CN115353110A - Method for removing boron impurities in industrial silicon by silicomanganese slagging and refining - Google Patents
Method for removing boron impurities in industrial silicon by silicomanganese slagging and refining Download PDFInfo
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 67
- 239000010703 silicon Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000012535 impurity Substances 0.000 title claims abstract description 26
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 24
- 238000007670 refining Methods 0.000 title claims abstract description 20
- 229910000720 Silicomanganese Inorganic materials 0.000 title claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000001301 oxygen Substances 0.000 claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 31
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 23
- 239000011572 manganese Substances 0.000 claims abstract description 23
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 21
- 239000000956 alloy Substances 0.000 claims abstract description 21
- PYLLWONICXJARP-UHFFFAOYSA-N manganese silicon Chemical compound [Si].[Mn] PYLLWONICXJARP-UHFFFAOYSA-N 0.000 claims abstract description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 238000005554 pickling Methods 0.000 claims abstract description 13
- 239000002893 slag Substances 0.000 claims abstract description 13
- 239000000047 product Substances 0.000 claims abstract description 12
- 238000004321 preservation Methods 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- 230000007935 neutral effect Effects 0.000 claims abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 61
- 238000007789 sealing Methods 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 11
- 230000007246 mechanism Effects 0.000 claims description 8
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 230000003028 elevating effect Effects 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 210000003437 trachea Anatomy 0.000 claims 3
- 230000008569 process Effects 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 2
- 229910021422 solar-grade silicon Inorganic materials 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 7
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 boron impurities Chemical compound 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
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- 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
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- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a method for removing boron impurities in industrial silicon by silicomanganese slagging refining, which comprises the following steps: s1: putting industrial silicon and metal manganese to be purified into an intermediate frequency furnace, and raising the temperature in the furnace to 1500-1700 ℃ to obtain silicon-manganese molten alloy; s2: preserving the heat of the silicomanganese molten alloy for 2-4 hours to obtain a silicon manganese molten alloy after heat preservation; s3: adding CaO and CaF into the heat-preserved silicon-manganese molten alloy 2 Slag agent to obtain reaction product; s4: continuously introducing oxygen into the reaction product, and slagging for 5-7 h to obtain a slagging product; s5: and (3) carrying out mixed acid pickling on the slagging product by hydrochloric acid and hydrofluoric acid, washing the product after pickling to be neutral, and drying to obtain the high-purity silicon. The method realizes the high-efficiency purification of the industrial silicon, particularly can effectively reduce the boron impurities in the silicon to the standard of solar grade silicon, has simple process and low cost, saves cost and manpower, and is very suitable for industrialized popularization and use.
Description
Technical Field
The invention belongs to the technical field of polysilicon purification, and particularly relates to a method for removing boron impurities in industrial silicon by silicomanganese slagging and refining.
Background
With the increasing severity of environmental issues, the search for new renewable energy is one of the problems to be solved urgently, and solar energy has attracted extensive attention to solar energy because of its natural advantages such as inexhaustible energy.
Solar cells have a very broad prospect as one of the main applications of solar energy, wherein the solar cells mainly comprise polycrystalline silicon solar cells, and the polycrystalline silicon used by the current solar cells is mainly prepared by two methods: one is a chemical method, namely, industrial silicon is converted into an intermediate product, the intermediate product is purified by the chemical method, and finally the intermediate product is reduced into high-purity silicon, and although the silicon obtained by the chemical method has high purity and good quality, the process is complex and the process cost is high; the other method is a metallurgical method, wherein the impurities in the silicon are removed in a grading manner mainly through different physical properties of the impurities and the combination of different processes, and the metallurgical method mainly comprises a slagging method, a vacuum refining method, a directional solidification method and the like.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a method for removing boron impurities in industrial silicon by silicon-manganese slagging refining.
The invention provides a method for removing boron impurities in industrial silicon by silicomanganese slagging and refining, which comprises the following steps:
s1: putting industrial silicon and metal manganese to be purified into an intermediate frequency furnace, and raising the temperature in the furnace to 1500-1700 ℃ to obtain a silicon-manganese molten alloy;
s2: preserving the heat of the silicomanganese molten alloy for 2-4 hours to obtain a silicon manganese molten alloy after heat preservation;
s3: adding CaO and CaF into the heat-preserved silicon-manganese molten alloy 2 Slag agent to obtain reaction product;
s4: continuously introducing oxygen into the reaction product, and slagging for 5-7 h to obtain a slagging product;
s5: and (3) carrying out mixed acid pickling on the slagging product by hydrochloric acid and hydrofluoric acid, washing the product after pickling to be neutral, and drying to obtain the high-purity silicon.
