WO2013157694A1 - Procédé et appareil pour récupérer du silicium à partir de laitier - Google Patents

Procédé et appareil pour récupérer du silicium à partir de laitier Download PDF

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Publication number
WO2013157694A1
WO2013157694A1 PCT/KR2012/004476 KR2012004476W WO2013157694A1 WO 2013157694 A1 WO2013157694 A1 WO 2013157694A1 KR 2012004476 W KR2012004476 W KR 2012004476W WO 2013157694 A1 WO2013157694 A1 WO 2013157694A1
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WO
WIPO (PCT)
Prior art keywords
slag
silicon
deoxidizer
reaction vessel
reaction
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/KR2012/004476
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English (en)
Korean (ko)
Inventor
손일
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Industry Academic Cooperation Foundation of Yonsei University
Original Assignee
Industry Academic Cooperation Foundation of Yonsei University
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 Industry Academic Cooperation Foundation of Yonsei University filed Critical Industry Academic Cooperation Foundation of Yonsei University
Publication of WO2013157694A1 publication Critical patent/WO2013157694A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
    • 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
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/157—After-treatment of gels
    • C01B33/158—Purification; Drying; Dehydrating

Definitions

  • the present invention relates to a method for recovering silicon, and more particularly, to a method and apparatus for economically recovering silicon from slag.
  • Metallurgical slag is typically produced in steel smelting process, and is an industrial by-product other than iron generated in blast furnaces, converters, and electric furnaces, and is classified into blast furnace slag generated in blast furnace process and steel slag generated in steelmaking process. Blast furnace slag is often derived from impurities of iron ore, reducing coke, and lime.
  • the main components are silicon and calcium oxide.
  • the world's crude steel production amounted to about 1 billion lons per year, which varies depending on the country's crude steel technology.
  • blast furnace slag produces about 300kg per tonne of crude steel and steel slag produces about 170kg of slag. Therefore, steel slag output can be estimated to be at least about 500 million tons.
  • the generation of POSCO accounts for more than 80% of the combined amount of blast furnace slag and steelmaking slag (electric converter).
  • the amount of slag generated in Korea is rapidly increasing as Hyundai Steel also promotes an integrated steelmaking process.
  • a technique for recovering silica from the slag is disclosed, for example, in Patent No. 10-1088901.
  • this technique recovers Si02 from slag and reduces Si02 to Si using C.
  • the reduction process by C should be carried out at a high temperature of about 2000 ° C or more, so economic efficiency is low.
  • silicon is contaminated again by impurities contained in C upon reduction by C, and therefore, an additional process must be performed.
  • a process using trichlorosilane is carried out (also called the Siemens process), which is expensive because of the gas phase method, and the production rate of silicon is very slow.
  • the present invention is to solve the above-mentioned problems in the prior art, to provide a method for recovering the silicon from the slag in a simple process.
  • Another object of the present invention is to provide a method for recovering silicon from slag economically at lower temperatures compared to the prior art of reducing silica using carbon.
  • a method for recovering silicon from slag comprising a reaction container made of a material that can withstand a high silver environment in the temperature range in which the slag is melted and exhibits stability against acids And preparing and mixing slag and a deoxidizer in the reaction vessel, and heating the reaction vessel to melt the slag to oxidize the deoxidizer and reduce silicon from the slag. Cooling the reaction vessel, adding an acid solution to the reaction vessel, performing an acid treatment step of dissolving slag, oxidized deoxidizer, and non-oxidized deoxidizer, except for silicon; It is characterized in that it comprises the step of recovering the silicon.
  • the reaction vessel may be made of carbon, AI2O3 or MgO crucible.
  • the deoxidizer may be a deoxidizer having a higher oxidation degree than silicon.
  • the deoxidizer may be at least one deoxidizer selected from Al, Ca and Mg.
  • the deoxidizer may be mixed with the slag is added to the increase ratio of 0.1 to 2 relative to the slag.
  • the reaction vessel may be heated to a temperature of about 1500 ° C.
  • the heating of the reaction vessel, reaction of the slag of oxygen by the reaction at the interface of the slag and deoxidizer is combined with the deoxidizer to oxidize the deoxidizer, the silica in the slag is reduced to silicon Can be.
  • the acid solution may be at least one acid solution selected from hydrochloric acid, nitric acid, sulfuric acid and aqua regia.
  • silicon deposition impurities may also be removed in an ionic state by the interface reaction between the acid solution and silicon.
  • the acid treatment may be performed in a reaction vessel for a time of 30 minutes or more and 24 hours or less, preferably for 30 minutes or more and 3 to 4 hours.
  • a silicon recovery device for recovering silicon from the slag, the device is installed in the reaction chamber containing the reaction vessel, the upper and lower ends of the reaction chamber, the inside of the reaction chamber outside Sealing means for controlling the atmosphere inside the reaction chamber by shielding from the atmosphere, Gas supply means for injecting an inert gas into the reaction chamber and discharge the inert gas from the chamber, and installed in the reaction chamber Heating means for heating a reaction vessel mounted in the tub, and mounted inside the reaction vessel, containing slag and deoxidizer, capable of withstanding high temperature environments in the temperature range in which the slag is melted and exhibiting stability against acids
  • the reaction vessel may be heated to silver in which the slag is melted to melt the slag of the reaction vessel, thereby oxidizing the deoxidizer and reducing silicon from the slag.
  • the reaction vessel of the silicon recovery device may be composed of carbon, AI2O3 or MgO crucible.
  • the deoxidizer may be at least one deoxidizer selected from Al, Ca and Mg.
  • control unit of the silicon recovery device may be configured to supply the deoxidizer from the deoxidizer supply unit to the reaction vessel in a weight ratio of 0.1 to 2 relative to the slag. In one embodiment, the control unit of the silicon recovery device may be configured to heat the reaction vessel to a temperature of about 1,500 ° C using the heating means. In one embodiment, by heating the reaction vessel of the silicon recovery device, the oxygen in the slag is combined with the deoxidizer through reaction at the interface of the slag and the deoxidizer, the deoxidizer is oxidized, and the slag silica Can be reduced to silicon.
