CN108328619A - A kind of method that industrial silicon hydrometallurgy removes boron - Google Patents
A kind of method that industrial silicon hydrometallurgy removes boron Download PDFInfo
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- CN108328619A CN108328619A CN201810268569.4A CN201810268569A CN108328619A CN 108328619 A CN108328619 A CN 108328619A CN 201810268569 A CN201810268569 A CN 201810268569A CN 108328619 A CN108328619 A CN 108328619A
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 47
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 40
- 239000010703 silicon Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000009854 hydrometallurgy Methods 0.000 title claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 26
- 229910021487 silica fume Inorganic materials 0.000 claims abstract description 26
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 12
- 229910021426 porous silicon Inorganic materials 0.000 claims abstract description 10
- 239000003446 ligand Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- 235000019441 ethanol Nutrition 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 235000013312 flour Nutrition 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000005530 etching Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 239000006210 lotion Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003599 detergent Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 2
- 230000002000 scavenging effect Effects 0.000 claims description 2
- LMHAGAHDHRQIMB-UHFFFAOYSA-N 1,2-dichloro-1,2,3,3,4,4-hexafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(Cl)C1(F)Cl LMHAGAHDHRQIMB-UHFFFAOYSA-N 0.000 claims 1
- 239000003929 acidic solution Substances 0.000 claims 1
- -1 dihydroxy naphthlene Chemical compound 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 4
- 239000002210 silicon-based material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 239000012535 impurity Substances 0.000 description 8
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 230000001939 inductive effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005272 metallurgy Methods 0.000 description 3
- 229920005591 polysilicon Polymers 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000721047 Danaus plexippus Species 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000010792 warming Methods 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
Abstract
The present invention relates to a kind of methods that industrial silicon hydrometallurgy removes boron, belong to wet purification and prepares solar energy level silicon technical field, the present invention is using industrial silicon as raw material, metal nanoparticle auxiliary etch (MACE) legal system is first passed through after crushing fine grinding and obtains porous silicon powder, and it is fully exposed that the porous silicon being prepared can make to wrap up inside silicon material is mingled with boron；Then obtained porous industrial silica fume is added in the acidic mixed solution containing boron complex ligand and is leached, heated and stir certain time；High-purity industrial silica fume that boron removal rate is more than 90% can be obtained after filtration, washing and drying；The method of the invention is easy to operate, at low cost, highly practical.
Description
Technical field
The present invention relates to a kind of methods that industrial silicon hydrometallurgy removes boron, belong to wet purification and prepare solar level silicon technology
Field.
Background technology
The fossil energies such as oil, the coal in the whole world are increasingly exhausted, and environmental problem and greenhouse effects are increasingly apparent, human development
It is faced with unprecedented challenge, environmentally protective, resourceful fungible energy source is found and has become a top priority.Solar energy
Because of advantages such as its resource is unlimited, clean environment firendly, safe and reliable, construction is quick, it has also become the mankind solve energy shortage, environmental pollution
With the important new energy of global warming.Polycrystalline silicon material is the main base material of solar cell, and supply is final industrialization
The deciding factor of degree.Silicon materials applied to solar cell require to be the solar-grade polysilicon more than 99.9999%,
Therefore, exploring developing low-cost solar energy level silicon new preparation process becomes the hot spot of the outer researcher's concern of Now Domestic.
Currently, the method for silicon purification can be divided mainly into two classes, one kind is chemical method, and another kind of is Physical.Chemical method with
Based on improved Siemens, although this method has many advantages, such as that technical maturity, product quality are high, purity is high, there are costs
Height, high energy consumption pollute the drawbacks such as big.Physical is commonly called as metallurgy method, is removed by oxidative slagging, pickling using industrial silicon as raw material
The means of the technologies such as miscellaneous, directional solidification, electron beam melting purification, vacuum refining will be in silicon under the premise of not changing the property of silicon main body
The removal of impurity step by step.Relative to chemical method, the method have it is at low cost, low energy consumption, advantages of environment protection, therefore, and most
It is likely to become the ideal technology route that solar-grade polysilicon is prepared other than chemical method.Solar level polycrystalline is prepared in metallurgy method
In silicon, number metal impurities big absolutely can be removed by the methods of pickling and directional solidification.But it is relatively tired to get rid of nonmetallic inclusion boron
Difficulty is primarily due to the larger segregation coefficient of boron (0.8) and is difficult to form impurity phase in grain boundaries.Therefore how efficiently to remove non-in silicon
Metal impurities boron is that metallurgy method purifying industrial silicon needs the problem solved.