Preferably, in the step S1, the industrial silicon and the metal manganese are respectively used in the form of silicon blocks and manganese blocks, the mass ratio of the addition amount of the industrial silicon to the addition amount of the manganese blocks is 1 (0.05-0.1), the purity of the industrial silicon is 2-3N, and the purity of the manganese blocks is 3-4N.
Preferably, the temperature in step S2 is 1400-1500 ℃.
Preferably, wherein in step S3, the CaO and CaF 2 Respectively used in the form of powder with the purity of 2-3N, the CaO and CaF 2 The mass ratio of the addition amount of (A) is 1 (0.1-0.15).
Preferably, the flow rate of the oxygen introduced in the step S4 is 200-400 ml/min.
Preferably, the concentration of hydrofluoric acid in the mixed acid in the step S5 is 2-3 mol/L, the concentration of hydrochloric acid is 1-3 mol/L, the pickling temperature is 50-80 ℃, and the pickling time is 3-6 h.
Preferably, the intermediate frequency furnace comprises an outer furnace body and an inner furnace body, the inner furnace body is fixedly installed in the outer furnace body, a heating layer is arranged between the inner furnace body and the outer furnace body, an air release pipe is fixedly installed at the bottom in the outer furnace body, a plurality of air ports are installed on the air release pipe, an arc-shaped pipe is arranged in the inner furnace body, the lower surface of the arc-shaped pipe is wedge-shaped, connectors are arranged at two ends of the arc-shaped pipe, the two connectors are respectively connected with two ends of the air release pipe, two connecting pipes are communicated with the arc-shaped pipe, a sealing cover is arranged at the upper end of the outer furnace body, a movable plate is rotatably connected to one side of the sealing cover, the two connecting pipes slidably penetrate through the sealing cover, and a lifting mechanism is arranged on the sealing cover;
elevating system is connected with two connecting pipes, two one side of connecting pipe upper end all communicates there is the gas-supply pipe, oxygen enters into in connecting pipe and the arc through the gas-supply pipe, oxygen in the arc enters into the bleeder through two connectors, and oxygen releases through the gas port on the bleeder, it is connected with the pivot to rotate on the bleeder, install first motor on the gland, first motor passes through drive end and pivot fixed connection, go back a plurality of mixing shafts of fixedly connected with in the pivot, industry silicon, manganese metal, caO, caF 2 The slag agents are all conveyed into the furnace through the movable plateIn the furnace body.
Preferably, the driving mechanism comprises a second motor, a threaded shaft and a linkage shaft, the second motor is fixedly mounted on the sealing cover, the driving end of the second motor is fixedly connected with the threaded shaft, the linkage shaft is provided with three tail ends, one end of the linkage shaft is sleeved on the threaded shaft in a threaded manner, and the other two ends of the linkage shaft are fixedly connected with the upper ends of the two connecting pipes.
Preferably, the both ends of gassing pipe are all rotated and are connected with the sealed slider of second, and rotate the junction and be provided with the return spring, the lower extreme of the sealed slider of second rotates with the downside of gassing pipe and is connected, the upper end of the sealed slider of second is provided with the sloping block, two the inner wall of connector respectively with the both ends side slip joint of gassing pipe, sliding connection has first sealed slider on the connector, connecting spring and connector fixed connection are passed through to the upper end of first sealed slider.
