CN110304634A - A kind of method of energy-efficient purifying industrial silicon - Google Patents
A kind of method of energy-efficient purifying industrial silicon Download PDFInfo
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- CN110304634A CN110304634A CN201910605441.7A CN201910605441A CN110304634A CN 110304634 A CN110304634 A CN 110304634A CN 201910605441 A CN201910605441 A CN 201910605441A CN 110304634 A CN110304634 A CN 110304634A
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 70
- 239000010703 silicon Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 46
- 239000000956 alloy Substances 0.000 claims abstract description 46
- 238000007711 solidification Methods 0.000 claims abstract description 33
- 230000008023 solidification Effects 0.000 claims abstract description 33
- 238000007670 refining Methods 0.000 claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000004321 preservation Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 230000005674 electromagnetic induction Effects 0.000 claims abstract description 9
- 238000007664 blowing Methods 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 34
- 239000012298 atmosphere Substances 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 21
- 229910052786 argon Inorganic materials 0.000 claims description 17
- 230000001681 protective effect Effects 0.000 claims description 11
- 229920001296 polysiloxane Polymers 0.000 claims description 10
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 7
- 229920005591 polysilicon Polymers 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910021364 Al-Si alloy Inorganic materials 0.000 claims description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 3
- 230000005496 eutectics Effects 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 230000008676 import Effects 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910000632 Alusil Inorganic materials 0.000 abstract description 20
- 239000012535 impurity Substances 0.000 abstract description 13
- 239000004411 aluminium Substances 0.000 abstract description 11
- 238000000926 separation method Methods 0.000 abstract description 8
- 239000004484 Briquette Substances 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 5
- 238000005554 pickling Methods 0.000 abstract description 4
- -1 aluminium siloxane Chemical class 0.000 abstract description 2
- 238000002955 isolation Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 2
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 15
- 238000001514 detection method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000010183 spectrum analysis Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005672 electromagnetic field Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006023 eutectic alloy Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 239000010891 toxic waste Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/026—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
A kind of method of energy-efficient purifying industrial silicon.The present invention discloses a kind of method for efficiently separating refined silicon, belongs to silicon purification & isolation technical field.The method of the invention is that hypereutectic al-si master alloy is made after mixing industrial silico briquette with industrial aluminum；Obtained mixing hypereutectic al-si master alloy is heated after alusil alloy parent whole melting and heat preservation with intermediate frequency electromagnetic induction furnace, solidification, blowing out after the completion of directional solidification are oriented to the hypereutectic al-si melt with the drop-down speed much higher than conventional rate.Enrichment of Si phase region and alusil alloy are cut separation after sample is cooling, take out Enrichment of Si phase region.Due to the refining of aluminium siloxane solvent can effective purifying industrial silicon, pass through and strengthen silicon mutually from the separation of hypereutectic al-si melt, the primary silicon after being purified forms enrichment；The impurity of the alusil alloy being mingled in primary silicon rich region and enrichment in the alloy can be removed by conventional pickling.
Description
Technical field
The present invention relates to a kind of methods of energy-efficient purifying industrial silicon, belong to silicon purification & isolation technical field.
Background technique
Current census's explosion, numerous population make resource gradually move towards barren.Meanwhile on the earth there are numerous can be again
Production-goods source, how to make good use of these renewable resources becomes the common recognition of the mankind.In all renewable resources, due to solar energy
The advantages that with distribution and its extensively, no reserves upper limit can operate with the outer space, and collection of energy is convenient etc. is by favor.Currently
The solar battery used mainly based on silicon substrate, and the purity strong influence of the polysilicon as raw material solar energy
The transformation efficiency of battery.Therefore, to go out high performance solar battery, be necessarily required to by polycrystalline silicon impurity remove so that
Its purity is used for solar battery not less than 99.9999%.