In order to realize the deep removal of nonmetallic inclusion boron in industrial silicon, it is attempted to develop various effective processing works
Skill.Chinese patent (application number：101913608 A of CN) it proposes to utilize electron-beam smelting technology, by the impurity element in polysilicon
Boron is removed to 0.0001% degree.Kunming University of Science and Technology 5 is open " a method of removal boron impurity in industrial silicon " after monarch etc.
(application number：102515168 A of CN), by refining agent (CaCl2、MgCl2、CaCl2-SiO2、MgCl2-SiO2) mixed with industrial silicon
It is fitted into graphite crucible 2 ~ 3h of refining at 1450-1800 DEG C, boron content in silicon can be made to be reduced to 0.77ppmw.Though the above method
So boron impurities have been carried out with certain removal, but deposit need in process higher reaction temperature, it is complicated for operation the deficiencies of.
The prior art also has using metal auxiliary etch method come purifying industrial silicon, but this method is to common metal impurity
Removal has a remarkable effect, but to the removal of nonmetallic inclusion B and P almost without any improvement effect and higher operating costs
AgNO3As etching agent.
Invention content
It is an object of the invention to for the difficult and of high cost problem of current industrial silicon removal nonmetallic inclusion boron, provide
A kind of method that industrial silicon hydrometallurgy removes boron, this method can be removed in silicon absolutely by liquid-solid two-phase reaction under cryogenic
Most of boron, specifically comprises the following steps：
（1）Industrial silica fume chopping fine is worn into 50 ~ 200 mesh powderies.
（2）By step（1）Obtained industrial silica fume is placed in 5 ~ 60min of ultrasonic cleaning in deionized water, at room temperature with dense
The liquid-solid ratio of alcohol 5 ~ 60min of ultrasonic cleaning that degree is 1 ~ 99wt%, alcohol and industrial silica fume is more than 3:1, deionization is used later
Water is rinsed to neutrality and is dried for standby.
（3）By step（2）In obtained silica flour be added to deposited metal nanometer in the mixed solution of metal salt, HF and alcohols
The liquid-solid ratio of 0.1 ~ 10min of particle, mixed solution and silica flour is 2:1~10:1, after having deposited in mixed solution be added 0.001 ~
10mol/L H2O21 ~ 200min is etched, etching temperature is 10 ~ 80 DEG C；Then the gold on porous silicon powder surface is washed with detergent
Belong to nano-particle, porous industrial silica fume is obtained through filtering, separation, washing, drying.
（4）By step（3）In obtained porous industrial silica fume be added to HF, HNO3It is molten with the acidity of the complex ligands of boron
Liquid is leached, and liquid-solid ratio is 2 between acid solution and porous silicon powder:1~10:1, extraction time is 1 ~ 300min, extraction temperature
It is 10 ~ 80 DEG C, leaches and cleaned later using deionized water, until washing lotion pH becomes neutral, is filtered, washed, dries, obtain high-purity
Silica flour.
Preferably, step of the present invention（3）Described in deposition separate progress with silica flour etching, wherein metal salt is CuSO4、
CuCl2Or CuNO3, alcohols be methanol, ethyl alcohol, propyl alcohol, butanol, ethylene glycol, propylene glycol, propenyl, one kind in vinyl alcohol or
Two kinds and the two or more mixtures being mixed to get in any proportion；HF's is dense in the mixed solution of metal salt, HF and alcohols
Degree is 0.1 ~ 20mol/L, and a concentration of 0.001 ~ 10mol/L of metal salt, alcohol concentration is 0.1 ~ 20 mol/L.