Compared with the prior art, the invention has the beneficial effects that:
1. the method is mainly used for industrial application, can effectively purify industrial silicon, particularly boron impurities, purifies metallurgical-grade silicon to solar-grade silicon, firstly puts industrial silicon and manganese metal into an intermediate frequency furnace for smelting and preserving heat for a period of time, then adds a slag agent and introduces oxygen from the bottom of the intermediate frequency furnace, and finally carries out acid cleaning treatment on a silicon ingot after slagging;
2. industrial silicon, manganese metal, caO, caF 2 In the mouth that the slag agent was opened through the fly leaf was put into interior furnace body, the heating layer heats the internal furnace body and makes the inside material react each other, through actuating mechanism downstream arc pipe for the both ends of arc pipe communicate with the both ends of bleeding pipe respectively, and oxygen passes through the gas-supply pipe, passes connecting pipe, arc pipe, bleeding pipe, carries out through each gas port, begins to carry oxygen from the bottom of medium frequency furnace, and oxygen is in the former of self gravityBecause of passing each material from bottom to top, the abundant contact of effectual assurance material and oxygen, oxygen can start first motor simultaneously at the in-process that reacts with the material, and first motor drives pivot and each mixing shaft through the drive end and rotates, mixes the reactant of inside, and intensive mixing makes it fully react, drives whole intermediate frequency furnace through the cylinder and rotates, and the material is emptyd out through fly leaf department after the reaction.
Drawings
FIG. 1 is a flow chart of a method for removing boron impurities in industrial silicon by silicomanganese slagging refining, which is provided by the invention;
FIG. 2 is a schematic structural diagram of an intermediate frequency furnace;
FIG. 3 is a schematic diagram of the internal structure of the intermediate frequency furnace;
fig. 4 is a partial structural schematic diagram of the intermediate frequency furnace.
In the figure: the furnace comprises an outer furnace body 1, an inner furnace body 2, a movable plate 3, a sealing cover 4, a threaded shaft 5, a connecting pipe 6, a gas pipe 7, a first motor 8, a second motor 9, a linkage shaft 10, a rotating shaft 11, a mixing shaft 12, an arc-shaped pipe 13, a gas discharging pipe 14, a first sealing slide block 15, a connecting port 16, a connecting spring 17, a gas port 18, an inclined block 19 and a second sealing slide block 20.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
The first embodiment is as follows:
referring to fig. 1-4, a method for removing boron impurities in industrial silicon by silicomanganese slagging refining comprises the following steps:
s1: putting 15kg of industrial silicon (with the purity of 99.8%) to be purified and 1.5kg of metal manganese blocks (with the purity of 99.99%) into an intermediate frequency furnace, raising the temperature in the furnace to 1600 ℃, wherein the industrial silicon and the metal manganese are respectively used in the forms of silicon blocks and manganese blocks, the purity of the industrial silicon is 2-3N, and the purity of the manganese blocks is 3-4N;
s2: the silicon-manganese molten alloy is subjected to heat preservation for 4 hours to obtain the heat-preserved silicon-manganese molten alloy, and the heat preservation temperature is 1400-1500 ℃;
s3: adding 15kg of CaO and 1.5kg of CaF into the silicon-manganese molten alloy after heat preservation 2 Slag agent, caO and CaF 2 Are respectively used in the form of powder with the purity of 2-3N;
s4: continuously introducing oxygen into the intermediate frequency furnace at the flow rate of 400ml/min, and slagging for 5 hours to obtain a slagging product;
s5: and (3) pickling the slagging silicon ingot with mixed acid consisting of 3mol/L hydrochloric acid and 3mol/L hydrofluoric acid at 70 ℃ for 5 hours, and then filtering and washing with deionized water for production.
The purity of the acid-washed silicon was 99.99978%, as determined by Glow Discharge Mass Spectrometry (GDMS), with a boron impurity content of 0.15ppmw.
The intermediate frequency furnace comprises an outer furnace body 1 and an inner furnace body 2, the inner furnace body 2 is fixedly arranged in the outer furnace body 1, a heating layer is arranged between the inner furnace body 2 and the outer furnace body 1, an air release pipe 14 is fixedly arranged at the bottom in the outer furnace body 1, a plurality of air ports 18 are arranged on the air release pipe 14, an arc-shaped pipe 13 is arranged in the inner furnace body 2, the lower surface of the arc-shaped pipe 13 is wedge-shaped, two ends of the arc-shaped pipe 13 are provided with connecting ports 16, the two connecting ports 16 are respectively connected with two ends of the air release pipe 14, the arc-shaped pipe 13 is communicated with two connecting pipes 6, a sealing cover 4 is arranged at the upper end of the outer furnace body 1, one side of the sealing cover 4 is rotatably connected with a movable plate 3, the two connecting pipes 6 slide through the sealing cover 4, and a lifting mechanism is arranged on the sealing cover 4;
elevating system is connected with two connecting pipes 6, one side of two connecting pipes 6 upper ends all communicates with gas-supply pipe 7, oxygen enters into connecting pipe 6 and arc 13 through gas-supply pipe 7 in, oxygen in arc 13 enters into bleeder 14 through two connectors 16, and oxygen releases through gas port 18 on the bleeder 14, it is connected with pivot 11 to rotate on the bleeder 14, install first motor 8 on the sealed lid 4, first motor 8 passes through drive end and 11 fixed connection in pivot, still a plurality of mixing shaft 12 of fixedly connected with in the pivot 11, industrial silicon, manganese metal, caO, caF 2 The slag agents are all conveyed into the inner furnace body 2 through the movable plate 3.