Currently, the material that solar battery uses is mainly polysilicon, it is mainly derived from the improvement west being widely used
Men Zifa.This is owned by France in chemical method, and advantage is mainly technical maturity, and the purification of obtained silicon is higher.The disadvantage is that yield compared with
It is low, it produces in pilot process and generates a large amount of toxic waste liquid and exhaust gas, there is the disadvantages of high energy consumption, high pollution.Another kind is raw
The method for producing polysilicon is commonly called as physical method, it is characterized in that premised on silicon main nature is constant, using pickling, and directional solidification, very
The features such as sky refining, is purified.Its advantage is mainly yield height, advantages of environment protection.
Aluminium siloxane solvent refining in metallurgy method is abundant with material source, and it is lower that silicon mutually purifies temperature, and aluminium is as good
Impurity element adsorbent, show huge potentiality.The method be it is a kind of can be under lower temperature (lower than 1000 DEG C)
Realize that the method for strengthening industrial silicon removal of impurities, this method have equipment requirement is simple, operation is easy, is suitble to scale industrial production etc.
Advantage.Chinese patent application (CN103343384A) proposes to first pass through on aluminium silicon refined base adds alternating magnetic field outside, while
Upper end feed then realizes industry in conjunction with the method for acidleach processing to realize the continuous casting process that primary silicon purification produces
The removing of impurity in silicon.It is more general than traditional although this method is significant to the centrifugation of alusil alloy and primary silicon after refining
Logical directional solidification good separating effect, but according to existing research, it separates and is not thorough, Enrichment of Si phase region includes a large amount of aluminium
Mutually it is mingled with, this will cause a large amount of acid solution to waste in subsequent acid cleaning process, meanwhile, the drop-down speed which uses
It is lower, significantly limit energy-saving index.Therefore, researcher still needs to improve the technology to reach the mesh for efficiently separating refined silicon
's.
Summary of the invention
For the above-mentioned problems of the prior art and deficiency, the present invention provides a kind of side for efficiently separating refiner silicon
Method.The additional alternating electromagnetic field of low frequency in this method use realizes hypereutectic al-si melt in conjunction with Rapid Directional Solidification
The separation of silicon phase and alusil alloy after purification；The invention is realized by the following technical scheme.
A method of refiner silicon being efficiently separated, specific steps include the following:
(1) industrial aluminum and industrial silicon are uniformly mixed, hypereutectic al-si master alloy are made after melting, wherein silicone content is lower than
45wt.%；
(2) master alloy that step (1) obtains is put into electromagnetic induction furnace and is heated, import protective atmosphere, into furnace with 30 ~ 35
DEG C/min heating rate is warming up to 800 ~ 1000 DEG C, 0.5h ~ 10h is kept the temperature, after heat preservation, to be higher than the lower pulling rate of conventional rate
2.4 ~ 60mm/min of degree is oriented solidification to melt, and after directional solidification, alloy melt is naturally cooling to room with furnace
Temperature has protective atmosphere protection in temperature-fall period, until obtaining the polycrystalline after cocrystallized Al-Si alloy and refining after temperature-fall period
Silicon；
(3) the directional solidification sample for obtaining step (2) carries out lift-off processing, and the polysilicon and eutectic aluminum-silicon after collecting refining close
Gold.
Preferably, the electromagnetic induction furnace frequency arrived used in step (2) of the present invention is intermediate frequency or Frequency, and frequency is
1~10kHz。
Preferably, protective atmosphere is argon gas or nitrogen in step (2) of the present invention, and blowing atmosphere pressures are 105Pa, protection
The flow of gas is 30 ~ 500ml/min.
The beneficial effects of the present invention are:
(1) the method for the invention, can be efficient in a manner of low frequency or the additional alternating electromagnetic field combination high speed directional solidification of intermediate frequency
Silicon phase and alusil alloy in energy-efficient separation hypereutectic al-si melt.
(2) present invention gained Enrichment of Si phase region silicone content is higher than 70wt.% or more.
