CN114735708A - Method for preparing low-iron-aluminum-calcium-content silicon - Google Patents
Method for preparing low-iron-aluminum-calcium-content silicon Download PDFInfo
- Publication number
- CN114735708A CN114735708A CN202210463862.2A CN202210463862A CN114735708A CN 114735708 A CN114735708 A CN 114735708A CN 202210463862 A CN202210463862 A CN 202210463862A CN 114735708 A CN114735708 A CN 114735708A
- Authority
- CN
- China
- Prior art keywords
- zinc
- silicon
- iron
- aluminum
- calcium
- 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.)
- Granted
Links
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
- C01B33/037—Purification
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for preparing silicon with low content of iron, aluminum and calcium, belonging to the technical field of industrial silicon smelting. The method breaks through the way that high-quality silicon is obtained by controlling the impurity content in the raw materials for production in the prior art, industrial zinc is refined outside a furnace, impurities such as iron, aluminum and calcium in the industrial silicon react with zinc to form a low-melting-point compound, the compound is volatilized by utilizing the high temperature of silicon melt to achieve the purpose of removing impurities, the zinc-iron, zinc-aluminum and zinc-calcium compounds which are not volatilized after the silicon is solidified are segregated at a crystal boundary, are removed by acid washing after being crushed, and redundant zinc is changed into gas at high temperature and is separated under the action of compressed gas; the method can effectively remove impurities of iron, aluminum and calcium in the silicon melt, does not introduce new impurities, solves the problem that the existing industrial silicon production depends on raw materials, has low cost and simple operation, can recycle redundant zinc, is energy-saving and environment-friendly, and is suitable for industrial large-scale production.
Description
Technical Field
The invention belongs to the technical field of industrial silicon smelting, and particularly relates to a method for preparing silicon with low content of iron, aluminum and calcium.
Background
In the industrial silicon smelting process, the raw material contains impurities such as Fe, Al, Ca, B, P, etc., and these impurity elements are reduced together with the silicon element during the silica reduction process to enter the industrial silicon and are deposited as impurities in the industrial silicon after the silicon melt is condensed, thereby lowering the purity of the industrial silicon. In order to reduce the content of impurities in the industrial silicon and improve the quality of the industrial silicon, the industrial silicon needs to be refined outside a furnace to remove most of the impurities in the industrial silicon. With the advancement of science and technology, the purity requirement of industrial silicon is higher and higher.
At present, the most common impurity removal method used in industrial silicon plants is that industrial silicon is refined outside the furnace in a two-man ladle, and chlorine, nitrogen, oxygen, and compressed air or a mixed gas of the above gases are blown into the two-man ladle to remove most of the impurities such as Al, Ca, B, and C, but other impurities such as Fe cannot be removed.
Another common impurity removal method is a refining method using a slagging agent, in which a combined component of oxides such as calcium oxide, silicon oxide, aluminum oxide, magnesium oxide, and calcium fluoride, or a raw mineral stone containing the above oxides is added to a ladle, and a slagging agent is used to remove a part of impurities in silicon, but the removal effect on impurities such as Fe is also not satisfactory, and the separation difficulty between silicon and slag after slagging refining greatly affects the yield of silicon.
The third common method is a directional solidification method, which comprises the steps of pouring industrial silicon into a unidirectional heat-dissipation crucible, and slowly solidifying from the bottom upwards to remove metal impurities with large segregation coefficient in the industrial silicon by utilizing the segregation principle.
With the development of modern industry, many downstream enterprises put higher requirements on impurities in refined silicon, particularly special-grade silicon for silicon steel industry, has higher requirements on iron, aluminum and calcium impurities in silicon, but the existing external refining technology cannot effectively separate main metal impurities of iron, aluminum and calcium in industrial silicon products, so that the iron, aluminum and calcium impurities become key impurity elements which directly affect the grade of industrial silicon. However, due to the fluctuation of raw material components and furnace conditions, the quality control effect of the industrial silicon product achieved by the method is unstable, and thus the quality of the industrial silicon product is significantly unstable, and therefore, a more economical and effective industrial silicon impurity removal method needs to be found.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for removing impurities of iron, aluminum and calcium in industrial silicon melt by external refining, which is simple to operate and low in cost.