By rotating the movable plate 3, industrial silicon, manganese metal, caO and CaF can be used 2 Slag agent is put into interior furnace body 2 through the opening that fly leaf 3 was opened, the heating layer heats interior furnace body 2 and makes inside material react each other, move down arc pipe 13 through actuating mechanism, make the both ends of arc pipe 13 communicate with the both ends of bleeder 14 respectively, oxygen passes through gas-supply pipe 7, pass connecting pipe 6, arc pipe 13, bleeder 14, carry out through each gas port 18, from the bottom of medium frequency furnace transport oxygen, oxygen passes each material from bottom to top at the reason of self gravity, the effectual abundant contact of guaranteeing material and oxygen, oxygen is at the in-process with the material reaction, can start first motor 8 simultaneously, first motor 8 drives pivot 11 and each mixing shaft 12 through the drive end and rotates, mix the reactant of inside, the intensive mixing makes its fully react, drive whole medium frequency furnace through the cylinder and rotates, the material is emptyd out through fly leaf 3 department after the reaction.
The driving mechanism comprises a second motor 9, a threaded shaft 5 and a linkage shaft 10, the second motor 9 is fixedly mounted on the sealing cover 4, the driving end of the second motor 9 is fixedly connected with the threaded shaft 5, the linkage shaft 10 is provided with three tail ends, one end of the linkage shaft 10 is in threaded sleeve connection with the threaded shaft 5, the other two ends of the linkage shaft 10 are fixedly connected with the upper ends of the two connecting pipes 6, and the inside industrial silicon, metal manganese, caO and CaF are fixedly connected 2 When the slag agents are mixed and react with each other, in order to avoid the influence of the arc-shaped pipe 13 on the reaction, the arc-shaped pipe is moved upwards, the second motor 9 drives the threaded shaft 5 to rotate through the driving end, and the linkage shaft 10 drives the linkage shaft 10 to move up and down along with the rotation of the threaded shaft 5 because the two connecting pipes 6 limit the angular position, so that the linkage shaft 10 drives the two connecting pipes 6 to move up and down.
The two ends of the air release pipe 14 are rotatably connected with second sealing slide blocks 20, return springs are arranged at the rotating connection positions, the lower ends of the second sealing slide blocks 20 are rotatably connected with the lower side of the air release pipe 14, inclined blocks 19 are arranged at the upper ends of the second sealing slide blocks 20, the inner walls of the two connecting ports 16 are respectively clamped with the side faces of the two ends of the air release pipe 14 in a sliding mode, the connecting ports 16 are connected with first sealing slide blocks 15 in a sliding mode, and the upper ends of the first sealing slide blocks 15 are fixedly connected with the connecting ports 16 through connecting springs 17;
when the arc-shaped pipe 13 is moved downwards, the two connecting ports 16 are aligned with the two ends of the air release pipe 14 up and down, when the connecting ports 16 move downwards, the lower ends of the connecting ports 16 are in contact with the inclined block 19, because the inclined block 19 is an inclined plane, the inclined block 19 can be inclined along with the downward movement of the connecting ports 16, the inclined block 19 drives the second sealing slide block 20 to incline, in the inclining process, the lower end of the first sealing slide block 15 is abutted against the air release pipe 14, the connecting ports 16 can be gradually aligned with and communicated with the two ends of the air release pipe 14 left and right, so that oxygen can be introduced into the arc-shaped pipe 13 through the connecting pipe 6, enter the air release pipe 14 and be output through the air ports 18, oxygen is introduced from the bottom of the inner furnace body 2, the sufficient contact between the oxygen and various materials is facilitated, the reaction is facilitated, when the connecting ports 16 are separated from the air release pipe 14, the second sealing slide block the two ends of the air release pipe 14 by resetting under the action of the return spring, and simultaneously, the first sealing slide block the connecting ports 16 under the elastic action of the connecting spring 17.
