CN104401999A - Method for wet impurity removal of industrial silicon - Google Patents
Method for wet impurity removal of industrial silicon Download PDFInfo
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- CN104401999A CN104401999A CN201410614912.8A CN201410614912A CN104401999A CN 104401999 A CN104401999 A CN 104401999A CN 201410614912 A CN201410614912 A CN 201410614912A CN 104401999 A CN104401999 A CN 104401999A
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- 238000000034 method Methods 0.000 title claims abstract description 75
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 38
- 239000010703 silicon Substances 0.000 title claims abstract description 38
- 239000012535 impurity Substances 0.000 title abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 46
- 239000002210 silicon-based material Substances 0.000 claims abstract description 25
- 238000005530 etching Methods 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 64
- 229910021487 silica fume Inorganic materials 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 40
- 239000008367 deionised water Substances 0.000 claims description 32
- 235000013312 flour Nutrition 0.000 claims description 32
- 239000000377 silicon dioxide Substances 0.000 claims description 32
- 238000005554 pickling Methods 0.000 claims description 31
- 238000000926 separation method Methods 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 28
- 238000000151 deposition Methods 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 230000008021 deposition Effects 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000011863 silicon-based powder Substances 0.000 claims description 10
- 238000010306 acid treatment Methods 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000013467 fragmentation Methods 0.000 claims description 8
- 238000006062 fragmentation reaction Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000006210 lotion Substances 0.000 claims description 8
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- 238000002203 pretreatment Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 101710134784 Agnoprotein Proteins 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000004070 electrodeposition Methods 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 claims description 4
- 238000002207 thermal evaporation Methods 0.000 claims description 4
- 238000010894 electron beam technology Methods 0.000 claims description 3
- 230000005284 excitation Effects 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 101150003085 Pdcl gene Proteins 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 238000000746 purification Methods 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 3
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- 238000007598 dipping method Methods 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000005272 metallurgy Methods 0.000 description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 4
- 229920005591 polysilicon Polymers 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for wet impurity removal of industrial silicon, and belongs to the technical field of the preparation of highly pure silicon through wet purification. The method is provided to solve the practical problem of difficult advanced impurity removal due to wrapping of impurities in silicon in the wet purification process of the industrial silicon. The method is characterized in that a large amount of nanopores are drilled on the surface of a silicon material and in the silicon material through a metal nanoparticle assisted etching (MACE) technology in order to make the wrapped impurities fully exposed, and acid dipping treatment is combined to achieve the advanced removal of the impurities in the industrial silicon material. The method has the advantages of simple equipment requirements, easy operation, and suitableness for scale industrial production.
Description
Technical field
The present invention relates to a kind of method of industrial silicon wet separation, belong to wet purification and prepare HIGH-PURITY SILICON technical field.
Background technology
Along with improving constantly of the day by day exhausted of fossil energy and environmental protection consciousness, find a kind of efficient and eco-friendly fungible energy source becomes domestic and international researcher international headache in the urgent need to address.Solar electrical energy generation is sent to great expectations because of advantages such as cleanliness without any pollution, resource are relatively extensive and sufficient, the life-span is long, becomes the focus of countries nowadays research.In numerous solar cell material, polysilicon is certainly use transition material the most widely, and how obtaining solar-grade polysilicon at low cost becomes the important factor directly affecting solar cell development.Wherein Impurity removal is again core link prepared by solar-grade polysilicon, and therefore, in a kind of industrial silicon of efficient, low cost, impurity deep removal technology is significant to solar cell development.
