011-06-21 Alexander Mukasyan Method of manufacturing high-surface-area silicon
WO2012000428A1 (fr) * 2010-06-29 2012-01-05 Byd Company Limited Procédé de préparation d'un silicium de pureté élevée
WO2013078220A1 (fr) * 2011-11-22 2013-05-30 Dow Corning Corporation Procédé de production de silicium pour applications solaires à partir de dioxyde de silicium
KR101306688B1 (ko) 2012-04-17 2013-09-17 연세대학교 산학협력단 슬래그로부터 실리콘을 회수하는 방법 및 장치
WO2013157694A1 (fr) * 2012-04-17 2013-10-24 연세대학교 산학협력단 Procédé et appareil pour récupérer du silicium à partir de laitier
KR20150099660A (ko) * 2014-02-21 2015-09-01 재단법인영월청정소재산업진흥원 고순도 메탈실리콘 제조를 위한 실리카의 물리적 및 화학적 처리방법
KR101595330B1 (ko) 2014-02-21 2016-02-19 재단법인영월청정소재산업진흥원 고순도 메탈실리콘 제조를 위한 실리카의 물리적 및 화학적 처리방법
RU2648436C2 (ru) * 2016-01-25 2018-03-26 Общество с Ограниченной Ответственностью Научно-Производственное Предприятие "КЛИН" Способ получения порошка кремния высокой чистоты из смеси диоксида кремния и алюминия
WO2018114861A1 (fr) * 2016-12-19 2018-06-28 Norwegian University Of Science And Technology (Ntnu) Procédé de production de silicium de qualité commerciale
RU2764670C2 (ru) * 2016-12-19 2022-01-19 Норведжиан Юниверсити Оф Сайенс Энд Текнолоджи (Нтну) Способ получения технического кремния (варианты)
RU2764670C9 (ru) * 2016-12-19 2022-07-28 Норведжиан Юниверсити Оф Сайенс Энд Текнолоджи (Нтну) Способ получения технического кремния (варианты)
US11780734B2 (en) 2016-12-19 2023-10-10 Norwegian University Of Science And Technology (Ntnu) Process for the production of commercial grade silicon
EP4279453A2 (fr) 2016-12-19 2023-11-22 Norwegian University of Science and Technology (NTNU) Procédé de production de silicium de qualité commerciale

Also Published As

Publication number Publication date
EA009888B1 (ru) 2008-04-28
EA200700341A1 (ru) 2007-08-31
EP1805106A1 (fr) 2007-07-11

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