The second embodiment:
referring to fig. 1-4, a method for removing boron impurities in industrial silicon by silicomanganese slagging refining comprises the following steps:
s1: putting 15kg of industrial silicon (with the purity of 99.8%) to be purified and 1.5kg of metal manganese blocks (with the purity of 99.99%) into an intermediate frequency furnace, raising the temperature in the furnace to 1750 ℃, wherein the industrial silicon and the metal manganese are respectively used in the form of silicon blocks and manganese blocks, the purity of the industrial silicon is 2-3N, and the purity of the manganese blocks is 3-4N;
s2: preserving the heat of the silicomanganese molten alloy for 3 hours to obtain the silicon manganese molten alloy after heat preservation;
s3: adding 15kg of CaO and 1.5kg of CaF into the silicon-manganese molten alloy after heat preservation 2 Slag agent, caO and CaF 2 Are respectively used in the form of powder with the purity of 2-3N;
s4: continuously introducing oxygen into the intermediate frequency furnace at the flow rate of 300ml/min, and slagging for 5 hours to obtain a slagging product;
s5: and (3) pickling the slagging silicon ingot with mixed acid consisting of 2mol/L hydrochloric acid and 3mol/L hydrofluoric acid at 80 ℃ for 6 hours, and then filtering and washing with deionized water for production.
The purity of the pickled silicon was 99.99948% as determined by Glow Discharge Mass Spectrometry (GDMS), with a boron impurity content of 0.11ppmw, wherein the structure and method of use of the intermediate frequency furnace was the same as in the first embodiment.
Example three:
referring to fig. 1-4, a method for removing boron impurities in industrial silicon by silicomanganese slagging refining comprises the following steps:
s1: putting 15kg of industrial silicon (with the purity of 99.8%) to be purified and 1.5kg of metal manganese blocks (with the purity of 99.99%) into an intermediate frequency furnace, raising the temperature in the furnace to 1550 ℃, and using the industrial silicon and the metal manganese in the form of silicon blocks and manganese blocks respectively, wherein the purity of the industrial silicon is 2-3N, and the purity of the manganese blocks is 3-4N;
s2: preserving the heat of the silicomanganese molten alloy for 3 hours to obtain the silicon manganese molten alloy after heat preservation;
s3: adding 15kg of CaO and 1.5kg of CaF into the silicon-manganese molten alloy after heat preservation 2 Slag agent, caO and CaF 2 Are respectively used in the form of powder with the purity of 2-3N;
s4: continuously introducing oxygen into the intermediate frequency furnace at the flow rate of 200ml/min, and slagging for 6 hours to obtain a slagging product;
s5: and (3) pickling the slagging silicon ingot with mixed acid consisting of 1mol/L hydrochloric acid and 2mol/L hydrofluoric acid at 50 ℃ for 3h, and then filtering and washing with deionized water for production.
The purity of the pickled silicon is 99.99943% measured by a Glow Discharge Mass Spectrometer (GDMS), wherein the content of boron impurities is 0.08ppmw, and the structure and the using method of the intermediate frequency furnace are the same as those of the first embodiment.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A method for removing boron impurities in industrial silicon by silicomanganese slagging and refining is characterized by comprising the following steps:
s1: putting industrial silicon and metal manganese to be purified into an intermediate frequency furnace, and raising the temperature in the furnace to 1500-1700 ℃ to obtain a silicon-manganese molten alloy;
s2: preserving the heat of the silicomanganese molten alloy for 2-4 hours to obtain the silicon manganese molten alloy after heat preservation;
s3: adding CaO and CaF into the heat-preserved silicon-manganese molten alloy 2 Slag agent to obtain reaction product;
s4: continuously introducing oxygen into the reaction product, and slagging for 5-7 h to obtain a slagging product;
s5: and (3) carrying out mixed acid pickling on the slagging product by hydrochloric acid and hydrofluoric acid, washing the product after pickling to be neutral, and drying to obtain the high-purity silicon.
2. The method for removing boron impurities in industrial silicon through silicon-manganese slagging refining according to claim 1, wherein in the step S1, the industrial silicon and the metal manganese are used in the form of silicon blocks and manganese blocks respectively, the mass ratio of the addition amount of the industrial silicon to the addition amount of the manganese blocks is 1 (0.05-0.1), the purity of the industrial silicon is 2-3N, and the purity of the manganese blocks is 3-4N.