  • the acid solution may be at least one acid solution selected from hydrochloric acid, nitric acid, sulfuric acid, and aqua regia.
  • silicon deposition impurities may also be removed in an ionic state by the interface reaction between the acid solution and silicon.
  • the control unit of the silicon recovery device may be configured to perform the treatment with the acid solution for 30 minutes to 24 hours, preferably 30 minutes to 3 to 4 hours in the reaction vessel.
  • the present invention it is possible to economically recover silicon, which is currently used as a semiconductor and solar cell material, by using a refining method applying a metallurgical refining process from slag disposed as a by-product in the steelmaking / steelmaking process through a very simple process.
  • the silicon recovery method is more cost-effective and easier to process than carbon reduction by conventional gas phase refining and quartzite, and can in principle eliminate the cause of environmental pollution.
  • FIG. 1 is a view schematically showing the configuration of a silicon rare water device according to an embodiment of the present invention.
  • FIGS. 2A to 2D show that after the slag reduction treatment using aluminum deoxidizer according to one embodiment of the present invention, the cross section is observed by SEM, and the amount of silicon is reduced.
  • 3A to 3D show each component of the cross-section before and after acid treatment after slag reduction using aluminum deoxidizer according to one embodiment of the present invention. Indicates that it is
  • FIG. 4 is a view showing the results of XRD analysis on the recovered silicon subjected to acid treatment after slag reduction using aluminum deoxidizer according to one embodiment of the present invention, observed through SEM before acid treatment. It is shown that the reducing metals can be removed to recover the almost pure Si.
  • the silicon recovery apparatus of the present invention comprises a reaction chamber (i.e., a vessel containing slag and deoxidizer) 50 containing a semi-unglube 10 (in one embodiment of the invention, mullite).
  • a reaction chamber i.e., a vessel containing slag and deoxidizer
  • a semi-unglube 10 in one embodiment of the invention, mullite
  • Rubber cap 20 (in one embodiment of the present invention, silicone) for controlling the atmosphere inside the reaction chamber by blocking the inside of the reaction chamber from the outside atmosphere.
  • Lance 30 for injecting and discharging inert gas In one embodiment, consisting of A1203), the inlet / exhaust gas injected into and out of the reaction tube 10 through the lance, installed around the reaction chamber 10, in the reaction tube
  • a heating element 40 in one embodiment of the invention, a SiC heating element is used) that heats the reaction chamber 50 to be mounted, mounted inside the reaction chamber 10, and containing slag and deoxidizer in a predetermined ratio.
  • Reaction vessel 50 in one embodiment of the invention, consisting of carbon
  • thermocouple 60 for measuring temperature.
  • the slag supply unit for supplying the slag and the deoxidizer to the semi-atomizer 50 and the deoxidizer supply unit (not shown) and the reaction solution for supplying an acid solution capable of dissolving the slag and the deoxidizer, etc.
  • An acid solution supply unit (not shown), and a filter device (not shown) for separating the component and silicon dissolved by the acid solution are also included, and a control unit (not shown) for controlling the overall operation of the silicon recovery device.
  • the control unit automatically controls the method according to the present invention under the control of the user as a whole operation and the operation of each component.
  • Such a control unit may be implemented in hardware and / or software, and the implementation form is not particularly limited.
  • a method for recovering the silicon from the slag in detail as follows.
  • the present invention provides a recovery technology of high-purity silicon that simultaneously realizes economic efficiency and production efficiency, that is, it is possible to economically recover silicon from metal smelting slag which is a by-product produced through steelmaking and steelmaking processes. Present the way.
  • the present invention provides a method for economically recovering silicon from slag using oxidation / reduction reaction. Specifically, first, the slag and the deoxidizer are mixed with the reaction container 50 by mixing. At this time, as the deoxidizer, a deoxidizer having a higher oxidation degree than silicon, such as Al, Mg, Ca, or the like is used. The slag is then melted at a temperature such as, for example, one embodiment of the present invention, which is heated to a temperature of approximately 1,50 C to oxidize the deoxidizer and reduce the silicon.
  • the reaction container is preferably made of a material that withstands such a high temperature environment.
  • the mixture is subjected to an acid treatment, and it is preferable to use a material having high stability against such an acid, that is, a material that does not significantly affect slag or deoxidizer contained in the reaction container. .
  • the reaction vessel is composed of carbon, A1203, MgO crucibles.
  • the reaction vessel is cooled to a temperature of about 150 ° C. (natural cooling or forced cooling).
  • silicon dioxide impurities can be removed in an ionic state by the interface reaction between the acid solution and silicon.
  • such acid solution treatment is carried out for 30 minutes or more and 24 hours or less, preferably 30 minutes or more and 3-4 hours.
  • the treatment with the acid solution is less than 30 minutes, the dissolution of impurities is not sufficient, and even if the acid solution is treated for 24 hours or more, the impurity removal effect is almost saturated.
  • the acid solution treatment for 3-4 hours the effect of removing impurities does not increase significantly over time, so the acid solution treatment is carried out for 30 minutes or more and 24 hours or less, preferably for 30 minutes or more and 3-4 hours.
  • the reduced silicon can be recovered. According to the conventional silicon recovery method, silica is reduced by using carbon. If you let
  • A1 was added as a deoxidizer to the metal smelting slag, and heated to about 1,500 ° C. to oxidize A1 and to reduce silicon from silica in the aule slag. The slag in this state was observed using SEM, and the results are shown in Figures 2a to 2d.
  • Figs. 3A to 3D show the samples before the subsequent acid treatment, and show that most of them are reduced to silicon although there are also calcium and aluminum (see Fig. 3B).
  • the aqua regia was added to the reaction vessel containing the reduced metal and slag as described above and wet treatment was performed at 20 ° C. for 1 hour. By this acid treatment, except for the reduced Si, the oxidized deoxidizer, slag, and impurities at the Si interface were dissolved.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Inorganic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Silicon Compounds (AREA)

