CN104817088A - Method of low-cost preparing solar-grade polycrystalline silicon - Google Patents
Method of low-cost preparing solar-grade polycrystalline silicon Download PDFInfo
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- CN104817088A CN104817088A CN201510220161.6A CN201510220161A CN104817088A CN 104817088 A CN104817088 A CN 104817088A CN 201510220161 A CN201510220161 A CN 201510220161A CN 104817088 A CN104817088 A CN 104817088A
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Abstract
The invention discloses a method of low-cost preparing solar-grade polycrystalline silicon. In the method, 3N-grade metallic silicon is employed as a raw material. The method includes following steps: (1) blowing slagging refining after the metallic silicon is molten through a medium-frequency induction furnace; (2) primary smashing and grinding; (3) pre-heating treatment with oxygen fed; (4) quenching; (5) primary acid pickling to remove impurities; (6) secondary smashing and grinding; (7) secondary acid pickling to remove impurities; and (8) directional solidification. By means of the method, the solar-grade polycrystalline silicon, which is not more than 0.25 ppmw in the content of boron, is not more than 0.3 ppmw in the content of phosphorus, is not more than 0.1 ppmw in the content of metal impurities and is not less than 99.9999% in purity, is obtained. The method is simple in operation and equipment and can overcome defects that a physical method requires large-size expensive devices such as plasma, electron beam, vacuum and the like, so that the solar-grade polycrystalline silicon can be produced in a low cost through the physical method.
Description
Technical field
The present invention relates to a kind of production method of silicon, particularly relate to a kind of method that low cost prepares solar-grade polysilicon.
Background technology
At present, global energy industry is faced with the dual-pressure of danger that the fossil energies such as coal, oil, Sweet natural gas exhaust gradually and environment protection, and develop actively renewable energy source has become world's common recognition.Compared with traditional energy, solar electrical energy generation has the advantages such as clean, safety, resource are sufficient, effectively can alleviate the problem of energy shortage and environmental pollution, therefore, photovoltaic energy is considered to 21 century most important new forms of energy, and photovoltaic industry has become one of the fastest industry of global evolution in recent years.The solar cell kind of photovoltaic energy is a lot, as crystal silicon solar energy battery, thin-film solar cells, compound solar cell etc., wherein crystal silicon solar energy battery is with aboundresources, nontoxic and stable performance and become first-selected, occupies more than 90% of world's photovoltaic cell output.
As the polysilicon of crystal silicon solar energy battery raw material, mainly contain two kinds of preparation were establisheds, a kind of is take improved Siemens as the chemical method preparation technology of representative; Another kind is Physical preparation technology.Improved Siemens is with hydrochloric acid and industrial silica fume synthesizing trichlorosilane at a certain temperature, then carries out separation rectification and purification to trichlorosilane, and the trichlorosilane after purification carries out CVD reaction and produces high purity polycrystalline silicon in hydrogen reduction furnace.This explained hereafter cost is high, investment is large, complex process, and intermediates trichlorosilane (or silicon tetrachloride) has severe toxicity, there is potential safety hazard.Physical technique mainly carries out removal of impurities by techniques such as carbothermic method, pickling, directional freeze, oxidation refining, vacuum refinement, plasma melting, electron beam meltings, and silicon chemical transformation does not occur in the purification process of impurity element.Compared with chemical method, Physical less investment, the construction period is short, production energy consumption is low, environmentally friendly, be acknowledged as more promising a kind of technique in polycrystalline silicon preparing process.
But Physical also comes with some shortcomings, such as, often to use the Large expensive equipment such as plasma, electron beam, vacuum in process of production, make production cost higher, reduce the competitiveness of Physical.
Summary of the invention
The present invention be directed to existing Physical and prepare the Large expensive equipment such as excessive use plasma, electron beam, vacuum in solar-grade polysilicon, cause production cost higher, degradation shortcoming under product competition, provides a kind of low cost to prepare the method for solar-grade polysilicon.
