CN115353110B - Method for removing boron impurities in industrial silicon by silicomanganese slagging refining - Google Patents
Method for removing boron impurities in industrial silicon by silicomanganese slagging refining Download PDFInfo
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 71
- 239000010703 silicon Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000012535 impurity Substances 0.000 title claims abstract description 24
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 22
- 238000007670 refining Methods 0.000 title claims abstract description 17
- 229910000720 Silicomanganese Inorganic materials 0.000 title claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 70
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001301 oxygen Substances 0.000 claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 30
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 28
- 239000011572 manganese Substances 0.000 claims abstract description 28
- 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
- 239000002893 slag Substances 0.000 claims abstract description 18
- 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
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000005554 pickling Methods 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 235000008373 pickled product Nutrition 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 238000007789 sealing Methods 0.000 claims description 40
- 239000007789 gas Substances 0.000 claims description 16
- 230000007246 mechanism Effects 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- 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
- 230000015572 biosynthetic process Effects 0.000 claims 4
- 230000003028 elevating effect Effects 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 2
- 229910021422 solar-grade silicon Inorganic materials 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 11
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 229910004261 CaF 2 Inorganic materials 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 3
- 229920005591 polysilicon Polymers 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- -1 boron impurities Chemical compound 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
Classifications
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- 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: placing 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 heat of the silicon-manganese molten alloy for 2-4 hours to obtain the preserved silicon-manganese molten alloy; s3: adding CaO and CaF into the heat-insulating silicon-manganese molten alloy 2 Slag agent, obtaining reaction product; s4: continuously introducing oxygen into the reaction product, and slagging for 5-7 hours to obtain a slagging product; s5: and (3) carrying out mixed acid pickling on the slag-making product by hydrochloric acid and hydrofluoric acid, washing the pickled product to be neutral by water, and drying to obtain the high-purity silicon. The method realizes the high-efficiency purification of the industrial silicon, particularly for removing boron impurities in the silicon, can effectively reduce the boron impurities to the solar grade silicon standard, 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
Along with the increasing severity of environmental problems, the search for new renewable energy sources becomes one of the problems to be solved urgently at present, and solar energy has the inexhaustible natural advantages and the like, so that people are focused on the solar energy.
Solar cells have very broad prospects as one of the main applications of solar energy, wherein the solar cells are mainly made of polysilicon solar cells, and at present, the polysilicon used by the 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 is a metallurgical method, wherein the metallurgical method mainly comprises the methods of slag forming, vacuum refining, directional solidification and the like through different physical properties of impurities in silicon and through the combination of different technologies, the impurities are removed in a grading manner.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides a method for removing boron impurities in industrial silicon by silicomanganese slagging refining.
The invention provides a method for removing boron impurities in industrial silicon by slag-making and refining of silicomanganese, which comprises the following steps:
s1: placing 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 heat of the silicon-manganese molten alloy for 2-4 hours to obtain the preserved silicon-manganese molten alloy;
s3: adding CaO and CaF into the heat-insulating silicon-manganese molten alloy 2 Slag agent, obtaining reaction product;
s4: continuously introducing oxygen into the reaction product, and slagging for 5-7 hours to obtain a slagging product;
s5: and (3) carrying out mixed acid pickling on the slag-making product by hydrochloric acid and hydrofluoric acid, washing the pickled product to be neutral by water, and drying to obtain the high-purity silicon.
Preferably, in the step S1, the industrial silicon and the metal manganese are used in the form of silicon blocks and manganese blocks respectively, wherein the mass ratio of the addition amount of the industrial silicon to 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 heat preservation temperature in the step S2 is 1400-1500 ℃.