Preferably, step of the present invention（3）Middle detergent is the diluted acid or ammonium hydroxide that mass percent concentration is 1 ~ 20 wt%
With H2O2Mixture, wherein ammonium hydroxide and H2O2For commercially available analysis pure, ammonium hydroxide and H2O2Volume ratio is arbitrary ratio；Scavenging period is 10
~100min。
Preferably, step of the present invention（4）The complex ligands of the boron are acetic acid, ethyl acetate, dihydroxy naphthlene, 2- hydroxyls
One or both of phosphine acyl acetic acid, acetone, glycerine and the two or more mixtures being mixed to get in any proportion；In acidity
A concentration of 0.1 ~ the 20mol/L, HNO of HF in solution3A concentration of 0.1 ~ 20mol/L, the complex ligands a concentration of 0.1 of boron ~
20 mol/L。
Beneficial effects of the present invention：
（1）Industrial silicon wet method can be realized under atmospheric low-temperature (10 ~ 80 DEG C) and remove boron by the present invention, not need special equipment, put down
Normal stirred autoclave achieves that, it is at low cost, equipment requirement is simple, operation is easy, it can be achieved that porous industrial silica fume it is larger
Technical scale metaplasia is produced, and to accelerate the generation of reaction, stirring can be added in leaching process.
（2）The method of the invention leachate and metal salt can be recycled, and gained industrial silica fume B removal rates are more than 90%.
Description of the drawings
Fig. 1 is the process flow chart of the present invention.
Specific implementation mode
The present invention is described in further details with reference to the accompanying drawings and detailed description, but protection scope of the present invention
It is not limited to the content.
Embodiment 1
A kind of method that industrial silicon hydrometallurgy removes boron（As shown in Figure 1）, specific steps include as follows：
（1）Industrial silicon (boron content 78pmw) crushing is finely ground into 150 mesh powderies and is placed in deionized water and is cleaned by ultrasonic 10min,
It is cleaned by ultrasonic 15 min with the alcohol of a concentration of 40 wt% at room temperature, the liquid-solid ratio of alcohol and industrial silica fume is 5:1, later
It is rinsed to neutrality and is dried for standby with a large amount of deionized waters.
（2）By step（1）Obtained silica flour is added to Cu2(NO)3, HF and ethylene glycol mixed solution in deposited metal receive
Rice corpuscles 2min（Liquid-solid ratio between mixed solution and silica flour is 3:1）, 0.001mol/ is added after having deposited in mixed solution
The H of L2O2100min is etched, etching temperature is 60 DEG C；A concentration of 4.6mol/L, Cu of HF in mixed solution2(NO)3It is dense
Degree is 0.01 mol/L, glycol concentration 5mol/L；After with 8 wt% dust technologies clean 60min, finally passed through again
Filter separation, washing, drying, obtain porous industrial silica fume.
（3）By step（2）Obtained porous industrial silica fume is added to HF, HNO3It is soaked with the acid solution of ethyl acetate
Go out, a concentration of 8mol/L, HNO of HF in acid solution3A concentration of 10mol/L, ethyl acetate a concentration of 8mol/L, it is acid
Liquid-solid ratio is 3 between solution and porous silicon powder:1, extraction time 100min, extraction temperature are 60 DEG C, leach to use later and go
Ionized water cleans, until washing lotion pH becomes neutral, is filtered, washed, dries, obtain high-purity silicon powder, with ion inductive coupling mass spectrum
It is 6.9ppmw that instrument (ICP-MS), which measures the boron content in HIGH-PURITY SILICON, and the removal rate of boron is 91.15%.
Embodiment 2
A kind of method that industrial silicon hydrometallurgy removes boron（As shown in Figure 1）, specific steps include as follows：
（1）Industrial silicon (boron content 108pmw) crushing is finely ground into 200 mesh powderies and is placed in deionized water and is cleaned by ultrasonic
15min is cleaned by ultrasonic 30 min with the alcohol of a concentration of 60 wt% at room temperature, and the liquid-solid ratio of alcohol and industrial silica fume is 5:
1, it is rinsed to neutrality be dried for standby with a large amount of deionized waters later.
（2）By step（1）Obtained silica flour is added to CuSO4, HF and methanol mixed solution in deposited metal nanoparticle
Sub- 0.1min（Liquid-solid ratio between mixed solution and silica flour is 5:1）, it is added 3mol/L's in mixed solution after having deposited
H2O2150min is etched, etching temperature is 10 DEG C；A concentration of 0.1mol/L, CuSO of HF in mixed solution4It is a concentration of
0.008 mol/L, methanol concentration 6mol/L；After with 6 wt% dilute sulfuric acids clean 40min, finally pass through filtering point again
From, washing, drying, obtain porous industrial silica fume.