For achieving the above object, technical solution of the present invention is:
The present invention is a kind of method that low cost prepares solar-grade polysilicon, comprises the following steps:
(1) medium-frequency induction furnace deposite metal silicon: be that in the plumbago crucible of the metal silico briquette material loading medium-frequency induction furnace of 3N, heat fused becomes silicon liquid by purity;
(2) air blowing slag refining: drop into slag former in the silicon liquid that step (1) melts, raised temperature passes into gas and carries out air blowing slag refining after slag former is melted completely; After refining terminates, the slag former on silicon liquid surface is extracted, more remaining silicon liquid is poured in iron pan be cooled to silicon ingot fast; The object of this step is the strong adsorption effect by slag former, by impurity absorption in silicon in slag former, is extracted by the slag former on silicon liquid surface after air blowing slag making simultaneously, alleviates the pressure of subsequent step removal of impurities.
(3) once grinding is pulverized: once pulverized by the silicon ingot that step (2) is obtained and grind to form 10 ~ 30 orders with thin silica flour;
(4) logical oxygen preheat process: the silica flour that step (3) is obtained is put into the logical oxygen preheat process of tubular oven; Because the partial impurities in silicon after air blowing slag making and the partial alkaline-metal in slag former can be separated out with the form of simple substance, if the rear pickling of direct pulverizing grinding can produce a large amount of hydrogen, silica flour is floated, weaken pickling impurity removal effect.The object of this step is exactly that the simple substance of precipitation is become metal oxide through logical oxygen heating rear oxidation, makes can not produce a large amount of hydrogen in acid cleaning process and cause silica flour to float.
(5) quench: the silica flour of logical for step (4) oxygen preheat process is dropped in acid solution and quenches; The object of this step is silica flour intercrystalline cracking after quenching that logical oxygen is heated, and impurity is exposed in acid solution completely, and the acid liquor temperature simultaneously after quenching raises, and is conducive to promoting pickling impurity removal effect.
(6) pickling impurity removals: the silica flour after step (5) being quenched carries out a pickling impurity removal in the acid solution of quenching, acid cleaning process keeps stirring, and silica flour cleans to neutral post-drying by the complete rear deionized water of pickling;
(7) separating twice grinding: the silica flour that step (6) is obtained is carried out separating twice and grinds to form 120 ~ 200 orders with thin silica flour; Silica flour is pulverized and is ground to more small particle size by this step, its objective is and makes silica flour break along the grain boundaries of smaller szie and allow impurity come out, promote pickling impurity removal effect further.
(8) white picking removal of impurities: the silica flour that step (7) is obtained carries out white picking removal of impurities, adds one-time surface promoting agent during second time pickling in right amount, and acid cleaning process keeps stirring, and silica flour cleans to neutral post-drying by the complete rear deionized water of pickling;
(9) directional freeze: silica flour obtained for step (8) is dropped in directional solidification furnace and carries out directional freeze formation silicon ingot; Take out silicon ingot after cooling, excision top, bottom and peripheral portion, remainder is just the solar-grade polysilicon of B content≤0.25ppmw, P content≤0.3ppmw, metals content impurity≤0.1ppmw, purity >=99.9999%.
The B content of Pure Silicon Metal described in step (1) is less than that 6ppm, P content is less than 20ppm, metallic impurity total content is less than 1000ppm.
The component of the slag former in described step (2) is Na
2cO
3-Li
2cO
3-CaCO
3-SiO
2-X, wherein, X is TiO
2, MgO, Al
2o
3, MnO
2, SnO
2, Fe
3o
4, Y
2o
3in one or more; The add-on of slag former is 30% ~ 100% of silicon liquid by mass percentage; The temperature of fusing slag former is 1500 ~ 1700 DEG C; Passing into gas is one in argon gas or nitrogen or argon gas and nitrogen mixed gas; In described argon gas and nitrogen mixed gas, by volume per-cent is: argon gas is 30 ~ 40%, and nitrogen is 60 ~ 70%, and ventilation flow rate is 3 ~ 10L/min, and aeration time is 0.3 ~ 2h.
Component and the content of the slag former in described step (2) are by mass percentage: Na
2cO
3account for 30% ~ 40%, Li
2cO
3account for 5% ~ 20%, CaCO
3account for 10% ~ 30%, SiO
2account for 20% ~ 40%, X and account for 3% ~ 15%, wherein, X is TiO
2, MgO, Al
2o
3, MnO
2, SnO
2, Fe
3o
4, Y
2o
3in one or more.
Preheat process temperature is 300 ~ 500 DEG C in step (4), and the flow of oxygen is 0.5 ~ 5L/min, and ventilation heat-up time is 0.5 ~ 4h.
