WO2015199636A1 - Procédé de production de silicium polycristallin - Google Patents

Procédé de production de silicium polycristallin Download PDF

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Publication number
WO2015199636A1
WO2015199636A1 PCT/UA2015/000016 UA2015000016W WO2015199636A1 WO 2015199636 A1 WO2015199636 A1 WO 2015199636A1 UA 2015000016 W UA2015000016 W UA 2015000016W WO 2015199636 A1 WO2015199636 A1 WO 2015199636A1
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Prior art keywords
silicon
polycrystalline silicon
chlorine
mixture
product
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PCT/UA2015/000016
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English (en)
Russian (ru)
Inventor
Леонид Яковлевич ШВАРЦМАН
Дмитрий Владимирович ПРУТЦКОВ
Владимир Николаевич ДОДОНОВ
Рольф Курт МЕРКЕР
Original Assignee
Леонид Яковлевич ШВАРЦМАН
Дмитрий Владимирович ПРУТЦКОВ
Владимир Николаевич ДОДОНОВ
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Application filed by Леонид Яковлевич ШВАРЦМАН, Дмитрий Владимирович ПРУТЦКОВ, Владимир Николаевич ДОДОНОВ filed Critical Леонид Яковлевич ШВАРЦМАН
Publication of WO2015199636A1 publication Critical patent/WO2015199636A1/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
    • 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
    • C01B33/025—Preparation by reduction of silica or free silica-containing material with carbon or a solid carbonaceous material, i.e. carbo-thermal process
    • 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
    • C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
    • C01B33/03—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition of silicon halides or halosilanes or reduction thereof with hydrogen as the only reducing agent
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B28/00—Production of homogeneous polycrystalline material with defined structure
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/06—Silicon
    • 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
    • C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
    • C01B33/029—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition of monosilane