(3) the method for the present invention is easy to operate, practical, and metallic aluminium can be recycled, and will not improve ready-made.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) photograph of the raw materials used metallurgical grade silicon of embodiment under different multiples: (a) 50 times, (b) 100 times.
Cooling sample micro-structure diagram after the aluminium silicon refining that Fig. 2 is Al-45wt.%Si described in embodiment 1.
Fig. 3 is the micro-structure diagram and EDS power spectrum elemental analysis figure that hypereutectic al-si refines sample in embodiment 1: (a) micro-
See structure chart；(b) the EDS energy spectrum analysis of point 1；(c) the EDS energy spectrum analysis of point 2；(d) the EDS energy spectrum analysis of point 3.
Fig. 4 is the scanning electron microscope (SEM) photograph of the alloyed region in the Enrichment of Si phase region and top of gained sample in embodiment 1.
Fig. 5 is the EPMA-mapping scan element distribution map in the Enrichment of Si phase region of 1 gained sample of embodiment.
Fig. 6 is (a) gained sample drawing according to the method for embodiment 1；(b) Enrichment of Si phase sector scanning electron microscope in sample.
Fig. 7 is the scanning electron microscope (SEM) photograph and spectroscopy detection result figure according to Enrichment of Si phase region obtained by embodiment.
What Fig. 8 was that a-c respectively indicates is used in embodiment 2-4 much higher than sample obtained by common directional solidification rates
Figure；
Fig. 9 is the scanning electron microscope (SEM) photograph in the Enrichment of Si phase region that a-c respectively indicates sample in embodiment 2-4.
Figure 10 is in (a) resistance furnace with gained sample under 0.6mm/min rate；It (b) is 1 gained sample of the embodiment of the present invention
Figure.
Figure 11 is that (a) is 30kHz electromagnetic induction furnace gained sample under 0.6mm/min rate；It (b) is the embodiment of the present invention
1 gained sample drawing.
Figure 12 be comparative example 2 in using 30kHz under 0.6mm/min rate gained sample different location at silicone content with
XRFS detection gained silicone content at obtained sample different location at sample different location obtained by 1 gained (3kHz) of the embodiment of the present invention
Figure.
Specific embodiment
With reference to the accompanying drawing and specific embodiment the invention will be further described, but protection scope of the present invention is not
It is limited to the content.
Embodiment 1
(1) industrial aluminum and industrial silicon are uniformly mixed, heating carries out heat preservation operation after refining half an hour, is made after melting hypereutectic
Al-45wt.%Si master alloy；Primary industry silicon is detected using scanning electron microscope, acquired results are as shown in Figure 1, can from Fig. 1
To see a large amount of impurity element (the predominantly high atomic weight metal impurities of brilliant white, Fe, Ti, Ca etc.) Dispersed precipitates in industrial silicon
In industrial silicon.