The purpose of the invention is realized by the following technical scheme: a method for preparing silicon with low content of iron, aluminum and calcium comprises the steps of introducing compressed gas into a ladle, adding solid zinc into industrial silicon melt to be subjected to impurity removal in the ladle, keeping the temperature of the silicon melt above 1700 ℃, converting the solid zinc into gaseous zinc at high temperature, removing a compound formed by reaction of the gaseous zinc and impurities through volatilization, and allowing redundant gaseous zinc to enter a pipeline under the action of the compressed gas so as to achieve the purpose of removing the impurities in the industrial silicon melt.
Further, the compressed gas is compressed argon.
Furthermore, the aeration pressure of the introduced compressed gas is 0.2-0.3 MPa, the gas flow is 800-1200L/h, and the aeration time is 20-60 min.
Further, the reaction time of the gas zinc and impurities of iron, aluminum and calcium is 30-60 min.
Furthermore, the mass of the added zinc is 0.15-0.3% of the mass of the industrial silicon.
Further, the temperature of the industrial silicon melt is 1700 ℃, and a compound formed by the reaction of zinc and impurities is removed by adopting a volatilization method.
Further, the content of impurity iron in the industrial silicon melt is 200ppm to 350ppm, the content of impurity aluminum is 150ppm to 220ppm, and the content of impurity calcium is 100ppm to 150 ppm.
And further, the method also comprises a refining step, specifically, after the silicon is solidified, non-volatile impurity compounds can be segregated at the crystal boundary, the solidified industrial silicon is crushed until zinc-iron, zinc-aluminum and zinc-calcium alloy at the crystal boundary are exposed outside, the crushed industrial silicon material is soaked in an acid solution, and the zinc-iron, zinc-aluminum and zinc-calcium alloy at the crystal boundary react with acid to generate inorganic salt to be dissolved, so that the aim of removing the impurity compounds is fulfilled.
Furthermore, the method also comprises a process of recovering the gaseous zinc in the pipeline in a condensation mode.
The invention has the following advantages: the invention discloses a method for preparing silicon with low iron, aluminum and calcium content, which breaks through the way of obtaining high-quality silicon by controlling the impurity content in production raw materials in the prior art, because the solubility of silicon in zinc is very low, the solubility of zinc in silicon is also very low, the silicon is basically incompatible at normal temperature, industrial zinc is adopted for refining outside a furnace, the impurities of iron, aluminum and calcium in the industrial silicon react with zinc to form a low-melting-point compound, the compound is volatilized by utilizing the high temperature of silicon melt to achieve the purpose of impurity removal, the zinc-iron, zinc-aluminum and zinc-calcium compounds which are not volatilized after the silicon is solidified are segregated at a crystal boundary, are removed by acid washing after being crushed, and the redundant zinc is changed into gas at high temperature and is separated under the action of compressed gas; the method can effectively remove impurities of iron, aluminum and calcium in the silicon melt, does not introduce new impurities, solves the problem that the existing industrial silicon production depends on raw materials, has low cost and simple operation, can recycle redundant zinc, saves energy, protects environment, and is suitable for industrial large-scale production.