Abstract

La présente invention concerne un procédé de récupération de silicium à partir de laitier. Le procédé comprend les étapes suivantes : la préparation d'un contenant de réaction comprenant un matériau capable d'endurer un environnement à température élevée dans une plage de températures auxquelles le laitier fond et présentant une stabilité aux acides ; l'injection de laitier et d'un agent désoxydant dans le contenant de réaction afin de les mélanger ; le chauffage du contenant de réaction afin de faire fondre le laitier pour oxyder l'agent de désoxydation et réduire le silicium à partir du laitier ; le refroidissement du contenant de réaction ; l'injection d'une solution acide dans le contenant de réaction pour dissoudre le laitier, l'agent de désoxydation oxydé et l'agent de désoxydation non oxydé, à l'exception du silicium, par traitement acide ; et la récupération du silicium par filtration.
PCT/KR2012/004476 2012-04-17 2012-06-07 Procédé et appareil pour récupérer du silicium à partir de laitier Ceased WO2013157694A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020120039578A KR101306688B1 (ko) 2012-04-17 2012-04-17 슬래그로부터 실리콘을 회수하는 방법 및 장치
KR10-2012-0039578 2012-04-17

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WO2013157694A1 true WO2013157694A1 (fr) 2013-10-24

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114307909A (zh) * 2022-01-04 2022-04-12 湖南烯富环保科技有限公司 一种除氯渣全自动再生除氯剂生产线及生产方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101744630B1 (ko) 2015-09-09 2017-06-09 포항공과대학교 산학협력단 철강 슬래그로부터 다공성 실리콘을 제조하는 방법, 이 방법에 의해 제조된 다공성 실리콘 및 이를 이용한 리튬이온전지

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4457903A (en) * 1982-03-11 1984-07-03 Heliotronic Forshungs Und Entwicklungsgesellschaft Fur Solarzellen Grundstoffe Mbh Semicontinuous process for the production of pure silicon
WO2006041271A1 (fr) * 2004-10-12 2006-04-20 The Ministry Of Education And Sciences Of Republic Kazakhstan Republican State Enterprise 'center Of Chemical-Technological Researches' Procede de production de silicium pur
JP2006282497A (ja) * 2005-03-07 2006-10-19 Nippon Steel Corp 高純度シリコンの製造方法
JP2008266075A (ja) * 2007-04-20 2008-11-06 Shin Etsu Chem Co Ltd シリコンの精製方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4457903A (en) * 1982-03-11 1984-07-03 Heliotronic Forshungs Und Entwicklungsgesellschaft Fur Solarzellen Grundstoffe Mbh Semicontinuous process for the production of pure silicon
WO2006041271A1 (fr) * 2004-10-12 2006-04-20 The Ministry Of Education And Sciences Of Republic Kazakhstan Republican State Enterprise 'center Of Chemical-Technological Researches' Procede de production de silicium pur
JP2006282497A (ja) * 2005-03-07 2006-10-19 Nippon Steel Corp 高純度シリコンの製造方法
JP2008266075A (ja) * 2007-04-20 2008-11-06 Shin Etsu Chem Co Ltd シリコンの精製方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114307909A (zh) * 2022-01-04 2022-04-12 湖南烯富环保科技有限公司 一种除氯渣全自动再生除氯剂生产线及生产方法

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