The acid solution quenched described in step (5) is made up of HF acid and HCl acid, and wherein, HF acid mass concentration is 5 ~ 15%, HCl acid mass concentration is 10 ~ 20%; The mass ratio of silica flour and acid solution is 1: 2 ~ 1:5.
In step (6), the pickling time of a pickling impurity removal is 2 ~ 6h.
In step (8) white picking except the acid solution used mixedly be sour by HF acid, HCl and HNO
3acid composition, wherein, HF acid mass concentration is 3 ~ 10%, HCl acid mass concentration is 5 ~ 15%, HNO
3acid mass concentration is 1 ~ 5%; The mass ratio of silica flour and acid solution is 1: 2 ~ 1:6, and pickling time is 4 ~ 8h; Described one-time surface promoting agent is any one in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, heptadecane yl carboxylic acid sodium, and its add-on is 0.01% ~ 0.5% of silica flour by mass percentage.
After adopting such scheme, the present invention has the following advantages:
1, because the present invention utilizes the strong adsorption effect of efficient slag former, by the impurity absorption in silicon in slag former; Then through step strengthening pickling impurity removal effects such as logical oxygen preheat process, quenching, twice pulverizing grinding, twice pickling, 6N solar-grade polysilicon is obtained finally by directional freeze.
2, the Large expensive equipment such as plasma, electron beam, vacuum are not related to due to the present invention, simple to operate, facility investment is little, can carry out scale operation, be conducive to reducing the cost that Physical prepares polysilicon.
3, due to the Na in slag former of the present invention
2cO
3, Li
2cO
3, CaCO
3at high temperature with SiO
2reaction generates Na
2siO
3, Li
2siO
3, CaSiO
3deng silicate, these silicate are by silicon-oxy tetrahedron [SiO
4] or [SiO
4] bunch be skeleton, Na
+, Li
+, Ca
2+be evenly distributed on the space net structure formed in tetrahedral framework space, simultaneously due to Na
+, Li
+, Ca
2+ionic radius different, make the space net structure of silicate have size different " mesh ", strengthen its adsorptive power to impurity in silicon, adding X(X in slag former is TiO
2, MgO, Al
2o
3, MnO
2, SnO
2, Fe
3o
4, Y
2o
3in one or more) impurity element sex change in silicon can be impelled to become stable compound, make it be easier to adsorb by the reticulated structure of silicate, make slag former of the present invention have strong adsorption effect.
Below in conjunction with the drawings and specific embodiments, the present invention is further illustrated.
Accompanying drawing explanation
Fig. 1 is the schema that a kind of low cost of the present invention prepares the method for solar-grade polysilicon.
Embodiment
As shown in Figure 1, embodiment 1
A kind of low cost of the present invention prepares the method for solar-grade polysilicon, comprises the following steps:
Step 1: medium-frequency induction furnace deposite metal silicon
Be that the metal silico briquette material (B content≤5ppmw, P content≤20ppm, metallic impurity total content≤1000ppm) of 3N loads heat fused in the plumbago crucible of medium-frequency induction furnace and becomes silicon liquid by 10KG purity;
Step 2: air blowing slag refining
In the silicon liquid that step 1 melts, drop into the slag former of 5KG, slag former component and content are 30%Na by mass percentage
2cO
3-10%Li
2cO
3-20%CaCO
3-30%SiO
2-5%SnO
2-5% TiO
2, be warming up to 1700 DEG C and slag former melted completely; Then pass into argon gas with the flow of 5L/min, aeration time is 0.5h; After ventilation terminates, the slag former on silicon liquid surface is extracted, then remaining silicon liquid is poured in iron pan and be cooled to silicon ingot fast;
Step 3: once pulverize grinding
Silicon ingot obtained for step 2 is pulverized and grinds to form 20 orders with thin silica flour;
Step 4: logical oxygen preheat process
The silica flour that step 3 is obtained is put into the logical oxygen preheat process of tubular oven, Heating temperature is 400 DEG C, and the flow of oxygen is 1L/min, and aeration time is 1h;
Step 5: quenching
Silica flour step 4 being led to oxygen preheat process drops in the acid solution of 30KG and quenches; The composition of acid solution counts the HF acid of 10% and the HCl acid of 20% by mass concentration;
Step 6 a: pickling impurity removal
Silica flour after step 5 is quenched pickling 3h in the acid solution of quenching, acid cleaning process keeps stirring, and the complete rear deionized water of pickling is by silica flour cleaning extremely neutral post-drying;
Step 7: separating twice grinds
Silica flour obtained for step 6 is pulverized and grinds to form 160 orders with thin silica flour;
Step 8: white picking removal of impurities
Silica flour obtained for step 7 is dropped into pickling 6h in the acid solution of 30KG; The composition of acid solution by mass concentration count the HF acid of 5%, the HCl acid of 10% and 3% HNO
3acid, adds the Sodium dodecylbenzene sulfonate of 5g in acid solution; Acid cleaning process keeps stirring, and the complete rear deionized water of pickling is by silica flour cleaning extremely neutral post-drying;
Step 9: directional freeze
Silica flour obtained for step 8 is dropped in directional solidification furnace and carries out directional freeze formation silicon ingot; Silicon ingot is taken out, excision top, bottom and peripheral portion, remainder silicon ingot ICP-MS(plasma mass spectrograph after cooling) record ppmw, P content=0.27, B content=0.17 ppmw, metals content impurity≤0.1ppmw.