Definitions

  • the technical solution relates to a technology for producing polycrystalline silicon, suitable, for example, for the manufacture of solar cells.
  • a known method of producing silicon of high purity comprising mixing silicon dioxide and a reducing agent, high-energy processing of the mixture, interaction of the obtained product with a chlorinating agent to form a chlorine-containing silicon compound, which is sent to obtain polycrystalline silicon from it, and by-products are processed.
  • silicon tetrachloride is prepared by carbochlorination of starting materials containing silicon dioxide, from which trichlorosilane is obtained by hydrogenation, hydrogen is reduced to polycrystalline silicon and / or trichlorosilane is disproportionated to monosilane with further pyrolysis of monosilane and deposition of silicon with desired properties.
  • By-products obtained in the known method recycle in it again.
  • High purity silicon is obtained by hydrogenation of silicon tetrachloride to produce chlorinated silanes and the decomposition of these silanes.
  • Hydrogen chloride obtained from the decomposition of chlorinated silanes is used for carbochlorination.
  • Hydrogen obtained in the carbochlorination reaction or in the disproportionation of chlorinated silanes is used for hydrogenation of silicon tetrachloride, for obtaining chlorinated silanes.
  • Silicon tetrachloride which is formed as a by-product of the decomposition of chlorinated silanes, is used to produce chlorinated silanes by reaction with hydrogen. Silicon tetrachloride is hydrogenated to chlorinated silanes.
  • Chlorinated silanes are converted by disproportionation into monosilane and silicon tetrachloride, and the resulting monosilane is decomposed to elemental silicon and hydrogen. Hydrogen, which is obtained during the carbochlorination reaction, is used together with additional hydrogen during the decomposition of silicon tetrachloride. Silicon tetrachloride, which is formed by the disproportionation of chlorinated silanes, is used to produce chlorinated silanes by reaction with hydrogen. Hydrogen, which is obtained during the carbochlorination reaction, is used in the plasma-chemical process. Silicon tetrachloride obtained by the pyrolysis of chlorinated silanes is fed to the stage of a plasma-chemical process.
  • Silicon tetrachloride is hydrogenated into chlorinated silanes, which are used in a plasma-chemical process to remove hydrogen chloride.
  • high purity silicon is obtained by pyrolysis of chlorinated silanes.
  • Hydrogen obtained from the carbochlorination reaction is used to hydrogenate silicon tetrachloride to remove hydrogen chloride.
  • Silicon tetrachloride obtained during the pyrolysis of chlorinated silanes to elemental silicon is used to produce chlorinated silanes by reaction with hydrogen. Hydrogen chloride and / or hydrogen and / or chlorinated monosilane released during the pyrolysis of chlorinated polysilanes are recycled to the process.
  • Chlorinated silanes are obtained in a plasma-chemical process with the removal of hydrogen chloride and using a mixture of silicon tetrachloride and chlorinated silanes. Carbon monoxide obtained in the production process of silicon tetrachloride by carbochlorination from silicon dioxide with hydrogen chloride is converted by converting carbon monoxide with water vapor to carbon dioxide and hydrogen.
  • a disadvantage of the known method for producing polycrystalline silicon is the insufficiently high degree of extraction of silicon into suitable products, high energy costs for the production of a unit of finished products, as well as the complexity of the hardware-technological scheme that implements the method.
  • the closest in technical essence and the achieved technical result to the claimed method is a method for producing polycrystalline silicon (see. "Silicon for of solar energy: technology competition, market influence, development problems ”Yarkin VN, Kisarin OA, Rekov Yu. V., Chervonyi IF, Theory and Practice of Metallurgy, N ° 1-2.20 South. , pp. 114-126), including mixing silicon dioxide and a reducing agent, high-energy processing of the mixture, interaction of the obtained product with a chlorinating agent to form a chlorine-containing silicon compound, which is sent to produce polycrystalline silicon from it, and by-products are processed.
  • This method involves first a high-energy processing of the mixture by obtaining at the first stage metallurgical (crystalline) silicon (according to GOST 2169-69) by the method of ore-heat smelting. Pure heat-resistant quartzite is used as raw material, and expensive and scarce charcoal is a reducing agent.
  • the gross reaction of this stage of the process is such —Si0 2 + 2C— * Si + 2CO.
  • High-energy processing of the mixture — melting — is carried out in one- or three-phase furnaces before the chlorination process. At the same time, the energy consumption is 12-13 thousand kWh / t, the extraction of silicon from oxide is 65-70%, and the dust yield is 0.6-0.8 t / t of silicon.
  • the hardware and technology design of the process is very complex. The resulting silicon ingots are crushed in jaw crushers, and then crushed in ball mills. Then the silicon powder is subjected to treatment with hydrogen chloride in a fluidized bed reactor to obtain a chlorine-containing compound - trichlorosilane by the reaction:
  • the resulting HC1 is also sent to the head of the process.
  • Hydrogen chloride is obtained by burning hydrogen in chlorine (H 2 + Cl 2 -> 2CH1).
  • Chlorine is obtained by electrolysis of sodium chloride solutions.
  • Silicon grinding and hydrogen chloride synthesis processes are fire and explosive and require special precautionary measures.
  • the raw materials used in the known method are vein quartzites of special deposits with high heat resistance and low impurity content. Quartzite is crushed, enriched, and technical silicon is made by ore thermal smelting in the presence of carbon-containing reducing agents. In this case, the main reducing agent is used - expensive and scarce charcoal, as well as an additional reducing agent, which is added in an amount of 10-20%, this is coke and wood chips. The process is conducted at a temperature of more than 2200 ° C.
  • High-energy processing of the mixture is carried out in an ore-thermal furnace to obtain molten technical silicon.
  • the release of molten silicon is carried out through a notch in a cast iron or graphite mold. After cooling, it is crushed in a jaw crusher, and then crushed in a ball mill. This process is explosive and requires increased safety measures.
  • the resulting product is a technical silicon powder. treated with a chlorinating agent - hydrogen chloride with the formation of trichlorosilane, from which the target product polycrystalline silicon is obtained by hydrogen reduction.
  • silicon tetrachloride is also obtained as a by-product, which is sent to hydrogenation to produce trichlorosilane, which is returned to the processing cycle.
  • Hydrogen chloride is produced by burning hydrogen in chlorine, which is also a complex and explosive process. Hydrogen is obtained by electrolysis of alkali solutions or steam reforming of methane with the division of products using a membrane, and chlorine is obtained by electrolysis of chloride solutions.
  • the energy costs of this method are close to 13 thousand kW / h per ton.
  • the extraction of silicon from quartzite is 60-65%, the dust yield is 600-800 kg / t.
  • the price of polycrystalline silicon from quartzite is high and is about $ 24 per kilogram.
  • the disadvantages of the known method for producing polycrystalline silicon from silicon dioxide - quartzite are the insufficiently high level of extraction of silicon into suitable products, high energy costs for the production of a unit of finished products, as well as the complexity of the hardware-technological scheme that implements the method.