Detailed Description
The invention is further described below with reference to examples, without limiting the scope of the invention to the following:
example 1: a method for preparing low iron aluminum calcium content silicon, compressed gas argon is introduced into a ladle, the aeration pressure is 0.2MPa, the gas flow is 800L/h, the aeration time is 20min, zinc is added into industrial silicon melt to be subjected to impurity removal in the ladle, the mass of the added industrial zinc is 0.15% of the mass of the industrial silicon, the reaction is carried out for 30min, the temperature of the silicon melt is maintained at 1700 ℃, and a compound formed by the reaction of the zinc and impurities of iron, aluminum and calcium is removed through volatilization; the zinc and impurities react to form compounds which are not volatilized and segregated at the grain boundary after the silicon is solidified, the compounds are washed by hydrochloric acid after being crushed, the aim of removing impurities of iron, aluminum and calcium in the industrial silicon melt is achieved, redundant gaseous zinc enters the pipeline under the action of compressed gas, and gaseous zinc in the pipeline is recovered by adopting a condensation mode.
Example 2: a method for preparing low iron aluminum calcium content silicon, compressed gas argon is introduced into a ladle, the aeration pressure is 0.3MPa, the gas flow is 1200L/h, the aeration time is 60min, zinc is added into industrial silicon melt to be subjected to impurity removal in the ladle, the mass of the added industrial zinc is 0.3% of the mass of the industrial silicon, the reaction is carried out for 35min, the temperature of the silicon melt is kept at 1800 ℃, and a compound formed by the reaction of the zinc and impurities of iron, aluminum and calcium is removed through volatilization; the compound which is formed by the reaction of zinc and impurities and is not volatilized is segregated at the crystal boundary after the silicon is solidified, and is removed by sulfuric acid cleaning after being crushed, so that the aim of removing impurities of iron, aluminum and calcium in the industrial silicon melt is achieved, redundant gas zinc enters a pipeline under the action of compressed gas, and the gas zinc in the pipeline is recovered by adopting a condensation mode.
Example 3: a method for preparing silicon with low iron, aluminum and calcium contents comprises the steps of introducing compressed gas argon into a ladle, wherein the ventilation pressure is 0.25MPa, the gas flow is 1000L/h, the ventilation time is 30min, adding zinc into industrial silicon melt to be subjected to impurity removal in the ladle, the mass of the added industrial zinc is 0.2% of that of the industrial silicon, reacting for 40min, keeping the temperature of the silicon melt at 2000 ℃, and removing compounds formed by reaction of zinc and impurities of iron, aluminum and calcium through volatilization; the compound which is formed by the reaction of zinc and impurities and is not volatilized is segregated at the crystal boundary after the silicon is solidified, hydrochloric acid is adopted to wash and remove the compound after the compound is crushed, the purpose of removing impurities of iron, aluminum and calcium in the industrial silicon melt is achieved, redundant gas zinc enters a pipeline under the action of compressed gas, and the gas zinc in the pipeline is recovered by adopting a condensing mode.
Example 4: a method for preparing low iron, aluminum and calcium content silicon, compressed gas argon is introduced into a ladle, the ventilation pressure is 0.2MPa, the gas flow is 1100L/h, the ventilation time is 50min, zinc is added into industrial silicon melt to be subjected to impurity removal in the ladle, the mass of the added industrial zinc is 0.2% of the mass of the industrial silicon, the reaction is carried out for 60min, the temperature of the silicon melt is kept at 1900 ℃, and a compound formed by the reaction of the zinc and impurities of iron, aluminum and calcium is removed through volatilization; the zinc and the impurity react to form a compound which is not volatilized and segregated at the grain boundary after the silicon is solidified, the compound is broken and then removed by sulfuric acid cleaning, the purpose of removing the impurities of iron, aluminum and calcium in the industrial silicon melt is achieved, redundant gaseous zinc enters the pipeline under the action of compressed gas, and the gaseous zinc in the pipeline is recovered by adopting a condensation mode.