Embodiment 2
Step 1: medium-frequency induction furnace deposite metal silicon
Be that the metal silico briquette material (B content≤6ppmw, P content≤20ppm, metallic impurity total content≤1000ppm) of 3N loads heat fused in the plumbago crucible of medium-frequency induction furnace and becomes silicon liquid by 10KG purity;
Step 2: air blowing slag refining
In the silicon liquid that step 1 melts, drop into the slag former of 10KG, slag former component and content are 30%Na by mass percentage
2cO
3-15%Li
2cO
3-15%CaCO
3-35%SiO
2-5% Y
2o
3, be warming up to 1650 DEG C and slag former melted completely; Then pass into nitrogen with the flow of 7L/min, aeration time is 1h; After ventilation terminates, the slag former on silicon liquid surface is extracted, then remaining silicon liquid is poured in iron pan and be cooled to silicon ingot fast;
Step 3: once pulverize grinding
Silicon ingot obtained for step 2 is pulverized and grinds to form 30 orders with thin silica flour;
Step 4: logical oxygen preheat process
The silica flour that step 3 is obtained is put into the logical oxygen preheat process of tubular oven, Heating temperature is 350 DEG C, and the flow of oxygen is 1.5L/min, and aeration time is 1h;
Step 5: quenching
Silica flour step 4 being led to oxygen preheat process drops in the acid solution of 40KG and quenches; The composition of acid solution counts the HF acid of 12% and the HCl acid of 15% by mass concentration;
Step 6 a: pickling impurity removal
Silica flour after step 5 is quenched pickling 5h in the acid solution of quenching, acid cleaning process keeps stirring, and the complete rear deionized water of pickling is by silica flour cleaning extremely neutral post-drying;
Step 7: separating twice grinds
Silica flour obtained for step 6 is pulverized and grinds to form 200 orders with thin silica flour;
Step 8: white picking removal of impurities
Silica flour obtained for step 7 is dropped into pickling 8h in the acid solution of 40KG; The composition of acid solution by mass concentration count the HF acid of 3%, the HCl acid of 10% and 1% HNO
3acid, adds the sodium lauryl sulphate of 10g in acid solution; Acid cleaning process keeps stirring, and the complete rear deionized water of pickling is by silica flour cleaning extremely neutral post-drying;
Step 9: directional freeze
Silica flour obtained for step 8 is dropped in directional solidification furnace and carries out directional freeze formation silicon ingot; Silicon ingot is taken out, excision top, bottom and peripheral portion, remainder silicon ingot ICP-MS(plasma mass spectrograph after cooling) record ppmw, P content=0.21, B content=0.24 ppmw, metals content impurity≤0.1ppmw.