  • the basis of the invention is the task of improvement a method for producing polycrystalline silicon, in which, through additional operations and new conditions for performing known operations and their sequences, intensification of the main technological processes is achieved, which allows to increase the degree of silicon extraction into suitable products while ensuring high quality of the obtained product with minimal energy and material costs and as a result, they achieve a reduction in the cost of the target product by almost 2 times.
  • the problem is solved in that in the known method for producing polycrystalline silicon, including mixing silicon dioxide and a reducing agent, high-energy processing of the mixture, the interaction of the obtained product with a chlorinating agent with the formation of a chlorine-containing silicon compound, which is directed to obtain polycrystalline silicon from it, while processing side of products, but it is the fact that silica sand and / or technogenic raw materials, soda are used as silica silica rusting, high-energy treatment of the mixture is carried out at a temperature of 1800-2000 ° C in the solid phase, chlorine is used as a chlorinating agent to obtain a chlorine-containing silicon compound - silicon tetrachloride, from which trichlorosilane is obtained by hydrogenation, which is directed, at least partially, to hydrogen reduction of polycrystalline silicon.
  • trichlorosilane is directed to the production of monosilane and polycrystalline silicon by the method of pyrolysis of monosilane.
  • silica is used as silica sand and / or man-made raw materials containing silica
  • the inventive method cheap and affordable components are used, namely quartz sand and / or technogenic raw materials containing silica, and petroleum coke fines are used as a reducing agent.
  • the reagents are mixed and preliminarily subjected to high-energy heat treatment either in stationary resistance furnaces or in electrothermal furnaces of a fluidized bed at temperatures of 1800-2000 ° C.
  • intermediate reaction products SiO, SiC and others
  • Electricity costs are 4-6 thousand kWh / t, and the extraction of silicon is more than 98%.
  • the powdery material is briquetted on an organic binder and heat treated.
  • the required temperature regime (more than 1400 ° C) is achieved due to the exothermic reaction of the interaction of silicon carbide with chlorine.
  • Trichlorosilane is directed partly to hydrogen reduction, and partly to monosilane production and monosilane pyrolysis to produce monosilane polycrystalline silicon. Silicon-containing by-products that require the cost of their disposal are not formed in this process redistribution.
  • the obtained HC1 is sent to the head of the process to obtain hydrochloric acid and chlorine with hydrogen.
  • the figure shows a flow chart of its implementation.
  • the process flow diagram of the method comprises a silicon dioxide supply unit 1, a carbon reducing agent supply unit 2, a mixture high-energy processing unit 3, a chlorination unit 4, a hydrogenation unit 5, a recovery unit 6, an electrolysis unit 7, a polycrystalline silicon receiving unit 8.
  • silica silica sand of the highest grades is used according to GOST 22551-77 or industrial raw materials containing silica.
  • Petroleum coke (coke breeze) (GOST 22898-78), or high-temperature coal tar pitch (GOST 1038-75), or technical lignosulfonate grade A (TU 13-0281036-05-89).
  • the starting components are weighed, mixed with the carbon-containing component and the mixture is subjected to high-energy processing.
  • High-energy processing of the mixture can be carried out in a resistance furnace with a fixed layer, while the resulting product is sorted, crushed and a fraction of -50 + 10 mm is isolated.
  • High-energy treatment of the mixture can be carried out in an electrothermal fluidized-bed furnace, while silicon dioxide and an organic binder are added to the product obtained in it, and then they are pelletized and calcined.
  • a highly reaction medium is created from silicon dioxide and carbon particles through which electric current passes, and as a result of intense heat and mass transfer, a dispersed powder is formed, which is mixed with silicon dioxide in a mass ratio of 1: (1-2), an organic binder is added, and then pelletize and calcine.
  • coal tar pitch and / or sodium lignosulfonate, and / or cellulosic sulphide can be used as the organic binder.
  • the mixture is pelletized using briquetting presses or pelletized. Received briquettes or pellets are subjected to heat treatment in gas-heated furnaces of periodic or continuous action.
  • these are pit furnaces, in which the material is calcined in retorts, in the second, it is either vertical furnaces with 5 continuous feeds, or horizontal dryers.
  • the claimed temperatures provide the simultaneous achievement of a high degree of chlorination at low specific energy costs for the production of the target product.
  • the value of the high-energy processing temperature which is lower than the declared boundary, 0 at low specific energy consumption is low and degree of chlorination.
  • the temperature of the high-energy treatment is higher than the declared limit, the degree of chlorination does not increase at high specific energy costs.
  • Hydrogen used in the process at the stages of hydrogenation of silicon tetrachloride and the reduction of trichlorosilane to obtain polycrystalline silicon, as well as chlorine, which is fed to the stage of production of silicon tetrachloride, are obtained simultaneously by hydrolysis of hydrochloric acid in bipolar electrolyzers.
  • Hydrochloric acid is formed when water absorbs hydrogen chloride, which is a by-product of the various stages of the process.
  • the products of high-energy processing of the mixture both in the form of lumpy material and in the form of granular material are chlorinated with chlorine in a vertical lined chlorinator with a moving layer and continuous unloading of the residue.
  • the chlorination process takes place in an exothermic mode; therefore, heat supply to the reaction zone is not necessary.
  • the start of the chlorinator is carried out by loading the products of high-energy processing of the mixture heated to 800-850 ° C.
  • the silicon tetrachloride obtained in the chlorinator is sent to a dust collection and condensation system. Then silicon tetrachloride is purified by distillation and sent to hydrogenation for conversion to trichlorosilane. Trichlorosilane is reduced with hydrogen to obtain polycrystalline silicon and / or by disproportionation, monosilane is obtained with further pyrolysis of monosilane and precipitation of polycrystalline silicon with desired properties.
  • the process of the claimed method allows to intensify the main technological processes by optimizing the temperature of the process and the intensification of the main technological processes, which allows to increase the degree of extraction of silicon into suitable products while ensuring high quality of the obtained product with minimal energy and material costs.
  • the price of polycrystalline silicon from quartz sand is about $ 12 per kilogram, that is, two times lower than for the product obtained by the prototype method.
  • the claimed technical solution provides an increase in the degree of extraction of silicon to 97 - 99% of the stoichiometrically possible, which is 10% higher compared to the prototype.
  • Unit costs for the production of a unit of finished products amounted to 12-15 dollars per kilogram, which is 2.0-2.2 times lower than by the prototype method.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Silicon Compounds (AREA)