The beneficial effects of the invention are illustrated by experiments as follows:
experimental example 1:
compressed gas argon is introduced into the ladle, the aeration pressure is 0.25MPa, the gas flow is 1000L/h, and the aeration time is 20 min. Adding zinc into the industrial silicon melt to be subjected to impurity removal in the two-man ladle, adding industrial zinc particles with the total mass being 0.1% of the mass of the industrial silicon, adding the industrial zinc particles at one time, standing for reaction for 30min after adding the industrial zinc, keeping the temperature of the silicon melt at 1800 ℃, and removing a compound formed by the reaction of the zinc and impurities of iron, aluminum and calcium through volatilization; the compound which is formed by the reaction of zinc and impurities and is not volatilized is segregated at the crystal boundary after the silicon is solidified, hydrochloric acid is adopted to wash away after the compound is crushed, the purpose of removing iron, aluminum and calcium which are impurities in the industrial silicon melt is achieved, redundant gas zinc enters a pipeline under the action of compressed gas, and the gas zinc in the pipeline is recovered by adopting a condensing mode.
The content of impurity iron in the industrial silicon before impurity removal is 330ppm, the content of impurity aluminum is 220ppm, and the content of impurity calcium is 100 ppm; the impurity iron content after refining is 218ppm, the impurity aluminum content after refining is 102ppm, and the impurity calcium content after refining is 52 ppm.
Experimental example 2:
compressed argon is introduced into the ladle, the aeration pressure is 0.25MPa, the gas flow is 1000L/h, and the aeration time is 20 min. Adding zinc into industrial silicon melt to be subjected to impurity removal in a two-man ladle, adding industrial zinc particles with the total mass being 0.2% of the mass of the industrial silicon, gradually adding the industrial zinc particles in batches, standing and reacting for 30min after adding the industrial zinc, keeping the temperature of the silicon melt at 1800 ℃, and removing compounds formed by the reaction of the zinc and impurities of iron, aluminum and calcium through volatilization; the zinc and impurities react to form compounds which are not volatilized and segregated at the grain boundary after the silicon is solidified, the compounds are washed by hydrochloric acid after being crushed, the aim of removing impurities of iron, aluminum and calcium in the industrial silicon melt is achieved, redundant gaseous zinc enters the pipeline under the action of compressed gas, and gaseous zinc in the pipeline is recovered by adopting a condensation mode.
The content of impurity iron in the industrial silicon before impurity removal is 330ppm, the content of impurity aluminum is 220ppm, and the content of impurity calcium is 100 ppm; the impurity iron content after refining is 176ppm, the impurity aluminum content after refining is 83ppm, and the impurity calcium content after refining is 41 ppm.
Experimental example 3:
compressed argon is introduced into the ladle, the aeration pressure is 0.25MPa, the gas flow is 1000L/h, and the aeration time is 30 min. Adding zinc into the industrial silicon melt to be subjected to impurity removal in the two-man ladle, adding industrial zinc particles with the total mass being 0.2% of the mass of the industrial silicon, gradually adding the industrial zinc particles in batches, and standing for reaction for 30min after adding the industrial zinc. Keeping the temperature of the silicon melt at 1800 ℃, and removing compounds formed by the reaction of zinc and impurities of iron, aluminum and calcium through volatilization; the compound which is formed by the reaction of zinc and impurities and is not volatilized is segregated at the crystal boundary after the silicon is solidified, hydrochloric acid is adopted to wash and remove the compound after the compound is crushed, the purpose of removing impurities of iron, aluminum and calcium in the industrial silicon melt is achieved, redundant gas zinc enters a pipeline under the action of compressed gas, and the gas zinc in the pipeline is recovered by adopting a condensing mode.
The content of impurity iron in the industrial silicon before impurity removal is 330ppm, the content of impurity aluminum is 220ppm, and the content of impurity calcium is 100 ppm; the impurity iron content after refining was 153ppm, the impurity aluminum content after refining was 72ppm, and the impurity calcium content after refining was 35 ppm.