（3）By step（2）Obtained porous industrial silica fume is added to HF, HNO3It is soaked with the acid solution of ethyl acetate
Go out, a concentration of 0.1mol/L, HNO of HF in acid solution3A concentration of 20mol/L, ethyl acetate a concentration of 6mol/L, acid
Property solution and porous silicon powder between liquid-solid ratio be 5:1, extraction time 150min, extraction temperature are 10 DEG C, leach and use later
Deionized water is cleaned, until washing lotion pH becomes neutral, is filtered, washed, is dried, obtain high-purity silicon powder, with ion inductive coupling matter
It is 10.7ppmw that spectrometer (ICP-MS), which measures the boron content in HIGH-PURITY SILICON, and the removal rate of boron is 90.09%.
Embodiment 3
A kind of method that industrial silicon hydrometallurgy removes boron（As shown in Figure 1）, specific steps include as follows：
（1）Industrial silicon (boron content 143pmw) crushing is finely ground into 50 mesh powderies and is placed in deionized water and is cleaned by ultrasonic 60min,
It is cleaned by ultrasonic 60 min with the alcohol of a concentration of 99wt% at room temperature, the liquid-solid ratio of alcohol and industrial silica fume is 6:1, Zhi Houyong
A large amount of deionized waters, which are rinsed to neutrality, to be dried for standby.
（2）By step（1）Obtained silica flour is added to CuCl2, HF, methanol and ethyl alcohol mixed solution in deposited metal receive
Rice corpuscles 1.5min（Liquid-solid ratio between mixed solution and silica flour is 8:1）, 2mol/L is added after having deposited in mixed solution
H2O2200min is etched, etching temperature is 50 DEG C；A concentration of 6.9mol/L, CuCl of HF in mixed solution2It is a concentration of
0.02 mol/L, methanol concentration 0.1mol/L, concentration of alcohol 3mol/L；After cleaned with 10 wt% dilute hydrochloric acid
50min is finally isolated by filtration, washs, dries again, obtains porous industrial silica fume.
（3）By step（2）Obtained porous industrial silica fume is added to HF, HNO3It is soaked with the acid solution of ethyl acetate
Go out, a concentration of 10mol/L, HNO of HF in acid solution3A concentration of 8mol/L, ethyl acetate a concentration of 6mol/L, it is acid
Liquid-solid ratio is 8 between solution and porous silicon powder:1, extraction time 120min, extraction temperature are 50 DEG C, leach to use later and go
Ionized water cleans, until washing lotion pH becomes neutral, is filtered, washed, dries, obtain high-purity silicon powder, with ion inductive coupling mass spectrum
It is 11.3ppmw that instrument (ICP-MS), which measures the boron content in HIGH-PURITY SILICON, and the removal rate of boron is 92.1%.
Embodiment 4
A kind of method that industrial silicon hydrometallurgy removes boron（As shown in Figure 1）, specific steps include as follows：
（1）Industrial silicon (boron content 198pmw) crushing is finely ground into 100 mesh powderies and is placed in deionized water and is cleaned by ultrasonic 5min,
It is cleaned by ultrasonic 5min with the alcohol of a concentration of 1wt% at room temperature, the liquid-solid ratio of alcohol and industrial silica fume is 3:1, it uses later big
Amount deionized water, which is rinsed to neutrality, to be dried for standby.
（2）By step（1）Obtained silica flour is added to CuCl2, HF, methanol and ethyl alcohol mixed solution in deposited metal receive
Rice corpuscles 10min（Liquid-solid ratio between mixed solution and silica flour is 2:1）, 10mol/L is added after having deposited in mixed solution
H2O21min is etched, etching temperature is 80 DEG C；A concentration of 20mol/L, CuCl of HF in mixed solution2A concentration of 10
Mol/L, methanol concentration 20mol/L, concentration of alcohol 0.1mol/L；After use ammonium hydroxide（Mass percent concentration is 28%）
And hydrogen peroxide（Mass percent concentration is 30%）Mixed solution（Volume ratio 1:1）50min is cleaned, finally passes through filtering again
Separation, washing, drying, obtain porous industrial silica fume.