Preferably, in step S3, the CaO and CaF are mixed with each other 2 The CaO and CaF are respectively used in the form of powder with the purity of 2-3N 2 The mass ratio of the addition amount of (2) 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 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 arranged in the outer furnace body, a heating layer is arranged between the inner furnace body and the outer furnace body, a gas discharging pipe is fixedly arranged at the bottom in the outer furnace body, a plurality of gas ports are arranged on the gas discharging pipe, an arc-shaped pipe is arranged in the inner furnace body, the lower surface of the arc-shaped pipe is wedge-shaped, two connecting ports are arranged at two ends of the arc-shaped pipe and are respectively connected with two ends of the gas discharging 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 rotationally connected to one side of the sealing cover, the two connecting pipes slide through the sealing cover, and a lifting mechanism is arranged on the sealing cover;
the lifting mechanism is connected with two connecting pipes, two one sides of the upper ends of the connecting pipes are respectively communicated with an air pipe, oxygen enters into the connecting pipes and the arc-shaped pipes through the air pipes, oxygen in the arc-shaped pipes enters into the air release pipes through two connecting ports, the oxygen is released through an air port on the air release pipes, the air release pipes are rotationally connected with a rotating shaft, a first motor is arranged on a sealing cover, the first motor is fixedly connected with the rotating shaft through a driving end, a plurality of mixing shafts are fixedly connected to the rotating shaft, and industrial silicon, manganese metal, caO and CaF are mixed with one another 2 Slag agent is conveyed into the inner furnace body through the movable plate.
Preferably, the driving mechanism comprises a second motor, a threaded shaft and a linkage shaft, the second motor is fixedly arranged 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 in threaded sleeve connection with the threaded shaft, and the other two ends of the linkage shaft are fixedly connected with the upper ends of the two connecting pipes.
Preferably, both ends of the air release pipe are all rotationally connected with a second sealing slide block, a return spring is arranged at the rotational connection position, the lower end of the second sealing slide block is rotationally connected with the lower side of the air release pipe, the upper end of the second sealing slide block is provided with an inclined block, the inner walls of the two connecting ports are respectively in sliding clamping connection with the side surfaces of both ends of the air release pipe, a first sealing slide block is slidingly connected on the connecting ports, and the upper end of the first sealing slide block is fixedly connected with the connecting ports through a connecting spring.
Compared with the prior art, the invention has the beneficial effects that:
1. the method mainly uses industrial application, and can effectively purify industrial silicon, particularly boron impurities, and purify metallurgical grade silicon to solar grade silicon, firstly, putting industrial silicon and metal manganese into an intermediate frequency furnace for smelting and preserving heat for a period of time, then adding a slag agent into the intermediate frequency furnace, introducing oxygen into the bottom of the intermediate frequency furnace, and finally, carrying out acid cleaning treatment on the silicon cast ingot after slagging.
2. Industrial silicon, manganese metal, caO and CaF 2 The slag agent is put into the inner furnace body through the opening of the movable plate, the heating layer heats the inner furnace body to enable internal substances to react with each other, the arc-shaped pipe is moved downwards through the driving mechanism, two ends of the arc-shaped pipe are respectively communicated with two ends of the air release pipe, oxygen passes through the air delivery pipe, the arc-shaped pipe and the air release pipe, the oxygen is delivered from the bottom of the medium frequency furnace through each air port, the oxygen passes through each substance from bottom to top due to self gravity, the full contact of the materials and the oxygen is effectively ensured, the oxygen can start a first motor in the process of reacting with the substances, the first motor drives the rotating shaft and each mixing shaft through the driving end to rotate, the internal reactants are fully mixed to enable the internal reactants to fully react, the whole medium frequency furnace is driven to rotate through the air cylinder, and the substances after the reaction are poured out through the movable plate.
Drawings
FIG. 1 is a flow chart of a method for removing boron impurities in industrial silicon by silicomanganese slagging refining;
FIG. 2 is a schematic structural view of an intermediate frequency furnace;
FIG. 3 is a schematic diagram of the internal structure of the intermediate frequency furnace;
fig. 4 is a schematic view of a partial structure of the intermediate frequency furnace.
In the figure: the device 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 transmission 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 release pipe 14, a first sealing slide block 15, a connecting port 16, a connecting spring 17, a gas port 18, a bevel block 19 and a second sealing slide block 20.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments.