Experimental example 4:
compressed argon is introduced into the ladle, the aeration pressure is 0.25MPa, the gas flow is 1000L/h, and the aeration time is 30 min. Adding zinc into industrial silicon melt to be subjected to impurity removal in a ladle, adding industrial zinc particles with the total mass being 0.2% of the mass of the industrial silicon, gradually adding the industrial zinc particles in batches, standing and reacting for 60min after adding the industrial zinc, keeping the temperature of the silicon melt at 1800 ℃, and removing a compound formed by the reaction of the zinc and impurities of iron, aluminum and calcium through volatilization; the compound which is formed by the reaction of zinc and impurities and is not volatilized is segregated at the crystal boundary after the silicon is solidified, hydrochloric acid is adopted to wash and remove the compound after the compound is crushed, the purpose of removing impurities of iron, aluminum and calcium in the industrial silicon melt is achieved, redundant gas zinc enters a pipeline under the action of compressed gas, and the gas zinc in the pipeline is recovered by adopting a condensing mode.
The content of impurity iron in the industrial silicon before impurity removal is 330ppm, the content of impurity aluminum is 220ppm, and the content of impurity calcium is 100 ppm; the impurity iron content after refining was 145ppm, the impurity aluminum content after refining was 65ppm, and the impurity calcium content after refining was 31 ppm.
Experimental example 5:
compressed argon is introduced into the ladle, the aeration pressure is 0.3MPa, the gas flow is 1000L/h, and the aeration time is 20 min. Adding zinc into industrial silicon melt to be subjected to impurity removal in a two-man ladle, adding industrial zinc particles with the total mass being 0.2% of the mass of the industrial silicon, gradually adding the industrial zinc particles in batches, standing and reacting for 60min after adding the industrial zinc, keeping the temperature of the silicon melt at 1800 ℃, and removing compounds formed by the reaction of the zinc and impurities of iron, aluminum and calcium through volatilization; the compound which is formed by the reaction of zinc and impurities and is not volatilized is segregated at the crystal boundary after the silicon is solidified, hydrochloric acid is adopted to wash and remove the compound after the compound is crushed, the purpose of removing impurities of iron, aluminum and calcium in the industrial silicon melt is achieved, redundant gas zinc enters a pipeline under the action of compressed gas, and the gas zinc in the pipeline is recovered by adopting a condensing mode.
The content of impurity iron in the industrial silicon before impurity removal is 330ppm, the content of impurity aluminum is 220ppm, and the content of impurity calcium is 100 ppm; the impurity iron content after refining is 110ppm, the impurity aluminum content after refining is 51ppm, and the impurity calcium content after refining is 20 ppm.
Comparative example:
introducing compressed argon into the ladle, introducing the compressed argon, wherein the aeration pressure is 0.25MPa, the gas flow is 1000L/h, the aeration time is 20min, and standing reaction is carried out for 30min without adding zinc. The content of impurity iron in the industrial silicon is 330ppm, the content of impurity aluminum is 220ppm, and the content of impurity calcium is 100 ppm; the content of impurity iron after refining is 328ppm, the content of impurity aluminum after refining is 120ppm, and the content of impurity calcium after refining is 65 ppm. It can be seen that there was essentially no change before and after the reaction.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution of the present invention and the inventive concept within the technical scope of the present invention.
Claims (9)
1. A method for preparing silicon with low content of iron, aluminum and calcium is characterized in that compressed gas is introduced into a ladle, solid zinc is added into industrial silicon melt to be subjected to impurity removal in the ladle, the temperature of the silicon melt is kept above 1700 ℃, the solid zinc is converted into gaseous zinc at high temperature, a compound formed by reaction of the gaseous zinc and impurities is removed through volatilization, and redundant gaseous zinc enters a pipeline under the action of the compressed gas, so that the purpose of removing the impurities in the industrial silicon melt is achieved.
2. The method of claim 1, wherein the compressed gas is compressed argon.
3. The method for preparing silicon with low content of iron, aluminum and calcium as claimed in claim 1, wherein the aeration pressure of the compressed gas is 0.2-0.3 MPa, the gas flow is 800-1200L/h, and the aeration time is 20-60 min.