(2) master alloy that step (1) obtains is put into electromagnetic induction furnace, progress vacuum pumping first vacuumizes behaviour
Work imports argon gas into furnace after terminating, and is then heated (frequency 3kHz), is warming up to 1000 with 30 DEG C/min heating rate
DEG C, 30min is kept the temperature, after heat preservation, the sample in the stage is cut, carries out scanning electron microscope detection and EDS energy after polishing
Spectrum detection, is as a result shown in Fig. 2 and Fig. 3, and a large amount of impurity preservations are being analysed after it can be seen that industrial silicon and industrial aluminum refining in result figure
In the alusil alloy around primary silicon out, and the primary silicon of obtained en plaque is then that purity is higher is purified silicon, therefore
In the refining process of industrial aluminum and silicon, industrial silicon is purified.After heat preservation, flow is being imported as 100ml/min guarantor
(atmosphere is argon gas, and blowing atmosphere pressures are 10 under shield atmosphere5Pa), with the drop-down rate higher than common directional solidification rates
2.4mm/min is oriented solidification to aluminium silicon melt, and after directional solidification, alloy melt is naturally cooling to room with furnace
Temperature has argon atmosphere protection in temperature-fall period, until obtaining the polycrystalline after cocrystallized Al-Si alloy and refining after temperature-fall period
Silicon.Gained Enrichment of Si phase region and eutectic alloy region are scanned Electronic Speculum detection, as a result as shown in Figure 4.Fig. 4 a is shown just
Crystal silicon forms good enrichment, and the impurity element of visible a small amount of brilliant white is mixed between primary silicon.And the alloy on top
Region is as shown in Fig. 4 b, it can be seen that a large amount of brilliant white impurity element.The scanning electron microscope (SEM) photograph of two different zones illustrates this hair
The primary silicon purified after refining can be effectively enriched with by bright the method in the bottom of sample, the subsequent silicon to after refining
Mutually carrying out conventional pickling may be used as the raw material of manufacture silica-based solar cell.And it is rich in the alusil alloy of a large amount of impurity elements
It can be used for the casting alusil alloy of less demanding to metallicity
(3) the directional solidification sample for obtaining step (2) carries out lift-off processing, and the polysilicon and eutectic aluminum-silicon after collecting refining close
Gold.To the EPMA-mapping detection that gained Enrichment of Si phase region carries out, from fig. 5, it is seen that Enrichment of Si phase region silicon contains
Amount has reached very high purity, and residual impurity is distributed in the aluminium alloy between the primary silicon after being mixed in refining, by normal
The pickling of rule can remove.Preferable separating effect can greatly reduce the acid solution in subsequent acid cleaning process, the wave of silicon and aluminium
Take.
Drop-down rate used in the present embodiment is 2.4mm/min, and refined silicon and alusil alloy have obtained good separation, institute
Obtaining sample Enrichment of Si phase region silicone content is 80wt.% or more；Fig. 6 is shown using using obtained by the method in claim
The separation sample of the primary silicon and alusil alloy that arrive, what Fig. 6 b was indicated is its micro-structure diagram；And what Fig. 7 was indicated is using EDS
Power spectrum is as a result, a small amount of impurity element is only contained in Enrichment of Si phase region as we can see from the figure.
Embodiment 2
A kind of method of energy-efficient purifying industrial silicon, specific steps include the following:
(1) Al-45wt.%Si master alloy is configured by industrial silico briquette and commercial-purity aluminium.
(2) master alloy that step (1) obtains is placed in graphite crucible, in vacuum electromagnetic induction furnace, argon gas always
Under conditions of being passed through, hypereutectic master alloy temperature is heated to 1000 DEG C and keeps the temperature 30 minutes.
(3) the aluminium silicon melt after step (2) heat preservation refining is oriented solidification processing, is 100ml/ importing flow
(atmosphere is argon gas, and blowing atmosphere pressures are 10 under min protective atmosphere5Pa), molten to aluminium silicon with the orientation drop-down rate of 6mm/min
Body is oriented solidification.After directional solidification, aluminium silicon melt is naturally cooling to room temperature with furnace temperature, has gas in temperature-fall period
Atmosphere (atmosphere is argon gas), until temperature-fall period terminates Enrichment of Si phase region and alusil alloy sample.
(4) the directional solidification sample that step (3) obtains is subjected to Enrichment of Si phase region and alusil alloy region is removed.
Drop-down rate used in the present embodiment is 6mm/min, and gained sample silicon phase silicone content is 70wt.% or more.
Embodiment 3
A kind of method of energy-efficient purifying industrial silicon, specific steps include the following:
(1) Al-45wt.%Si master alloy is configured by industrial silico briquette and commercial-purity aluminium.
(2) master alloy that step (1) obtains is placed in graphite crucible, in vacuum electromagnetic induction furnace, argon gas always
Under conditions of being passed through, hypereutectic master alloy temperature is heated to 1000 DEG C and keeps the temperature 30 minutes.