Embodiment one:
referring to fig. 1-4, a method for removing boron impurities in industrial silicon by silicomanganese slagging refining comprises the following steps:
s1: 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%) are put into an intermediate frequency furnace, the temperature in the furnace is increased to 1600 ℃, 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 heat of the silicon-manganese molten alloy for 4 hours to obtain the preserved silicon-manganese molten alloy, wherein the heat preservation temperature is 1400-1500 ℃;
s3: 15kg CaO and 1.5kg CaF are added into the heat-preserving silicon-manganese molten alloy 2 Slag, caO and CaF 2 The pure components are respectively used in the form of powder, and the purity is 2-3N;
s4: continuously introducing oxygen into the intermediate frequency furnace at a flow rate of 400ml/min, and slagging for 5 hours to obtain a slagging product;
s5: and (3) pickling the silicon ingot after slagging by using mixed acid consisting of 3mol/L hydrochloric acid and 3mol/L hydrofluoric acid, pickling for 5 hours at 70 ℃, filtering, and cleaning with deionized water to produce the silicon ingot.
Silicon purity after pickling was 99.99978% with a boron impurity content of 0.15ppmw, as determined by Glow Discharge Mass Spectrometry (GDMS).
The intermediate frequency furnace comprises an outer furnace body 1 and an inner furnace body 2, wherein 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, a gas release pipe 14 is fixedly arranged at the bottom in the outer furnace body 1, a plurality of gas ports 18 are arranged on the gas 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 connecting ports 16 are arranged at two ends of the arc-shaped pipe 13, the two connecting ports 16 are respectively connected with two ends of the gas release 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 rotationally 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;
the lifting mechanism is connected with two connecting pipes 6, one side of the upper ends of the two connecting pipes 6 is communicated with an air pipe 7, oxygen enters into the connecting pipes 6 and an arc-shaped pipe 13 through the air pipe 7, oxygen in the arc-shaped pipe 13 enters into a deflation pipe 14 through two connecting ports 16, the oxygen is released through an air port 18 on the deflation pipe 14, a rotating shaft 11 is rotationally connected on the deflation pipe 14, a first motor 8 is mounted on a sealing cover 4, the first motor 8 is fixedly connected with the rotating shaft 11 through a driving end, a plurality of mixing shafts 12 are fixedly connected on the rotating shaft 11, and industrial silicon, metal manganese, caO and CaF are fixedly connected with one another 2 Slag agent is conveyed into the inner furnace body 2 through the movable plate 3.
Industrial silicon, manganese metal, caO and CaF can be obtained by rotating the movable plate 3 2 Slag is put into the inner furnace body 2 through the opening of the movable plate 3, the heating layer heats the inner furnace body 2 to enable internal substances to react with each other, the arc-shaped pipe 13 is moved downwards through the driving mechanism, two ends of the arc-shaped pipe 13 are respectively communicated with two ends of the air release pipe 14, oxygen is conveyed out through the air conveying pipe 7, the connecting pipe 6, the arc-shaped pipe 13 and the air release pipe 14 and through the air ports 18, oxygen is conveyed from the bottom of the intermediate frequency furnace, the oxygen penetrates through all substances from bottom to top due to self gravity, the sufficient contact between the materials and the oxygen is effectively ensured, the first motor 8 can be started in the process of reacting with the substances, the first motor 8 drives the rotating shaft 11 and all the mixing shafts 12 to rotate through the driving end to mix the internal reactants, the internal reactants are sufficiently mixed to enable the internal reactants to react, and the whole intermediate frequency furnace is driven through the air cylinder to perform the reactionAnd rotating, and pouring out the reacted substances through the movable plate 3.