3. The method for removing boron impurities in industrial silicon through silicomanganese slagging refining according to claim 1, wherein the temperature in step S2 is 1400-1500 ℃.
4. The method for removing boron impurities in industrial silicon by silicomanganese slagging refining according to claim 1, wherein in step S3, caO and CaF are added 2 Respectively used in the form of powder with the purity of 2-3N, the CaO and CaF 2 The mass ratio of the addition amount of (A) is 1 (0.1-0.15).
5. The method for removing boron impurities in industrial silicon through silicomanganese slagging refining according to claim 1, wherein the flow rate of the oxygen introduced in the step S4 is 200-400 ml/min.
6. The method for removing boron impurities in industrial silicon through silicon-manganese slagging refining as claimed in claim 1, wherein in step S5, the concentration of hydrofluoric acid in the mixed acid is 2-3 mol/L, the concentration of hydrochloric acid is 1-3 mol/L, the pickling temperature is 50-80 ℃, and the pickling time is 3-6 h.
7. The method for removing boron impurities in industrial silicon through silicomanganese slagging refining according to claim 1, characterized in that the intermediate frequency furnace comprises an outer furnace body (1) and an inner furnace body (2), the inner furnace body (2) is fixedly installed in the outer furnace body (1), a heating layer is arranged between the inner furnace body (2) and the outer furnace body (1), an air exhaust pipe (14) is fixedly installed at the bottom in the outer furnace body (1), a plurality of air ports (18) are installed on the air exhaust pipe (14), an arc-shaped pipe (13) is arranged in the inner furnace body (2), the lower surface of the arc-shaped pipe (13) is wedge-shaped, two ends of the arc-shaped pipe (13) are provided with connecting ports (16), the two connecting ports (16) are respectively connected with two ends of the air exhaust pipe (14), the arc-shaped pipe (13) is communicated with two connecting pipes (6), the upper end of the outer furnace body (1) is provided with a sealing cover (4), one side of the sealing cover (4) is rotatably connected with a movable plate (3), the two connecting pipes (6) slidably pass through the sealing cover (4), and a lifting mechanism is arranged on the sealing cover (4);
elevating system is connected, two with two connecting pipe (6) one side of connecting pipe (6) upper end all communicates there is gas-supply pipe (7), oxygen enters into in connecting pipe (6) and arc pipe (13) through gas-supply pipe (7), oxygen in arc pipe (13) enters into out trachea (14) through two connector (16), and oxygen releases through gas port (18) on out trachea (14), it is connected with pivot (11) to rotate on out trachea (14), install first motor (8) on sealed lid (4), first motor (8) are through drive end and pivot (11) fixed connection, go back a plurality of hybrid shaft (12) of fixedly connected with in pivot (11), industry silicon, metal manganese, caO, caF 2 The slag agents are all conveyed into the inner furnace body (2) through the movable plate (3).
8. The method for removing boron impurities in industrial silicon through silicon-manganese slagging refining according to claim 7, wherein the driving mechanism comprises a second motor (9), a threaded shaft (5) and a linkage shaft (10), the second motor (9) is fixedly installed on the sealing cover (4), the driving end of the second motor (9) is fixedly connected with the threaded shaft (5), the linkage shaft (10) has three ends, one end of the linkage shaft (10) is in threaded sleeve connection with the threaded shaft (5), and the other two ends of the linkage shaft (10) are fixedly connected with the upper ends of the two connecting pipes (6).
9. The method for removing boron impurities in industrial silicon through silicon-manganese slagging refining according to claim 7, wherein the two ends of the gas release pipe (14) are rotatably connected with second sealing sliders (20), a return spring is arranged at the rotary connection position, the lower end of each second sealing slider (20) is rotatably connected with the lower side of the gas release pipe (14), the upper end of each second sealing slider (20) is provided with an inclined block (19), the inner walls of the two connecting ports (16) are respectively in sliding clamping connection with the side surfaces of the two ends of the gas release pipe (14), the connecting ports (16) are slidably connected with first sealing sliders (15), and the upper ends of the first sealing sliders (15) are fixedly connected with the connecting ports (16) through connecting springs (17).
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