(3) the aluminium silicon melt after step (2) heat preservation refining is oriented solidification processing, is 100ml/ importing flow
(atmosphere is argon gas, and blowing atmosphere pressures are 10 under min protective atmosphere5Pa), with the orientation drop-down rate of 12mm/min to aluminium silicon
Melt is oriented solidification.After directional solidification, aluminium silicon melt is naturally cooling to room temperature with furnace temperature, has in temperature-fall period
Atmosphere (atmosphere is argon gas), until temperature-fall period terminates Enrichment of Si phase region and alusil alloy sample.
(4) the directional solidification sample that step (3) obtains is subjected to Enrichment of Si phase region and alusil alloy region is removed.
Drop-down rate used in the present embodiment is 12mm/min, and gained sample silicon phase silicone content is 65wt.% or more.
Embodiment 4
A kind of method of energy-efficient purifying industrial silicon, specific steps include the following:
(1) Al-45wt.%Si master alloy is configured by industrial silico briquette and commercial-purity aluminium.
(2) master alloy that step (1) obtains is placed in graphite crucible, in vacuum electromagnetic induction furnace, argon gas always
Under conditions of being passed through, hypereutectic master alloy temperature is heated to 1000 DEG C and keeps the temperature 30 minutes.
(3) the aluminium silicon melt after step (2) heat preservation refining is oriented solidification processing, is 100ml/ importing flow
(atmosphere is argon gas, and blowing atmosphere pressures are 10 under min protective atmosphere5Pa), with the orientation drop-down rate of 18mm/min to aluminium silicon
Melt is oriented solidification.After directional solidification, aluminium silicon melt is naturally cooling to room temperature with furnace temperature, has in temperature-fall period
Atmosphere (atmosphere is argon gas), until temperature-fall period terminates Enrichment of Si phase region and alusil alloy sample.
(4) Enrichment of Si phase region in directional solidification sample that step (3) obtains and alusil alloy region are removed.
Drop-down rate used in the present embodiment is 18mm/min, and gained sample silicon phase silicone content is 60wt.% or more.Implement
The result figure of 2 ~ embodiment of example, 4 gained sample is respectively as shown in figure 8, Fig. 9 respectively indicates sweeping for corresponding Enrichment of Si phase region
Electron microscope is retouched, as can be seen from the figure primary silicon has mutually obtained good separation.
Comparative example 1
Industrial silicon and commercial-purity aluminium composition Al-45wt.%Si master alloy are placed directly in resistance furnace and carry out melt process, in argon
Under gas atmosphere protection, 1000 DEG C carry out heat preservation 30min, are then oriented drop-down with 0.6mm/min rate, after drop-down silicon mutually simultaneously
It is not enriched with.Drop-down rate is 0.6mm/min, and the mutually not formed enrichment of silicon, acquired results are as shown in Figure 10.
Comparative example 2
(1) Al-45wt.%Si master alloy is configured by industrial silico briquette and commercial-purity aluminium；
(2) master alloy that step (1) obtains is placed in graphite crucible, in 30kHz alternating electromagnetism induction furnace, argon gas always
Under conditions of being passed through, hypereutectic master alloy temperature is heated to 550 DEG C -1000 DEG C.
(3) the aluminium silicon melt after step (2) heat preservation refining is oriented solidification processing, is 100ml/ importing flow
(atmosphere is argon gas, and blowing atmosphere pressures are 10 under min protective atmosphere5Pa), with the orientation drop-down rate of 0.6mm/min to aluminium silicon
Melt is oriented solidification；After directional solidification, aluminium silicon melt is naturally cooling to room temperature with furnace temperature, has in temperature-fall period
Atmosphere (atmosphere is argon gas), until temperature-fall period terminates Enrichment of Si phase region and alusil alloy sample；Comparison is shown in Figure 11 b
The sample drawing that example 2 and the method for the invention obtain.