The driving mechanism comprises a second motor 9, a threaded shaft 5 and a linkage shaft 10, wherein the second motor 9 is fixedly arranged 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 inner industrial silicon, manganese metal, caO and CaF are fixedly connected with each other 2 When slag agent is mixed with each other to react, in order to avoid the reaction influence of the arc tube 13, the arc tube 13 is moved upwards, the second motor 9 drives the threaded shaft 5 to rotate through the driving end, the linkage shaft 10 limits the angle position due to the two connecting pipes 6, and then the threaded shaft 5 drives the linkage shaft 10 to move up and down along with the rotation of the threaded shaft 5, 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 both rotationally connected with a second sealing slide block 20, a return spring is arranged at the rotational connection position, the lower end of the second sealing slide block 20 is rotationally connected with the lower side of the air release pipe 14, the upper end of the second sealing slide block 20 is provided with an inclined block 19, the inner walls of two connecting ports 16 are respectively in sliding clamping connection with the side surfaces of the two ends of the air release pipe 14, a first sealing slide block 15 is slidingly connected on the connecting ports 16, and the upper end of the first sealing slide block 15 is fixedly connected with the connecting ports 16 through a connecting spring 17;
when the arc tube 13 moves downwards, the two connecting ports 16 are vertically aligned with the two ends of the air release tube 14, when the connecting ports 16 move downwards, the lower ends of the connecting ports 16 are in contact with the inclined blocks 19, the inclined blocks 19 incline along with the downward movement of the connecting ports 16 due to the inclined surfaces of the inclined blocks 19, the inclined blocks 19 drive the second sealing slide blocks 20 to incline, the lower ends of the first sealing slide blocks 15 are abutted against the air release tube 14 in the inclining process, the connecting ports 16 are gradually aligned and communicated with the left and right ends of the air release tube 14, so that oxygen can be introduced into the arc tube 13 through the connecting tubes 6, enter the air release tube 14 and are output through the air ports 18, oxygen is introduced from the bottom of the inner furnace body 2, the oxygen is in full contact with all materials, the reaction is facilitated, when the connecting ports 16 are separated from the air release tube 14, the two ends of the air release tube 14 are blocked by the second sealing slide blocks 20 under the action of the return spring, and meanwhile, the connecting ports 16 are blocked by the first sealing slide blocks 15 under the action of the elasticity of the connecting springs 17.
Embodiment two:
referring to fig. 1-4, a method for removing boron impurities in industrial silicon by silicomanganese slagging refining comprises the following steps:
s1: 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%) are put into an intermediate frequency furnace, the temperature in the furnace is raised to 1750 ℃, 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 heat of the silicon-manganese molten alloy for 3 hours to obtain the preserved silicon-manganese molten alloy;
s3: 15kg CaO and 1.5kg CaF are added into the heat-preserving silicon-manganese molten alloy 2 Slag, caO and CaF 2 The pure components are respectively used in the form of powder, and the purity is 2-3N;
s4: continuously introducing oxygen into the intermediate frequency furnace at a flow rate of 300ml/min, and slagging for 5 hours to obtain a slagging product;
s5: and (3) pickling the silicon ingot after slagging by using mixed acid consisting of 2mol/L hydrochloric acid and 3mol/L hydrofluoric acid, pickling for 6 hours at 80 ℃, filtering, and cleaning with deionized water to obtain the silicon ingot.
The silicon purity after pickling was 99.99948% by Glow Discharge Mass Spectrometry (GDMS), wherein the boron impurity content was 0.11ppmw, and the structure and method of use of the intermediate frequency furnace were the same as those of the first embodiment.
Embodiment III:
referring to fig. 1-4, a method for removing boron impurities in industrial silicon by silicomanganese slagging refining comprises the following steps:
s1: 15kg of industrial silicon (purity is 99.8%) to be purified and 1.5kg of metal manganese blocks (purity is 99.99%) are put into an intermediate frequency furnace, the temperature in the furnace is raised to 1550 ℃, 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 heat of the silicon-manganese molten alloy for 3 hours to obtain the preserved silicon-manganese molten alloy;
s3: 15kg CaO and 1.5kg CaF are added into the heat-preserving silicon-manganese molten alloy 2 Slag, caO and CaF 2 The pure components are respectively used in the form of powder, and the purity is 2-3N;
s4: continuously introducing oxygen into the intermediate frequency furnace at a flow rate of 200ml/min, and slagging for 6 hours to obtain a slagging product;
s5: and (3) pickling the silicon ingot after slagging by using mixed acid consisting of 1mol/L hydrochloric acid and 2mol/L hydrofluoric acid, pickling for 3 hours at 50 ℃, filtering, and cleaning with deionized water to obtain the silicon ingot.