Embodiment 3
Step 1: medium-frequency induction furnace deposite metal silicon
Be that the metal silico briquette material (B content≤4ppmw, P content≤15ppm, metallic impurity total content≤1000ppm) of 3N loads heat fused in the plumbago crucible of medium-frequency induction furnace and becomes silicon liquid by 10KG purity;
Step 2: air blowing slag refining
In the silicon liquid that step 1 melts, drop into the slag former of 4KG, slag former component and content mass percent count 30%Na
2cO
3-10%Li
2cO
3-17%CaCO
3-30%SiO
2-7%MgO-6%Fe
3o
4, be warming up to 1650 DEG C and slag former melted completely; Then pass into the mixed gas (form by volume percentages argon gas is for 30%, nitrogen is 70%) of argon gas and nitrogen with the flow of 8L/min, aeration time is 1.5h; After ventilation terminates, the slag former on silicon liquid surface is extracted, then remaining silicon liquid is poured in iron pan and be cooled to silicon ingot fast;
Step 3: once pulverize grinding
Silicon ingot obtained for step 2 is pulverized and grinds to form 15 orders with thin silica flour;
Step 4: logical oxygen preheat process
The silica flour that step 3 is obtained is put into the logical oxygen preheat process of tubular oven, Heating temperature is 400 DEG C, and the flow of oxygen is 1L/min, and aeration time is 2h;
Step 5: quenching
Silica flour step 4 being led to oxygen preheat process drops in the acid solution of 30KG and quenches; The composition of acid solution counts the HF acid of 8% and the HCl acid of 20% by mass concentration;
Step 6 a: pickling impurity removal
Silica flour after step 5 is quenched pickling 6h in the acid solution of quenching, acid cleaning process keeps stirring, and the complete rear deionized water of pickling is by silica flour cleaning extremely neutral post-drying;
Step 7: separating twice grinds
Silica flour obtained for step 6 is pulverized and grinds to form 140 orders with thin silica flour;
Step 8: white picking removal of impurities
Silica flour obtained for step 7 is dropped into pickling 6h in the acid solution of 30KG; The composition of acid solution by mass concentration count the HF acid of 5%, the HCl acid of 15% and 4% HNO
3acid, adds the heptadecane yl carboxylic acid sodium of 8g in acid solution; Acid cleaning process keeps stirring, and the complete rear deionized water of pickling is by silica flour cleaning extremely neutral post-drying;
Step 9: directional freeze
Silica flour obtained for step 8 is dropped in directional solidification furnace and carries out directional freeze formation silicon ingot; Silicon ingot is taken out, excision top, bottom and peripheral portion, remainder silicon ingot ICP-MS(plasma mass spectrograph after cooling) record ppmw, P content=0.26, B content=0.19 ppmw, metals content impurity≤0.1ppmw.
State in several embodiment on the invention, the component of described slag former and content are by mass percentage: Na
2cO
3account for 30% ~ 40%, Li
2cO
3account for 5% ~ 20%, CaCO
3account for 10% ~ 30%, SiO
2account for 20% ~ 40%, X and account for 3% ~ 15%, wherein, X is TiO
2, MgO, Al
2o
3, MnO
2, SnO
2, Fe
3o
4, Y
2o
3in one or more.
The above, be only present pre-ferred embodiments, therefore can not limit scope of the invention process with this, and the equivalence namely done according to the present patent application the scope of the claims and description changes and modifies, and all should still remain within the scope of the patent.
Claims (8)
1. low cost prepares a method for solar-grade polysilicon, it is characterized in that: comprise the following steps:
(1) medium-frequency induction furnace deposite metal silicon: be that in the plumbago crucible of the metal silico briquette material loading medium-frequency induction furnace of 3N, heat fused becomes silicon liquid by purity;
(2) air blowing slag refining: drop into slag former in the silicon liquid that step (1) melts, raised temperature passes into gas and carries out air blowing slag refining after slag former is melted completely; After refining terminates, the slag former on silicon liquid surface is extracted, more remaining silicon liquid is poured in iron pan be cooled to silicon ingot fast;
(3) once grinding is pulverized: once pulverized by the silicon ingot that step (2) is obtained and grind to form 10 ~ 30 orders with thin silica flour;
(4) logical oxygen preheat process: the silica flour that step (3) is obtained is put into the logical oxygen preheat process of tubular oven;
(5) quench: the silica flour of logical for step (4) oxygen preheat process is dropped in acid solution and quenches;
(6) pickling impurity removals: the silica flour after step (5) being quenched carries out a pickling impurity removal in the acid solution of quenching, acid cleaning process keeps stirring, and silica flour cleans to neutral post-drying by the complete rear deionized water of pickling;
(7) separating twice grinding: the silica flour that step (6) is obtained is carried out separating twice and grinds to form 120 ~ 200 orders with thin silica flour;
(8) white picking removal of impurities: the silica flour that step (7) is obtained carries out white picking removal of impurities, adds one-time surface promoting agent during second time pickling in right amount, and acid cleaning process keeps stirring, and silica flour cleans to neutral post-drying by the complete rear deionized water of pickling;
(9) directional freeze: silica flour obtained for step (8) is dropped in directional solidification furnace and carries out directional freeze formation silicon ingot; Take out silicon ingot after cooling, excision top, bottom and peripheral portion, remainder is just the solar-grade polysilicon of B content≤0.25ppmw, P content≤0.3ppmw, metals content impurity≤0.1ppmw, purity >=99.9999%.