(4) the directional solidification sample that step (3) obtains is subjected to Enrichment of Si phase region and alusil alloy region is removed.
Drop-down rate used in the present embodiment is only 0.6mm/min, and the trend of gradual change is presented in gained sample silicone content, not
Good separating effect is formed, as shown in Figure 11；And by primary silicon phase and alusil alloy in sample obtained by the method for the invention
Mutually realize good separation；To realize the purpose for efficiently separating refined silicon.
Claims (3)
1. a kind of method of energy-efficient purifying industrial silicon, which is characterized in that specific steps include the following:
(1) industrial aluminum and industrial silicon are uniformly mixed, hypereutectic al-si master alloy are made after melting, wherein silicone content is lower than
45wt.%；
(2) master alloy that step (1) obtains is put into electromagnetic induction furnace and is heated, import protective atmosphere, into furnace with 30 ~ 35
DEG C/min heating rate is warming up to 800 ~ 1000 DEG C, 0.5h ~ 10h is kept the temperature, after heat preservation, to be higher than the lower pulling rate of conventional rate
2.4 ~ 60mm/min of degree is oriented solidification to melt, and after directional solidification, alloy melt is naturally cooling to room with furnace
Temperature has protective atmosphere protection in temperature-fall period, until obtaining the polycrystalline after cocrystallized Al-Si alloy and refining after temperature-fall period
Silicon；
(3) the directional solidification sample for obtaining step (2) carries out lift-off processing, and the polysilicon and eutectic aluminum-silicon after collecting refining close
Gold.
2. the method for purifying industrial silicon according to claim 1, it is characterised in that: the electromagnetism sense arrived used in step (2)
Answering furnace frequency is intermediate frequency or Frequency, and frequency is 1 ~ 10kHz.
3. the method for purifying industrial silicon according to claim 1, it is characterised in that: in step (2) protective atmosphere be argon gas or
Person's nitrogen, blowing atmosphere pressures are 105Pa, the flow of protective gas are 30 ~ 500ml/min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333073A (en) * | 2020-03-16 | 2020-06-26 | 昆明理工大学 | Method for obtaining bulk silicon from high-silicon aluminum alloy |
| CN111762786A (en) * | 2020-07-13 | 2020-10-13 | 昆明理工大学 | Method for removing impurity elements by controllable solidification of silicon melt |
| CN112456499A (en) * | 2020-12-11 | 2021-03-09 | 昆明理工大学 | Method for preparing high-purity silicon by using silicon cutting waste |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85201157U (en) * | 1985-04-01 | 1986-06-11 | 大连工学院 | Aluminium directional solidifying and purifying equipment |
| CN101109046A (en) * | 2007-08-17 | 2008-01-23 | 东北大学 | Alloying method for restraining hypereutectic aluminum-silicon alloy silicon gross segregation |
| CN101274359A (en) * | 2007-03-28 | 2008-10-01 | 宝山钢铁股份有限公司 | Electromagnetic centrifugal casting quick-cutting steel composite roller operational layer material |
| CN101307487A (en) * | 2007-05-16 | 2008-11-19 | 佳科太阳能硅(厦门)有限公司 | Directional solidification method and its device for continuous production for polycrystalline silicon ingot |
| CN101733395A (en) * | 2008-11-19 | 2010-06-16 | 中国科学院金属研究所 | High-temperature gradient directional solidification equipment |