4. The method for preparing silicon with low content of iron, aluminum and calcium as claimed in claim 1, wherein the reaction time of the gaseous zinc and impurities of iron, aluminum and calcium is 30-60 min.
5. The method for preparing silicon with low content of iron, aluminum and calcium as claimed in claim 1 or 4, wherein the mass of added zinc is 0.15-0.3% of the mass of industrial silicon.
6. The method for preparing silicon with low content of iron, aluminum and calcium as claimed in claim 1, wherein the temperature of the industrial silicon melt is 1700 ℃, and the compounds formed by the reaction of zinc and impurity iron are removed by a volatilization method.
7. The method as claimed in claim 1, wherein the industrial silicon melt contains 200ppm to 350ppm of impurity iron, 150ppm to 220ppm of impurity aluminum, and 100ppm to 150ppm of impurity calcium.
8. The method for preparing silicon with low Fe, Al and Ca contents as claimed in claim 1, further comprising a refining step, specifically, non-volatile impurity compounds will be segregated at the grain boundary after the solidification of silicon, the solidified industrial silicon is crushed until the Zn-Fe, Zn-Al and Zn-Ca alloys at the grain boundary are exposed, the crushed industrial silicon is soaked in an acid solution, and the Zn-Fe, Zn-Al and Zn-Ca alloys at the grain boundary react with the acid to generate inorganic salts to be dissolved, thereby achieving the purpose of removing the impurity compounds.
9. The method for preparing silicon with low content of iron, aluminum and calcium as claimed in claim 1, which further comprises a process of recovering gaseous zinc in the pipeline by means of condensation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210463862.2A CN114735708B (en) | 2022-04-29 | 2022-04-29 | Method for preparing silicon with low content of iron, aluminum and calcium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210463862.2A CN114735708B (en) | 2022-04-29 | 2022-04-29 | Method for preparing silicon with low content of iron, aluminum and calcium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114735708A true CN114735708A (en) | 2022-07-12 |
| CN114735708B CN114735708B (en) | 2023-06-02 |
Family
ID=82286072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210463862.2A Active CN114735708B (en) | 2022-04-29 | 2022-04-29 | Method for preparing silicon with low content of iron, aluminum and calcium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114735708B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB755279A (en) * | 1954-05-26 | 1956-08-22 | Union Carbide Ltd | An improved method for decreasing the amount of aluminium and calcium in silicon metal or ferro-silicon alloys |
| JPH08325618A (en) * | 1995-05-26 | 1996-12-10 | Nippon Steel Corp | Method for concentrating zinc component from zinc-containing material by dephosphorization of low-silicon molten iron |
| WO2006100114A1 (en) * | 2005-03-24 | 2006-09-28 | Umicore | Process for the production of si by reduction of siclj with liquid zn |
| US20060270199A1 (en) * | 2002-09-12 | 2006-11-30 | Takayuki Shimamune | Process for producing high-purity silicon and apparatus |
| JP2010235322A (en) * | 2009-03-30 | 2010-10-21 | Cosmo Oil Co Ltd | Production method of polycrystalline silicon ingot |
| CN102311121A (en) * | 2011-08-29 | 2012-01-11 | 大连理工大学 | Method for segregation and purification of industrial silicon by alloying |
| US20120164055A1 (en) * | 2009-06-24 | 2012-06-28 | The Governing Council Of The University Of Toronto | Method of removal of impurities from silicon |
| CN102583389A (en) * | 2012-03-05 | 2012-07-18 | 昆明理工大学 | Method for purifying industrial silicon through external refining |
-
2022
- 2022-04-29 CN CN202210463862.2A patent/CN114735708B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB755279A (en) * | 1954-05-26 | 1956-08-22 | Union Carbide Ltd | An improved method for decreasing the amount of aluminium and calcium in silicon metal or ferro-silicon alloys |