2. low cost as claimed in claim 1 prepares the method for solar-grade polysilicon, it is characterized in that: the B content of Pure Silicon Metal described in step (1) is less than that 6ppm, P content is less than 20ppm, metallic impurity total content is less than 1000ppm.
3. low cost as claimed in claim 1 prepares the method for solar-grade polysilicon, it is characterized in that: the component of the slag former in described step (2) is Na
2cO
3-Li
2cO
3-CaCO
3-SiO
2-X, wherein, X is TiO
2, MgO, Al
2o
3, MnO
2, SnO
2, Fe
3o
4, Y
2o
3in one or more; The add-on of slag former is 30% ~ 100% of silicon liquid by mass percentage; The temperature of fusing slag former is 1500 ~ 1700 DEG C; Passing into gas is one in argon gas or nitrogen or argon gas and nitrogen mixed gas; In described argon gas and nitrogen mixed gas, by volume per-cent is: argon gas is 30 ~ 40%, and nitrogen is 60 ~ 70%, and ventilation flow rate is 3 ~ 10L/min, and aeration time is 0.3 ~ 2h.
4. the low cost as described in claim 1 or 3 prepares the method for solar-grade polysilicon, it is characterized in that: component and the content of the slag former in described step (2) are by mass percentage: Na
2cO
3account for 30% ~ 40%, Li
2cO
3account for 5% ~ 20%, CaCO
3account for 10% ~ 30%, SiO
2account for 20% ~ 40%, X and account for 3% ~ 15%, wherein, X is TiO
2, MgO, Al
2o
3, MnO
2, SnO
2, Fe
3o
4, Y
2o
3in one or more.
5. low cost as claimed in claim 1 prepares the method for solar-grade polysilicon, it is characterized in that: in step (4), preheat process temperature is 300 ~ 500 DEG C, and the flow of oxygen is 0.5 ~ 5L/min, and ventilation heat-up time is 0.5 ~ 4h.
6. low cost as claimed in claim 1 prepares the method for solar-grade polysilicon, it is characterized in that: the acid solution quenched described in step (5) is made up of HF acid and HCl acid, wherein, HF acid mass concentration is 5 ~ 15%, HCl acid mass concentration is 10 ~ 20%; The mass ratio of silica flour and acid solution is 1: 2 ~ 1:5.
7. low cost as claimed in claim 1 prepares the method for solar-grade polysilicon, it is characterized in that: in step (6), the pickling time of a pickling impurity removal is 2 ~ 6h.
8. low cost as claimed in claim 1 prepares the method for solar-grade polysilicon, it is characterized in that: in step (8) white picking except the acid solution used mixedly be sour by HF acid, HCl and HNO
3acid composition, wherein, HF acid mass concentration is 3 ~ 10%, HCl acid mass concentration is 5 ~ 15%, HNO
3acid mass concentration is 1 ~ 5%; The mass ratio of silica flour and acid solution is 1: 2 ~ 1:6, and pickling time is 4 ~ 8h; Described one-time surface promoting agent is any one in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, heptadecane yl carboxylic acid sodium, and its add-on is 0.01% ~ 0.5% of silica flour by mass percentage.
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| CN108793170B (en) * | 2018-06-23 | 2020-06-02 | 新疆中诚硅材料有限公司 | Industrial silicon acid pickling process after ventilation, slagging, smelting and pretreatment |
| CN115353110A (en) * | 2022-07-28 | 2022-11-18 | 商南中剑实业有限责任公司 | Method for removing boron impurities in industrial silicon by silicomanganese slagging and refining |
| CN115353110B (en) * | 2022-07-28 | 2023-11-21 | 商南中剑实业有限责任公司 | Method for removing boron impurities in industrial silicon by silicomanganese slagging refining |
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