| CN102373351A (en) * | 2011-10-26 | 2012-03-14 | 昆明理工大学 | Method for preparing high-purity silicon and aluminum silicon alloy by electromagnetic method |
| CN103072992A (en) * | 2013-01-30 | 2013-05-01 | 昆明理工大学 | Preparation method of high-purity silicon |
| CN103343384A (en) * | 2013-07-08 | 2013-10-09 | 昆明理工大学 | Device for separating hypereutectic aluminum-silicon alloy and application of device |
| CN104928486A (en) * | 2015-06-11 | 2015-09-23 | 重庆大学 | Method for separating out silicon and aluminum-silicon alloy |
| WO2017072655A1 (en) * | 2015-10-29 | 2017-05-04 | Bay Zoltán Alkalmazott Kutatási Közhasznú Nonprofit Kft. Mérnöki Divízió | Method for the enrichment and separation of silicon crystals from a molten metal for the purification of silicon |
| CN108546987A (en) * | 2018-07-26 | 2018-09-18 | 孟静 | The method of purifying solar energy level polysilicon |
-
2019
- 2019-07-05 CN CN201910605441.7A patent/CN110304634A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85201157U (en) * | 1985-04-01 | 1986-06-11 | 大连工学院 | Aluminium directional solidifying and purifying equipment |
| CN101274359A (en) * | 2007-03-28 | 2008-10-01 | 宝山钢铁股份有限公司 | Electromagnetic centrifugal casting quick-cutting steel composite roller operational layer material |
| CN101307487A (en) * | 2007-05-16 | 2008-11-19 | 佳科太阳能硅(厦门)有限公司 | Directional solidification method and its device for continuous production for polycrystalline silicon ingot |
| CN101109046A (en) * | 2007-08-17 | 2008-01-23 | 东北大学 | Alloying method for restraining hypereutectic aluminum-silicon alloy silicon gross segregation |
| CN101733395A (en) * | 2008-11-19 | 2010-06-16 | 中国科学院金属研究所 | High-temperature gradient directional solidification equipment |
| CN102373351A (en) * | 2011-10-26 | 2012-03-14 | 昆明理工大学 | Method for preparing high-purity silicon and aluminum silicon alloy by electromagnetic method |
| CN103072992A (en) * | 2013-01-30 | 2013-05-01 | 昆明理工大学 | Preparation method of high-purity silicon |
| CN103343384A (en) * | 2013-07-08 | 2013-10-09 | 昆明理工大学 | Device for separating hypereutectic aluminum-silicon alloy and application of device |
| CN104928486A (en) * | 2015-06-11 | 2015-09-23 | 重庆大学 | Method for separating out silicon and aluminum-silicon alloy |
| WO2017072655A1 (en) * | 2015-10-29 | 2017-05-04 | Bay Zoltán Alkalmazott Kutatási Közhasznú Nonprofit Kft. Mérnöki Divízió | Method for the enrichment and separation of silicon crystals from a molten metal for the purification of silicon |
| CN108546987A (en) * | 2018-07-26 | 2018-09-18 | 孟静 | The method of purifying solar energy level polysilicon |
Non-Patent Citations (3)
| Title |
|---|
| HE, YF: "<An efficient method to separate silicon from high-silicon aluminum alloy melts by electromagnetic directional solidification>", 《JOURNAL OF CLEANER PRODUCTION》 * |
| 余文轴: "《电磁定向结晶从过共晶铝硅合金中富集初晶硅及提纯硅的研究》", 《中国优秀博硕士学位论文全文数据库(博士)工程科技Ⅰ辑》 * |
| 葛丰德: "电磁场对铝合金凝固过程的影响", 《哈尔滨理工大学学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333073A (en) * | 2020-03-16 | 2020-06-26 | 昆明理工大学 | Method for obtaining bulk silicon from high-silicon aluminum alloy |
| CN111762786A (en) * | 2020-07-13 | 2020-10-13 | 昆明理工大学 | Method for removing impurity elements by controllable solidification of silicon melt |
| CN111762786B (en) * | 2020-07-13 | 2022-08-12 | 昆明理工大学 | Method for removing impurity elements by controllable solidification of silicon melt |
| CN112456499A (en) * | 2020-12-11 | 2021-03-09 | 昆明理工大学 | Method for preparing high-purity silicon by using silicon cutting waste |
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