The silicon purity after pickling was 99.99943% as determined by Glow Discharge Mass Spectrometry (GDMS), wherein the boron impurity content was 0.08ppmw, and the structure and method of use of the intermediate frequency furnace were the same as those of the first embodiment.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (6)
1. The method for removing boron impurities in industrial silicon by silicomanganese slagging refining is characterized by comprising the following steps:
s1: placing 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: carrying out heat preservation on the silicon-manganese molten alloy for 2-4 h to obtain a heat-preserved silicon-manganese molten alloy;
s3: adding CaO and CaF into the heat-insulating silicon-manganese molten alloy 2 Slag agent, obtaining reaction product;
s4: continuously introducing oxygen into the reaction product, and slagging 5-7 and h to obtain a slagging product;
s5: carrying out mixed acid pickling on the slag-making product by hydrochloric acid and hydrofluoric acid, washing the pickled product to be neutral by water, and drying to obtain high-purity silicon;
the intermediate frequency furnace comprises an outer furnace body (1) and an inner furnace body (2), wherein 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), a gas release pipe (14) is fixedly arranged at the bottom in the outer furnace body (1), a plurality of gas ports (18) are arranged on the gas 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, connecting ports (16) are formed in two ends of the arc-shaped pipe (13) and are respectively connected with two ends of the gas release pipe (14), two connecting pipes (6) are communicated with each other on the arc-shaped pipe (13), a sealing cover (4) is arranged at the upper end of the outer furnace body (1), a movable plate (3) is rotationally connected to one side of the sealing cover (4), 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), two one side of connecting pipe (6) upper end all is linked together 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 bleed pipe (14) through two connector (16), and oxygen is released through gas port (18) on bleed pipe (14), rotate on bleed pipe (14) and be connected with pivot (11), install first motor (8) on sealed lid (4), first motor (8) pass through drive end and pivot (11) fixed connection, still fixedly connected with a plurality of hybrid shaft (12) on pivot (11), industrial silicon, metal manganese, caO, caF 2 Slag agent is conveyed into the inner furnace body (2) through the movable plate (3);
the driving mechanism comprises a second motor (9), a threaded shaft (5) and a linkage shaft (10), wherein the second motor (9) is fixedly arranged 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), and the other two ends of the linkage shaft (10) are fixedly connected with the upper ends of the two connecting pipes (6);
the utility model discloses a gas-discharging pipe, including gas-discharging pipe (14), gas-discharging pipe, connecting port (16), sealing slide (15), connecting spring (17) and connecting port (16) fixed connection are passed through to the both ends of gas-discharging pipe (14) all rotate and are connected with second sealing slide (20), and rotate the junction and be provided with back power spring, the lower extreme of second sealing slide (20) is rotated with the downside of gas-discharging pipe (14) and is connected, the upper end of second sealing slide (20) is provided with sloping block (19), two the inner wall of connecting port (16) respectively with the both ends side slip joint of gas-discharging pipe (14), sliding connection has first sealing slide (15) on connecting port (16), the upper end of first sealing slide (15).
2. The method for removing boron impurities in industrial silicon by slag formation and refining of silicon and manganese 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 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 by slag formation and refining of silicon and manganese according to claim 1, wherein the heat preservation temperature in the 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, said CaO and CaF are 2 The CaO and CaF are used in the form of powder with the purity of 2-3N respectively 2 The mass ratio of the addition amount of (2) is 1 (0.1-0.15).
5. The method for removing boron impurities in industrial silicon by slag formation and refining of silicon and manganese according to claim 1, wherein the flow rate of the introduced oxygen in the step S4 is 200-400 ml/min.
6. The method for removing boron impurities in industrial silicon by slag formation and refining of silicon and manganese according to claim 1, wherein 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 time is 3-6 h.
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