At present, the method that silicon is purified mainly can be divided into two classes, and a class is chemical method, and mainly comprise improved Siemens, silane thermal decomposition process, fluidized bed process etc., another kind of is Physical, is commonly called as metallurgy method.Current commercial applications is more is improved Siemens, the method has technical maturity, can realize continuous prodution and product has quality advantages of higher, but also has that technical process is many, capital cost is high, cost is high, energy consumption is high, core technology constantly forces us to seek more how feasible production of polysilicon technology primarily of problems such as minority developed country monopolize.Wherein metallurgy method is because its initial cost is few, energy consumption is relatively low, advantages of environment protection, be acknowledged as the most promising a kind of technique of HIGH-PURITY SILICON preparation, it mainly comprises: the methods such as directional freeze, vacuum melting, slag refining, oxidative slagging, wet purification, fused salt electrolysis, in order to realize the requirement of solar energy level silicon to impurity, multiple method in metallurgy method, is usually taked to combine the object realizing preparing HIGH-PURITY SILICON.Because wet purification process has the advantage such as less energy-consumption, low cost, usually become the link that in metallurgy method purifying industrial silicon technology one is necessary, this also makes the wet purification process of industrial silicon become the focus of domestic and international researcher research.
Wet purification is based on silicon substrate and impurity chemically stable difference existing in acid solvent system, utilizes the process that foreign ionization leaches by the corrosive property of acid.But there is the feature of stochastic distribution due to impurity phase shape, size and position in silicon, it is almost impossible for making Metallic Inclusion in silicon, solid solution nonmetallic impurity contact abundant reaction completely with leach liquor in acidleach treating processes, and this also causes wet processing to be difficult to realize the problem of impurity deep removal in silicon.
In order to realize the deep removal of impurity, people attempt to develop various effective wet processing process, and Chinese patent (application number: CN 102079524 A) proposes two-stage wet purification to prepare HIGH-PURITY SILICON, and the silica flour purity obtained is 99.94%.The people such as Chinese Academy of Sciences Wang Zhi proposes to cool after industrial silicon and calcium metal mixing, heating congruent melting, silicon recrystallization is separated out, then adopts acidleach process to realize the object (application number: CN 103693648 A) of the impurity strengthening removal in silicon material.But, in aforesaid method or there is impurity is difficult to the degree of depth and removes, or deposit deficiencies such as needing higher temperature of reaction in process.Given this, the present invention proposes the novel method that one can realize strengthening industrial silicon wet separation under lesser temps (10 ~ 100 DEG C).The method is by adopting metal nanoparticle auxiliary etch (MACE) method in silicon material surface and inner " getting out " a large amount of nano level duct, what make silicon material internal package is mingled with abundant exposure, then reaches the object being mingled with deep removal in industrial silicon material in conjunction with acidleach process.The method has the advantages such as equipment requirements is simple, processing ease, applicable large-scale industrial production.
Summary of the invention
The object of the invention is to the problem being difficult to realize deep impurity-removing for the wet purification of current industrial silicon, a kind of method of industrial silicon wet separation is provided, method is using the industrial silica fume compared with low-purity as raw material, first " get out " a large amount of nano level duct by metal nanoparticle auxiliary etch (MACE) method at silicon powder surface and inside, reach the object of impurity deep removal in industrial silicon material again in conjunction with acidleach process, detailed process is as follows:
(1) pre-treatment of silicon material: industrial silicon material is carried out fragmentation, grinding, washed with de-ionized water silica flour (granularity 0.5 ~ 1000 μm), be that the HF of 1 ~ 40wt% is by silica flour immersion 1 ~ 120min by concentration, its liquid-solid ratio is greater than 3:1, soaking temperature is between 10 ~ 100 DEG C, uses washed with de-ionized water, filtering separation afterwards;
(2) introducing of vesicular structure: by the katalysis of metal nanoparticle, adopts one-step or two-step metal nanoparticle auxiliary etch method at 10 ~ 100 DEG C, forms nano level duct on industrial silica fume surface and inner etching;
(3) removal of metal nanoparticle: the porous industrial silica fume containing nano metal particles obtained in step (2) is placed in oxidizing solution immersion 0.1 ~ 6h that concentration is 0.1 ~ 90 wt%, between industrial silica fume and oxidizing solution, liquid-solid ratio is greater than 3:1, then use washed with de-ionized water, filtering separation, obtain porous industrial silica fume;
(4) the porous industrial silica fume obtained in (3) step being placed in concentration is that the acidic solution of 0.1 ~ 98wt% carries out cleanup acid treatment, between industrial silica fume and acidic solution, liquid-solid ratio is greater than 3:1, pickling time is 0.5 ~ 72h, pickling temperature is 10 ~ 100 DEG C, washed with de-ionized water is adopted after pickling, until washing lotion pH becomes neutrality, filter, dry, obtain high-purity silicon powder.