Abstract

La présente invention se rapporte aux techniques de production de silicium polycristallin, et peut par exemple être utilisée dans la production de panneaux solaires. L'invention concerne essentiellement un procédé de production de silicium polycristallin qui consiste à mélanger du dioxyde de silicium et un réducteur, à effectuer un traitement à haute énergie du mélange, à faire interagir le produit obtenu avec un agent chlorant afin de produire du silicium polycristallin contenant du chlore à partir duquel on produit du silicium polycristallin, tout en effectuant un traitement du produit secondaire. L'invention se caractérise en ce que l'on utilise, en qualité de dioxyde de silicium, du sable de quartz et/ou une matière première technogène contenant de la silice, en ce que le traitement à haute énergie du mélange se fait à une température de 1800-2000°С en phase solide, en ce que l'agent chlorant consiste en du chlore pour produire un composé de silicium contenant du chlore, ou tetrachlorure de silicium, à partir duquel on obtient par hydrogénation du trichlorosilane qui est ensuite utilisé en partie au moins pour produire du silicium polycristallin par réduction hydrogène. L'invention se caractérise également en ce que le traitement à haute énergie du mélange se fait dans un four à résistance avec couche immobile, après quoi le produit obtenu est trié, broyé et on sépare les la fraction -50+10 mm. L'invention se caractérise également en ce que le traitement à haute énergie du mélange se fait dans un four électrothermique à couche en ébullition, et en ce qu'on ajoute au produit qui est obtenu du dioxyde de silicium et un liant organique, après quoi on procède à une mise en pastilles et une calcination. L'invention se caractérise également en ce que l'hydrogène pour l'hydrogénation et la réduction et le chlore sont obtenus par décomposition électrolytique d'un acide salin obtenu lors du traitement des produits secondaires. L'invention se caractérise également en ce qu'une partie au moins du trichlorosilane est utilisée pour produire du monosilane et du silicium polycristallin selon un procédé de pyrolyse du monosilane. Le résultat technique consiste en une intensification des processus industriels de base, ce qui permet d'augmenter le taux d'extraction de silicium en production minière tout en garantissant une qualité élevée du produit obtenu avec des consommations minimes en énergies et en matériaux, ce qui permet de réduire le coût du produit fini de presque deux fois.
PCT/UA2015/000016 2014-06-23 2015-03-06 Procédé de production de silicium polycristallin WO2015199636A1 (fr)

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UAU201407091U UA95096U (uk) 2014-06-23 2014-06-23 Спосіб одержання полікристалічного кремнію

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110589842A (zh) * 2019-08-28 2019-12-20 大同新成新材料股份有限公司 一种半导体材料的制备方法

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CN103086378B (zh) * 2013-01-28 2014-07-23 东北大学 一种用晶体硅切割废料电热冶金制备太阳能多晶硅的方法

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US4676967A (en) * 1978-08-23 1987-06-30 Union Carbide Corporation High purity silane and silicon production
RU2373147C1 (ru) * 2008-02-26 2009-11-20 Александр Владимирович Щепелев Способ получения хлорсиланов, способ хлорирования содержащего двуокись кремния сырья и способ конверсии тетрахлорсилана в трихлорсилан
CN103086378B (zh) * 2013-01-28 2014-07-23 东北大学 一种用晶体硅切割废料电热冶金制备太阳能多晶硅的方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110589842A (zh) * 2019-08-28 2019-12-20 大同新成新材料股份有限公司 一种半导体材料的制备方法

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