（3）By step（2）Obtained porous industrial silica fume is added to HF, HNO3It is soaked with the acid solution of ethyl acetate
Go out, a concentration of 20mol/L, HNO of HF in acid solution3A concentration of 20mol/L, ethyl acetate a concentration of 6mol/L, acid
Property solution and porous silicon powder between liquid-solid ratio be 2:1, extraction time 300min, extraction temperature are 80 DEG C, leach and use later
Deionized water is cleaned, until washing lotion pH becomes neutral, is filtered, washed, is dried, obtain high-purity silicon powder, with ion inductive coupling matter
It is 13.2ppmw that spectrometer (ICP-MS), which measures the boron content in HIGH-PURITY SILICON, and the removal rate of boron is 93.3%.
Claims (5)
1. a kind of method that industrial silicon hydrometallurgy removes boron, which is characterized in that specific steps include as follows：
（1）Industrial silica fume chopping fine is worn into 50 ~ 200 mesh powderies；
（2）By step（1）Obtained industrial silica fume is placed in 5 ~ 60min of ultrasonic cleaning in deionized water, at room temperature with a concentration of 1
The liquid-solid ratio of alcohol 5 ~ 60min of ultrasonic cleaning of ~ 99wt%, alcohol and industrial silica fume is more than 3:1, it is rinsed later with deionized water
It is dried for standby to neutrality；
（3）By step（2）In obtained silica flour be added to deposited metal nano-particle in the mixed solution of metal salt, HF and alcohols
The liquid-solid ratio of 0.1 ~ 10min, mixed solution and silica flour is 2:1~10:1, after having deposited in mixed solution be added 0.001 ~
10mol/L H2O21 ~ 200min is etched, etching temperature is 10 ~ 80 DEG C；Then porous silicon powder surface is washed with matched detergent
Metal nanoparticle, obtain porous industrial silica fume through filtering, separation, washing, drying；
（4）By step（3）In obtained porous industrial silica fume be added to HF, HNO3With the acid solutions of the complex ligands of boron into
Row leaches, and liquid-solid ratio is 2 between acid solution and porous silicon powder:1~10:1, extraction time is 1 ~ 300min, extraction temperature 10
It ~ 80 DEG C, leaches and is cleaned later using deionized water, until washing lotion pH becomes neutral, be filtered, washed, dry, obtain HIGH-PURITY SILICON
Powder.
2. the method that industrial silicon hydrometallurgy according to claim 1 removes boron, it is characterised in that：Step（3）It is middle deposition with
Silica flour etching separately carries out, and wherein metal salt is CuSO4、CuCl2Or CuNO3, alcohols is methanol, ethyl alcohol, propyl alcohol, butanol, second
One kind, two or more mixture being mixed to get in any proportion in glycol, propylene glycol, propenyl, vinyl alcohol.
3. the method that industrial silicon hydrometallurgy according to claim 1 removes boron, it is characterised in that：Metal salt, HF and alcohols
Mixed solution in HF a concentration of 0.1 ~ 20mol/L, a concentration of 0.001 ~ 10mol/L of metal salt, alcohol concentration be 0.1 ~
20 mol/L。
4. the method that industrial silicon hydrometallurgy according to claim 1 removes boron, it is characterised in that：Step（3）Middle detergent
For the diluted acid or ammonium hydroxide and H that mass percent concentration is 1 ~ 20 wt%2O2Mixture, scavenging period be 10 ~ 100min,
In, diluted acid is dilute sulfuric acid, dust technology or dilute hydrochloric acid.
5. the method that industrial silicon hydrometallurgy according to claim 1 removes boron, it is characterised in that：Step（4）The boron
Complex ligands be one or both of acetic acid, ethyl acetate, dihydroxy naphthlene, 2- hydroxyphosphonoacetic acid, acetone, glycerine and
The two or more mixtures being mixed to get in any proportion；A concentration of 0.1 ~ the 20mol/L, HNO of HF in an acidic solution3It is dense
Degree is 0.1 ~ 20mol/L, a concentration of 0.1 ~ 20 mol/L of complex ligands of boron.
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| CN111591999A (en) * | 2020-05-06 | 2020-08-28 | 江西盛丰新能源科技有限公司 | Preparation method of high-performance silicon material for lithium ion battery cathode |
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