In a single metal nano particle auxiliary etch method described in step of the present invention (2), the deposition of metal nanoparticle and being etched in same reaction system of silica flour are carried out simultaneously, and selected reaction system is the mixing solutions of HF/ metal-salt, and wherein metal-salt is AgNO
3, KAuCl
4, HAuCl
4, K
2ptCl
6, H
2ptCl
6, PdCl
2or CuNO
3, in mixing solutions, the concentration of HF is 0.1 ~ 33mol/L, and the concentration of metal-salt is 0.001 ~ 10 mol/L, and etching time is 0.1 ~ 48h.
In two single metal nano particle auxiliary etch methods described in step of the present invention (2), the deposition of metal nanoparticle etches to separate with silica flour and carries out, the one in magnetron sputtering deposition, thermal evaporation deposition, electron-beam excitation deposition, electrochemical deposition, electroless deposition methods is adopted to be deposited on silica flour by Ag, Au, Pt, Pd or Cu metal nanoparticle, its nanoparticle is of a size of 10 ~ 500nm, etched by the mixing solutions that the silica flour depositing metal nanoparticle is placed in HF/ oxygenant, oxygenant is H
2o
2, HNO
3, Fe (NO
3)
3, KMnO
4, KBrO
3, K
2cr
2o
7or Na
2s
2o
8, in mixing solutions, the concentration of HF is 0.1 ~ 33mol/L, and the concentration of oxygenant is 0.01 ~ 20mol/L, and etching time is 0.1 ~ 48h.
Magnetron sputtering deposition of the present invention, thermal evaporation deposition, electron-beam excitation deposition, electrochemical deposition, electroless deposition methods are ordinary method.
If reaction system have chosen HF/AgNO in the present invention
3system, its reaction unit should do lucifuge process.
Step of the present invention (3) described oxidizing solution is nitric acid, hydrogen peroxide or ammoniacal liquor.
Step of the present invention (4) described acid is one or both and the two or more mixture be mixed to get in any proportion in hydrochloric acid, sulfuric acid, nitric acid, chloroazotic acid, hydrofluoric acid, acetic acid, and acid cleaning process can be taked a step acidleach or multistep to combine and leach process.
Industrial silica fume and be not less than 3:1 with the volume ratio of etching liquid in step of the present invention (2), can realize the fairly large suitability for industrialized production of porous industrial silica fume, be the generation accelerating etching reaction, can add stirring in etching process.
Beneficial effect of the present invention is:
(1) the present invention relates to a kind of method of industrial silicon wet separation, the method introduces a large amount of nano level duct by metal nanoparticle auxiliary etch in silicon grain inside, increase the touch opportunity of silicon grain internal package impurity and acid solution, the deep removal of impurity in industrial silicon can be realized;
(2) the present invention relates to a kind of method of industrial silicon wet separation, is a kind of high-efficiency wet impurity-removing method of low cost, and the method has the advantages such as equipment is simple, processing ease, applicable large-scale industrial production.
Accompanying drawing explanation
Fig. 1 strengthens wet method acid immersion and prepares high-purity silicon powder schematic diagram.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further details, but protection scope of the present invention is not limited to described content.
Embodiment 1
(1) pre-treatment of silicon material: industrial silicon material (purity: 99.8wt%) is carried out fragmentation, grinding, washed with de-ionized water silica flour (0.5 ~ 50 μm), with the HF that concentration is 1wt%, silica flour is soaked 120min, its liquid-solid ratio is 4:1, soaking temperature is between 80 DEG C, uses washed with de-ionized water, filtering separation afterwards;
(2) introducing of vesicular structure: by the katalysis of metal nanoparticle, adopts a single metal nano particle auxiliary etch method at 10 DEG C, forms nano level duct on industrial silica fume surface and inner etching; In a described single metal nano particle auxiliary etch method, the deposition of metal nanoparticle and being etched in same reaction system of silica flour are carried out simultaneously, and selected reaction system is HF/AgNO
3mixing solutions, reaction system is placed in darkroom stir (rotating speed: 180 turns/min) react 48h, in mixing solutions, the concentration of HF is 33mol/L, AgNO
3concentration be 0.001mol/L;
(3) removal of metal nanoparticle: by obtain in step (2) to be placed in concentration containing the porous industrial silica fume of nano metal particles be that the salpeter solution of 0.1wt% soaks 6h, between industrial silica fume and salpeter solution, liquid-solid ratio is 3:1, then use washed with de-ionized water, filtering separation, obtain porous industrial silica fume;
(4) the porous industrial silica fume obtained in (3) step is placed in the hydrofluoric acid that concentration is 0.1wt% and hydrochloric acid mixed solution carries out cleanup acid treatment, between industrial silica fume and mixed acid solution, liquid-solid ratio is 3:1, pickling time is 72h, pickling temperature is 10 DEG C, washed with de-ionized water is adopted after pickling, until washing lotion pH becomes neutrality, filter, dry, obtain high-purity silicon powder.
Embodiment 2
(1) pre-treatment of silicon material: industrial silicon material (purity: 99.8wt%) is carried out fragmentation, grinding, washed with de-ionized water silica flour (50 ~ 150 μm), with the HF that concentration is 5wt%, silica flour is soaked 100min, its liquid-solid ratio is 3:1, soaking temperature is between 10 DEG C, uses washed with de-ionized water, filtering separation afterwards;
(2) introducing of vesicular structure: by the katalysis of metal nanoparticle, adopts a single metal nano particle auxiliary etch method at 100 DEG C, forms nano level duct on industrial silica fume surface and inner etching; Selected reaction system is HF/KAuCl
4mixing solutions, in mixing solutions, the concentration of HF is 0.1mol/L, KAuCl
4concentration be 5mol/L, etching time is 20h;
(3) removal of metal nanoparticle: by obtain in step (2) to be placed in concentration containing the porous industrial silica fume of nano metal particles be that the ammonia soln of 10wt% soaks 0.1h, between industrial silica fume and ammonia soln, liquid-solid ratio is greater than 3:1, then use washed with de-ionized water, filtering separation, obtain porous industrial silica fume;
(4) the porous industrial silica fume obtained in (3) step is placed in the hydrofluoric acid that concentration is 20wt% and hydrochloric acid soln carries out cleanup acid treatment, between industrial silica fume and mixed acid solution, liquid-solid ratio is greater than 3:1, pickling time is 72h, pickling temperature is 30 DEG C, washed with de-ionized water is adopted after pickling, until washing lotion pH becomes neutrality, filter, dry, obtain high-purity silicon powder.
Embodiment 3
(1) pre-treatment of silicon material: industrial silicon material (purity: 99.8wt%) is carried out fragmentation, grinding, washed with de-ionized water silica flour (150 ~ 250 μm), with the HF that concentration is 12wt%, silica flour is soaked 80min, its liquid-solid ratio is 5:1, soaking temperature is between 30 DEG C, uses washed with de-ionized water, filtering separation afterwards;
(2) introducing of vesicular structure: by the katalysis of metal nanoparticle, adopts a single metal nano particle auxiliary etch method at 25 DEG C, forms nano level duct on industrial silica fume surface and inner etching; Selected reaction system is HF/K
2ptCl
6solution, in mixing solutions, the concentration of HF is 33mol/L, K
2ptCl
6concentration be 10 mol/L, etching time is 0.1h;
(3) removal of metal nanoparticle: by obtain in step (2) to be placed in concentration containing the porous industrial silica fume of nano metal particles be that the hydrogen peroxide solution of 10wt% soaks 4h, between industrial silica fume and hydrogen peroxide solution, liquid-solid ratio is 5:1, then use washed with de-ionized water, filtering separation, obtain porous industrial silica fume;
(4) the porous industrial silica fume obtained in (3) step being placed in concentration is that the acidic solution of 45wt% carries out cleanup acid treatment, between industrial silica fume and acidic solution, liquid-solid ratio is 5:1, pickling time is 50h, pickling temperature is 60 DEG C, washed with de-ionized water is adopted after pickling, until washing lotion pH becomes neutrality, filter, dry, obtain high-purity silicon powder.
Embodiment 4
(1) pre-treatment of silicon material: industrial silicon material (purity: 99.8wt%) is carried out fragmentation, grinding, washed with de-ionized water silica flour (250 ~ 500 μm), with the HF that concentration is 28wt%, silica flour is soaked 50min, its liquid-solid ratio is greater than 3:1, soaking temperature is between 50 DEG C, uses washed with de-ionized water, filtering separation afterwards;
(2) introducing of vesicular structure: by the katalysis of metal nanoparticle, adopts two single metal nano particle auxiliary etch methods at 40 DEG C, forms nano level duct on industrial silica fume surface and inner etching; Adopt magnetron sputtering deposition to be deposited on silica flour by Ag nanoparticle (being of a size of 10nm), the silica flour depositing metal nanoparticle is placed in HF/ H
2o
2mixing solutions, in mixing solutions, the concentration of HF is 33mol/L, H
2o
2concentration be 20mol/L, etching time is 48h;
(3) removal of metal nanoparticle: by obtain in step (2) to be placed in concentration containing the porous industrial silica fume of nano metal particles be that the ammonia soln of 90 wt% soaks 1h, between industrial silica fume and ammonia soln, liquid-solid ratio is greater than 3:1, then use washed with de-ionized water, filtering separation, obtain porous industrial silica fume;
(4) the porous industrial silica fume obtained in (3) step is placed in chloroazotic acid and carries out cleanup acid treatment, between industrial silica fume and chloroazotic acid, liquid-solid ratio is greater than 3:1, pickling time is 4h, pickling temperature is 25 DEG C, afterwards porous industrial silica fume being placed in concentration is that the hydrochloric acid soln of 60wt% carries out white picking process, between industrial silica fume and hydrochloric acid soln, liquid-solid ratio is greater than 3:1, pickling time is 40h, pickling temperature is 80 DEG C, washed with de-ionized water is adopted after pickling, until washing lotion pH becomes neutrality, filter, dry, obtain high-purity silicon powder.
Embodiment 5
(1) pre-treatment of silicon material: industrial silicon material (purity: 99.8wt%) is carried out fragmentation, grinding, washed with de-ionized water silica flour (500 ~ 750 μm), with the HF that concentration is 35wt%, silica flour is soaked 30min, its liquid-solid ratio is greater than 3:1, soaking temperature is between 70 DEG C, uses washed with de-ionized water, filtering separation afterwards;
(2) introducing of vesicular structure: by the katalysis of metal nanoparticle, adopts two single metal nano particle auxiliary etch methods at 60 DEG C, forms nano level duct on industrial silica fume surface and inner etching; Adopt thermal evaporation deposition Pt(size at 300nm) be deposited on silica flour, the silica flour depositing metal nanoparticle is placed in HF/KMnO
4mixing solutions in etch, in mixing solutions, the concentration of HF is 20mol/L, KMnO
4concentration be 10mol/L, etching time is 0.1h;
(3) removal of metal nanoparticle: by obtain in step (2) to be placed in concentration containing the porous industrial silica fume of nano metal particles be that the salpeter solution of 50 wt% soaks 3h, between industrial silica fume and salpeter solution, liquid-solid ratio is greater than 3:1, then use washed with de-ionized water, filtering separation, obtain porous industrial silica fume;
(4) the porous industrial silica fume obtained in (3) step being placed in concentration is that the sulphuric acid soln of 80wt% carries out cleanup acid treatment, between industrial silica fume and sulphuric acid soln, liquid-solid ratio is greater than 3:1, pickling time is 30h, pickling temperature is 100 DEG C, afterwards porous industrial silica fume being placed in concentration is that the hydrofluoric acid solution of 25wt% carries out white picking process, between industrial silica fume and hydrofluoric acid solution, liquid-solid ratio is greater than 3:1, and pickling time is 3h, and pickling temperature is 70 DEG C of pickling.Later adopt washed with de-ionized water, until washing lotion pH becomes neutrality, filter, dry, obtain high-purity silicon powder.
Embodiment 6
(1) pre-treatment of silicon material: industrial silicon material (purity: 99.8wt%) is carried out fragmentation, grinding, washed with de-ionized water silica flour (750 ~ 1000 μm), with the HF that concentration is 40wt%, silica flour is soaked 1min, its liquid-solid ratio is greater than 3:1, soaking temperature is between 100 DEG C, uses washed with de-ionized water, filtering separation afterwards;
(2) introducing of vesicular structure: by the katalysis of metal nanoparticle, adopts two single metal nano particle auxiliary etch methods at 80 DEG C, forms nano level duct on industrial silica fume surface and inner etching; Adopt electrochemical deposition Cu metal nanoparticle (being of a size of 500nm) to be deposited on silica flour, the silica flour depositing metal nanoparticle is placed in HF/ KBrO
3etch in the mixing solutions of oxygenant, in mixing solutions, the concentration of HF is 0.1mol/L, KBrO
3concentration be 0.01mol/L, etching time is 25h;
(3) removal of metal nanoparticle: by obtain in step (2) to be placed in concentration containing the porous industrial silica fume of nano metal particles be that the potassium permanganate solution of 30wt% soaks 6h, between industrial silica fume and potassium permanganate solution, liquid-solid ratio is greater than 3:1, then use washed with de-ionized water, filtering separation, obtain porous industrial silica fume;
(4) the porous industrial silica fume obtained in (3) step being placed in concentration is that the sulphuric acid soln of 98wt% carries out cleanup acid treatment (stir speed (S.S.) is 180 turns/min), between industrial silica fume and sulphuric acid soln, liquid-solid ratio is greater than 3:1, pickling time is 0.5h, pickling temperature is 70 DEG C, porous industrial silica fume being placed in concentration is that the acetum of 36wt% carries out white picking process (stir speed (S.S.) is 180 turns/min), between industrial silica fume and acetum, liquid-solid ratio is greater than 3:1, pickling time is 5h, pickling temperature is 25 DEG C, porous industrial silica fume being placed in concentration is that the hydrofluoric acid solution of 10wt% carries out three cleanup acid treatment (stir speed (S.S.) is 180 turns/min) again, between industrial silica fume and hydrofluoric acid solution, liquid-solid ratio is greater than 3:1, pickling time is 10h, pickling temperature is 45 DEG C, adopt washed with de-ionized water afterwards, until washing lotion pH becomes neutrality, filter, dry, obtain high-purity silicon powder.
Claims (8)
1. a method for industrial silicon wet separation, is characterized in that, specifically comprises the following steps:
(1) pre-treatment of silicon material: industrial silicon material is carried out fragmentation, grinding, washed with de-ionized water silica flour, be that silica flour is soaked 1 ~ 120min by the HF of 1 ~ 40wt% by concentration, its liquid-solid ratio is greater than 3:1, soaking temperature is between 10 ~ 100 DEG C, uses washed with de-ionized water, filtering separation afterwards;
(2) introducing of vesicular structure: by the katalysis of metal nanoparticle, adopts one-step or two-step metal nanoparticle auxiliary etch method at 10 ~ 100 DEG C, forms nano level duct on industrial silica fume surface and inner etching;
(3) removal of metal nanoparticle: the porous industrial silica fume containing nano metal particles obtained in step (2) is placed in oxidizing solution immersion 0.1 ~ 6h that concentration is 0.1 ~ 90wt%, between industrial silica fume and oxidizing solution, liquid-solid ratio is greater than 3:1, then use washed with de-ionized water, filtering separation, obtain porous industrial silica fume;
(4) the porous industrial silica fume obtained in (3) step being placed in concentration is that the acidic solution of 0.1 ~ 98wt% carries out cleanup acid treatment, between industrial silica fume and acidic solution, liquid-solid ratio is greater than 3:1, pickling time is 0.5 ~ 72h, pickling temperature is 10 ~ 100 DEG C, washed with de-ionized water is adopted after pickling, until washing lotion pH becomes neutrality, filter, dry, obtain high-purity silicon powder.
2. the method for industrial silicon wet separation according to claim 1, is characterized in that: the granularity of described industrial silicon material is 0.5 ~ 1000 μm.
3. the method for industrial silicon wet separation according to claim 1, it is characterized in that: in a single metal nano particle auxiliary etch method described in step (2), the deposition of metal nanoparticle and being etched in same reaction system of silica flour are carried out simultaneously, selected reaction system is the mixing solutions of HF/ metal-salt, and wherein metal-salt is AgNO
3, KAuCl
4, HAuCl
4, K
2ptCl
6, H
2ptCl
6, PdCl
2or CuNO
3, in mixing solutions, the concentration of HF is 0.1 ~ 33mol/L, and the concentration of metal-salt is 0.001 ~ 10 mol/L, and etching time is 0.1 ~ 48h.
4. the method for industrial silicon wet separation according to claim 1, it is characterized in that: in two single metal nano particle auxiliary etch methods described in step (2), the deposition of metal nanoparticle etches to separate with silica flour and carries out, adopt magnetron sputtering deposition, thermal evaporation deposition, electron-beam excitation deposits, electrochemical deposition, a kind of method in electroless deposition is by Ag, Au, Pt, Pd or Cu metal nanoparticle is deposited on silica flour, its nanoparticle is of a size of 10 ~ 1000nm, the mixing solutions that the silica flour depositing metal nanoparticle is placed in HF/ oxygenant is etched, oxygenant is H
2o
2, HNO
3, Fe (NO
3)
3, KMnO
4, KBrO
3, K
2cr
2o
7or Na
2s
2o
8, in mixing solutions, the concentration of HF is 0.1 ~ 33mol/L, and the concentration of oxygenant is 0.01 ~ 20mol/L, and etching time is 0.1 ~ 48h.
5. the method for the industrial silicon wet separation according to claim 3 or 4, is characterized in that: if reaction system have chosen HF/AgNO
3system, its reaction unit should do lucifuge process.
6. the method for industrial silicon wet separation according to claim 1, is characterized in that: step (3) described oxidizing solution is nitric acid, hydrogen peroxide, ammoniacal liquor or potassium permanganate solution.
7. the method for industrial silicon wet separation according to claim 1, it is characterized in that: step (4) described acid is one or both and the two or more mixture be mixed to get in any proportion in hydrochloric acid, sulfuric acid, nitric acid, chloroazotic acid, hydrofluoric acid, acetic acid, acid cleaning process can be taked a step acidleach or multistep to combine and leach process.
8. the method for industrial silicon wet separation according to claim 1, is characterized in that: industrial silica fume and be not less than 3:1 with the volume ratio of etching liquid in step (2).
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| CN115989192A (en) * | 2020-08-27 | 2023-04-18 | 株式会社德山 | Broken polycrystalline silicon blocks and manufacturing method thereof |
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