| JPH08325618A (en) * | 1995-05-26 | 1996-12-10 | Nippon Steel Corp | Method for concentrating zinc component from zinc-containing material by dephosphorization of low-silicon molten iron |
| US20060270199A1 (en) * | 2002-09-12 | 2006-11-30 | Takayuki Shimamune | Process for producing high-purity silicon and apparatus |
| WO2006100114A1 (en) * | 2005-03-24 | 2006-09-28 | Umicore | Process for the production of si by reduction of siclj with liquid zn |
| JP2010235322A (en) * | 2009-03-30 | 2010-10-21 | Cosmo Oil Co Ltd | Production method of polycrystalline silicon ingot |
| US20120164055A1 (en) * | 2009-06-24 | 2012-06-28 | The Governing Council Of The University Of Toronto | Method of removal of impurities from silicon |
| CN102311121A (en) * | 2011-08-29 | 2012-01-11 | 大连理工大学 | Method for segregation and purification of industrial silicon by alloying |
| CN102583389A (en) * | 2012-03-05 | 2012-07-18 | 昆明理工大学 | Method for purifying industrial silicon through external refining |
Non-Patent Citations (2)
| Title |
|---|
| 侯彦青;谢刚;陶东平;俞小花;田林;杨妮;: "太阳能级多晶硅生产工艺" * |
| 罗大伟: "太阳能级硅冶金制备技术研究" * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114735708B (en) | 2023-06-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101903543B (en) | Method for refining copper concentrate | |
| AU773569B2 (en) | Process for refining silver bullion with gold separation | |
| CN102807220B (en) | Silicon purification method | |
| CN109609769B (en) | Process for directly producing anode plate by adopting oxygen-enriched smelting furnace | |
| CN110194456B (en) | Method for smelting metal silicon by using waste silicon sludge | |
| CN101712474B (en) | Method for preparing solar-grade high-purity silicon by dilution purifying technology | |
| CN114735708A (en) | Method for preparing low-iron-aluminum-calcium-content silicon | |
| CN108675306B (en) | Method for efficiently recovering silicon metal in silicon slag | |
| CN108950143B (en) | Comprehensive utilization method of phosphorus and iron as yellow phosphorus smelting by-product | |
| CN116287737A (en) | Method for realizing cyclic utilization of titanium, vanadium, iron, calcium, silicon, sulfur and nitrogen | |
| CN111041240B (en) | Method for preparing ferrotitanium alloy by using perovskite concentrate as raw material | |
| CN110218836B (en) | Method for dealuminizing and purifying ferrosilicon | |
| CN113061755A (en) | Process for producing ammonium paratungstate by flotation type tungsten raw material oxygen-enriched leaching full-wet method | |
| CN114890428B (en) | Ternary slag former for external refining of industrial silicon and impurity removing method thereof | |
| JP2000327488A (en) | Production of silicon substrate for solar battery | |
| CN112095014A (en) | Method for efficiently recycling copper and cadmium from copper-cadmium slag | |
| CN117385203A (en) | Method for recycling metal beryllium from beryllium-containing waste | |
| CN117446840A (en) | Method for preparing ammonium fluoberyllide from beryllium-containing waste | |
| US11807538B1 (en) | Method for removing phosphorus and boron impurity from industrial silicon melt by secondary refining | |
| KR101453149B1 (en) | Method for collection of in and sn-containing alloy and method for processing ito recycle material | |
| CN115976341B (en) | Method for removing silicon and phosphorus in vanadium slag sodium roasting production system | |
| CN110541078A (en) | Method for recovering antimony, arsenic and alkali from secondary arsenic alkali residue | |
| CN113502377B (en) | Rapid reducing agent for ladle top slag and preparation method and use method thereof | |
| CN117049550A (en) | Method for removing impurity Fe by external refining of industrial silicon | |
| CN114644339B (en) | Method for removing impurities in silicon by adopting inorganic zinc salt |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |