CN110467185A - A kind of silicon materials dephosphorization purification additive and method of purification - Google Patents
A kind of silicon materials dephosphorization purification additive and method of purification Download PDFInfo
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Abstract
The present invention relates to a kind of silicon materials dephosphorization purification additive and methods of purification.The additive is mixed in any proportion by raw material ice crystal, containing one or more of titanium halide, vanadium containing brine compound, alkali halide, alkaline-earth halide, aluminum fluoride.Using the additive silicon materials are carried out with the method for purification of dephosphorization: by silicon raw material, metal medium and the additive heating fusing, stirring evenly carry out slag refining；After slag refining, it is cooling again after the slag phase of acquisition is separated with silicon alloy or will the slag phase of acquisition cooled down with silicon alloy after separate again；The silicon alloy obtained after separation is placed in acid solution and is impregnated, the silicon material of acquisition is carried out drying and processing later by the metal medium in dissolution removal silicon alloy；It repeats abovementioned steps 1~4 time, until phosphorus content meets purity requirement in silicon material.Additive of the present invention makes refining except boron temperature is reduced to 600 DEG C~1300 DEG C, and low energy consumption, and phosphorus ligands significant effect.
Description
Technical field
The invention belongs to silicon materials purification technique field, it is specifically related to a kind of silicon materials dephosphorization purification additive and mentions
Pure method.
Background technique
Rapid growth is presented in solar energy power generating market in recent years, manufactures high-purity solar-grade silicon material used for solar batteries
Demand also rapid growth.In traditional silicon material purification technology, chemical method is always mainstream, the purity of silicon of chemical method purification
Height, high-quality, technology maturation, but chemical method purifying technique is complicated and more difficult to control, and seriously polluted, investment is big, cost
It is high.And silicon is purified using chemical method, in the industrial chain of manufacture of solar cells, the accounting of energy consumption and carbon emission is high
Up to 50% or more.Therefore, exploitation has low energy consumption, low emission, and inexpensive silicon material purification technology has great importance.
Slag practice conducts extensive research both at home and abroad as a kind of method for effectively removing impurity in silicon, but insufficient
Place is that selected is all dystectic slag former, and temperature needed for slag refining is all higher than the fusing point of silicon
It is 1414 DEG C, excessively high excessively high with energy consumption so as to cause temperature.
Patent application CN102951645A discloses a kind of method that slag refining removes boron phosphorus, the slag former that this method is selected
For iron oxide, SiO2, MnO and CaF2；The iron oxide is Fe2O3、FeO、Fe3O4One of；Slag former and industrial silicon are pressed
It is (20~26): (5~9) according to mass ratio.1550~1850 DEG C or more, which are heated to, using induction furnace carries out slag refining, charging side
Formula is first to melt slag former, and industrial silicon is then poured into liquid slag former progress slag making processing, while to leading to inside melt
Enter Ar+H2O is repeated slag making 8 times, and the content of phosphorus is down to 0.5ppmw.
Patent application CN02135841.9A discloses a kind of high-purity silicon for solar energy cell and its production method, this is specially
Described in benefit it is a kind of add lime into melt, iron oxide, the slagging process of fluorite obtains used for solar batteries high-purity
Silicon.
Patent application CN201010109835.2A discloses a kind of using rare earth oxide removal boron from industrial silicon phosphorus impurities
Method, which introduces rare earth oxide in slag former ingredient, and specific ingredient is RXOY(Y2O3、La2O3、CeO2、
Sm2O3)-SiO2-BaO-CaF2, with Medium frequency induction slag making 40min under vacuum, slag silicon weight ratio is 1:1, and P content is from 15ppmw
It is reduced to 1.5ppmw.
By comparing the patent and document analyzed in terms of current slag practice dephosphorization it is found that the type of existing slag former is main
It is based on oxide, such as CaO-SiO2, Na2O-SiO2, CaO-SiO2-CaF2, CaO-MgO-SiO2, CaO-BaO-SiO2, simultaneously
Auxiliary adds the compound of a small amount of low melting point to reduce the viscosity of melt, improves the mobility of melt, imitates to the removal of impurities of boron in silicon
Fruit is much better than phospha prime element；Above to study used slag making temperature at 1414 DEG C or more, energy consumption is higher, is also unfavorable for future
Industrialized application.
Summary of the invention
In order to solve the above-mentioned technical problem, present invention firstly provides a kind of silicon materials dephosphorization to purify additive.The type adds
Agent is added to have fusing point low, 600 DEG C~1300 DEG C of slag refining temperature, low energy consumption, has significant ground removal effect to phosphorus.
In order to achieve the object of the present invention, the invention adopts the following technical scheme:
A kind of silicon materials dephosphorization purifies additive, the additive by raw material ice crystal, containing titanium halide, vanadium containing brine compound,
One or more of alkali halide, alkaline-earth halide, aluminum fluoride are mixed in any proportion.
Preferred embodiment: described containing titanium halide is TiClx, TiBrx, TiIx, one or more of TiFx, wherein x value
It is 1~10.
Preferred embodiment: the vanadium containing brine compound is VClx, VBrx, VIx, one of VFx, and wherein x value is 1~10.
Preferred embodiment: the alkali halide includes by the member of alkali metal element Li, Na, K, Rb and VIIA race of IA race
One or more of compounds that plain F, Cl, Br, I are formed.
Preferred embodiment: the alkaline-earth halide include by Group IIA alkali metal element Be, Mg, Ca, Sr, Ba with
One or more of compounds that element F, Cl, Br, I of VIIA race are formed.
Preferred embodiment: the vanadium containing brine compound is vanadium trichloride, and the alkaline-earth halide is calcium halide.
It is a further object to provide a kind of purification sides that using the additive silicon materials are carried out with dephosphorization
Method.The method of purification the following steps are included:
Step 1, by silicon raw material, metal medium and the additive all heating fusing, stir evenly, and 600~
It is carried out slag refining 2~6 hours at 1300 DEG C；
Step 2, cooling again after the slag phase of acquisition is separated with silicon alloy or by the slag of acquisition after slag refining
Mutually separated again with after silicon alloy cooling；
Step 3, the silicon alloy obtained after separation is placed in acid solution and is impregnated, the metal in dissolution removal silicon alloy is situated between
The silicon material of acquisition is carried out drying and processing later by matter；
Step 4, step 1~step 3 is repeated 1~4 time, until phosphorus content meets purity requirement in silicon material.
Further technical solution: the ratio of additive usage amount and the silicon raw material, metal medium total amount in the step 1
Example is 0.1~10.
Further technical solution: silicon alloy is sial, ferrosilicon, silico-calcium, silicon gallium, silicon titanium, silicomanganese, silicon in the step 2
One or more of tin, SiGe, silicon vanadium, copper silicon, silicon zinc, silicozirconium, the ratio of silicon is 0.1%~99% in silicon alloy.
Further technical solution: acid solution is hydrochloric acid solution, nitric acid solution, sulfuric acid solution, hydrofluoric acid in the step 3
One or more of solution, phosphoric acid solution.
The beneficial effects of the present invention are:
Additive of the present invention has fusing point low, and 600 DEG C~1300 DEG C of slag refining temperature, low energy consumption, has to phosphorus aobvious
Land removal effect.The method of purification smelting temperature is low, and the time is short, and the energy consumption of melting can be greatly lowered, and technique is relatively simple
Single, removal of impurity is high, is conducive to be mass produced.Using additive and method of purification of the invention, by a slag making essence
The content of phosphorus can be down to 0.3ppmw in silicon after refining processing, and removal rate is up to 99.78% or more.
Detailed description of the invention
Fig. 1 is method of purification flow chart of the present invention.
Specific embodiment
More specific detail is made to technical solution of the present invention below with reference to embodiment:
Silicon materials dephosphorization of the present invention purifies additive, by raw material ice crystal, contains titanium halide, vanadium containing brine compound, alkali
One or more of metal halide, alkaline-earth halide, aluminum fluoride are mixed in any proportion.The additive
Raw material can be powder-material and/or particulate material.
The titanium halide that contains is TiClx, TiBrx, TiIx, one or more of TiFx.
The vanadium containing brine compound is VClx, VBrx, VIx, one of VFx.The preferred vanadium trichloride of vanadium containing brine compound.
Since there are a variety of valence states for transition metal, so above-mentioned x value is a variate-value, the preferred x value of the present invention is 1~10.
The alkali halide include by alkali metal element Li, Na, K, Rb and VIIA race of IA race element F, Cl,
One or more of compounds that Br, I are formed.
The alkaline-earth halide includes by the element of alkali metal element Be, Mg, Ca, Sr, Ba and VIIA race of Group IIA
F, one or more of compounds that Cl, Br, I are formed.The preferred calcium halide of alkaline-earth halide.
Additive described in use of the present invention carries out the method for purification of dephosphorization to silicon materials, comprising the following steps:
Step 1, by silicon raw material, metal medium and the additive all heating fusing, stir evenly, and 600~
It is carried out slag refining 2~6 hours at 1300 DEG C, additive usage amount and the silicon raw material, the ratio of metal medium total amount are 0.1
~10.
Silicon raw material can be metallurgical grade silicon, top grade silicon, Buddha's warrior attendant wire cutting waste silicon powder, electronic-grade silicon waste material in above-mentioned steps 1
Or other types of silicon tailing.The metal medium can form alloy with silicon, and the fusion temperature of alloy is molten far below silicon
Change temperature.
Container when fusing is heated in above-mentioned steps 1 using graphite crucible or corundum crucible or silica crucible, and heating is set
Standby is induction furnace or Si-Mo rod furnace or silicon carbide rod furnace or resistance furnace.
The concrete operations of silicon raw material in above-mentioned steps 1, metal medium and additive heating fusing can there are two types of
Mode, first way are as follows: the additive is added to silicon raw material, carries out heating fusing together in metal medium；Second
Mode are as follows: pre-melted additive is added in the silicon alloy melt by being formed after silicon raw material, metal medium fusing.
Stirring can use mechanical stirring or electromagnetic agitation in above-mentioned steps 1, every 10min when using mechanical stirring
~30min carries out primary, 0~300V of voltage of control stirring electromagnetic field when using electromagnetic agitation.
Step 2, cooling again after the slag phase of acquisition is separated with silicon alloy or by the slag of acquisition after slag refining
Mutually separated again with after silicon alloy cooling.The silicon alloy is sial, ferrosilicon, silico-calcium, silicon gallium, silicon titanium, silicomanganese, silicon tin, SiGe, silicon
One or more of vanadium, copper silicon, silicon zinc, silicozirconium, the ratio of silicon is 0.1%~99% in silicon alloy.
It is cooled down again after being separated the slag phase of acquisition with silicon alloy in above-mentioned steps 2, it may be assumed that slag phase is directly inclined when separation
It pours out or is separated by filtration slag phase.Temperature overheats 10 for the liquidus temperature of silicon alloy melt when slag phase being used directly to be poured out
℃；Using, using porous aluminas or porous graphite filtering container, the diameter control of filter hole is in 3mm when being separated by filtration slag phase
Within.Certainly according to the difference of silicon alloy melt and slag phase viscosity, filtering point can also be realized using extruding or centrifugation
From.
It will be separated again after the slag phase of acquisition and silicon alloy cooling in above-mentioned steps 2, it may be assumed that do not topple over slag phase at high temperature, allow
Slag inclusion alloy after solidification is used diamond wire saw machine-cut as silicon alloy melt is with certain cooling rate solidification by slag phase
Cut separation or grinder buffing removal slag phase, the silicon alloy phase after being solidified again.
Step 3, the silicon alloy obtained after separation is placed in acid solution and is impregnated, the metal in dissolution removal silicon alloy is situated between
The silicon material of acquisition is carried out drying and processing later by matter.The acid solution is hydrochloric acid solution, nitric acid solution, sulfuric acid solution, hydrofluoric acid
One or more of solution, phosphoric acid solution can refer to known in this field as technological parameters such as concentration, the temperature of acid solution
Technology, silicon alloy can be dissolved by being subject to.
Step 4, step 1~step 3 is repeated 1~4 time, until phosphorus content meets purity requirement in silicon material.Phosphorus in silicon material
Content is detected using inductively coupled plasma atomic emission technology.
The difference of the present invention with traditional silicon materials dephosphorization purification is described below:
The fusing point of traditional oxide addition (slag former) is all at 1400 DEG C or more, the present invention has the advantages that selected
The low melting point additive selected can make slag making temperature be reduced to 1300 DEG C from 1500 DEG C hereinafter, 600 DEG C~1300 DEG C of slag making temperature,
Lower than the operation temperature of the refining of oxidative slagging in the prior art, energy consumption is significantly reduced, while additive proposed by the invention
Good fluidity is conducive to the removal of impurity, and technique is relatively easy, is conducive to be mass produced.
During traditional oxidative slagging, the fusing point for being limited by silicon is excessively high (1414 DEG C), in order to ensure silicon is completely melt, needs
Want slag refining temperature all at 1414 DEG C or more, this patent proposes the mode of alloying with silicon to reduce silicon melt in slagging process
Temperature, thus realize silicon cold melt refining.
Traditional oxidative slagging phosphor-removing effect is bad, generally requires multiple Refining, and the low temperature that this patent uses is non-
The efficient removal of phosphorus may be implemented in oxide addition, and the tp removal rate of single is significantly larger than the effect of oxidative slagging dephosphorization, this
And the present invention is different from an advantage of conventional oxidation slag making.
The fusing point of conventional oxide additive is higher than the density of silicon melt, causes silicon melt to float on slag phase, is unfavorable for
The mixing of slag silicon easily causes the oxidation of silicon melt surface, and then generates a large amount of oxidizing slag.And the non-oxidized substance that this patent proposes
The density of additive be lower than silicon melt density, it is ensured that slag phase floats on silicon melt, thus play prevent silicon melt with
Air contact aoxidizes, and reduces the loss of silicon, improves the recovery rate of silicon.
Non-oxidized substance additive proposed by the present invention have the characteristics that it is volatile, can use itself volatilization characteristic, will
Phospha prime element in silicon alloy is evaporated from silicon melt, to achieve the purpose that removal of impurities, this is also traditional oxide
Advantage not available for additive.
Non-oxidized substance additive proposed by the invention not only can use the volatile feature of additive, can also utilize
Chemical reaction between phosphorus and additive so that phosphorus is entered in additive in the form of certain specific compound, and then reaches
The purpose of removal of impurities.
By using low temperature non-oxidized substance additive above-mentioned, by refining treatment, the content of phosphorus can be down in silicon raw material
0.3ppmw, removal rate is up to 99.78% or more, simultaneously because refining temperature is low, energy consumption can be significantly reduced, be conducive to it is low at
This purification silicon.
Embodiment 1
25g silicon powder and 75g aluminium block are placed in alumina crucible, 100g ice crystal particle is then added, crucible is placed in
In resistance furnace, 900 DEG C, constant temperature 2h are at the uniform velocity warming up to, centre is stirred every 30min quartz pushrod once, to silicon alloy and slag making
Agent is completely melt uniformly, to be then cooled to room temperature with 0.01 DEG C/min.Sample after solidification is longitudinally cutd open with diamond custting machine
It opens, the slag former at top is mutually separated with the silicon alloy of lower part, then impregnates silicon alloy with hydrochloric acid solution, dissolve aluminum substrate,
Large-sized silicon wafer is obtained, using filtering, washing and dry mode, by silicon chip drying.Silicon wafer after drying is used into ICP-
The molten sample of OES analyzes phosphorus content therein, and acquired results are shown in Table 1.
Changes of contents before and after P slag making melting in 1. raw material of table
| Raw silicon (ppmw) | After purification (ppmw) | Removal rate (%) | |
| P impurity | 64 | 0.96 | 98.5 |
Embodiment 2
30g silicon powder and 70g aluminium block are placed in alumina crucible, 30g ice crystal particle and 30g calcium fluoride powder is then added
Crucible is placed in resistance furnace by mixture, is at the uniform velocity warming up to 1000 DEG C, constant temperature 3h, centre stirs one every 30min quartz pushrod
It is secondary, it is completely melt uniformly, to be then cooled to room temperature with 0.01 DEG C/min to silicon alloy and slag former.By the sample gold after solidification
Hard rock cutting machine is longitudinally splitted, and the slag former at top is mutually separated with the silicon alloy of lower part, then by silicon alloy hydrochloric acid solution
It impregnates, dissolves aluminum substrate, obtain large-sized silicon wafer, using filtering, washing and dry mode, by silicon chip drying.It will drying
Silicon wafer afterwards analyzes phosphorus content therein using the molten sample of ICP-OES, and acquired results are shown in Table 2.
Changes of contents before and after P slag making melting in 2. raw material of table
| Raw silicon (ppmw) | After purification (ppmw) | Removal rate (%) | |
| P impurity | 64 | 0.3 | 99.53 |
Embodiment 3
70g silicon powder and 130g aluminium block are placed in alumina crucible, 30g calcium chloride is then added, crucible is placed in resistance
In furnace, 1050 DEG C, constant temperature 2h are at the uniform velocity warming up to, centre is stirred once every 30min quartz pushrod, complete with slag former to silicon alloy
Running down is uniform, is then cooled to room temperature with 0.01 DEG C/min.Sample after solidification is longitudinally splitted with diamond custting machine, it will
The slag former at top is mutually separated with the silicon alloy of lower part, then impregnates silicon alloy with hydrochloric acid solution, dissolves aluminum substrate, is obtained big
The silicon wafer of size, using filtering, washing and dry mode, by silicon chip drying.Silicon wafer after drying is used into the molten sample of ICP-OES
Phosphorus content therein is analyzed, acquired results are shown in Table 3.
Changes of contents before and after P slag making melting in 3. raw material of table
| Raw silicon (ppmw) | After purification (ppmw) | Removal rate (%) | |
| P impurity | 235 | 1.1 | 99.53 |
Embodiment 4
37.5g silicon powder and 112.5g aluminium block are placed in alumina crucible, 30g sodium chloride and 30g calcium chloride is then added
Powder mixture, crucible is placed in resistance furnace, is at the uniform velocity warming up to 900 DEG C, constant temperature 6h, centre is stirred every 30min with quartz pushrod
Once, it is completely melt uniformly, to be then cooled to room temperature with 0.01 DEG C/min to silicon alloy and slag former.Sample after solidification is used
Diamond custting machine is longitudinally splitted, and the slag former at top is mutually separated with the silicon alloy of lower part, then that silicon alloy hydrochloric acid is molten
Liquid impregnates, and dissolves aluminum substrate, obtains large-sized silicon wafer, using filtering, washing and dry mode, by silicon chip drying.It will dry
Silicon wafer after dry analyzes phosphorus content therein using the molten sample of ICP-OES, and acquired results are shown in Table 4.
Changes of contents before and after P slag making melting in 4. raw material of table
| Raw silicon (ppmw) | After purification (ppmw) | Removal rate (%) | |
| P impurity | 235 | 0.8 | 99.65 |
Embodiment 5
70g silicon powder and 130g aluminium block are placed in alumina crucible, 30g aluminum fluoride and the mixing of 30g calcium chloride is then added
Material, crucible is placed in resistance furnace, is at the uniform velocity warming up to 1200 DEG C, constant temperature 6h, and centre is stirred once every 30min quartz pushrod,
It is completely melt uniformly, to be then cooled to room temperature with 0.01 DEG C/min to silicon alloy and slag former.By the sample Buddha's warrior attendant after solidification
Stone cutting machine is longitudinally splitted, and the slag former at top is mutually separated with the silicon alloy of lower part, then soaks silicon alloy with hydrochloric acid solution
Bubble dissolves aluminum substrate, obtains large-sized silicon wafer, using filtering, washing and dry mode, by silicon chip drying.After drying
Silicon wafer phosphorus content therein is analyzed using the molten sample of ICP-OES, acquired results are shown in Table 5.
Changes of contents before and after P slag making melting in 5. raw material of table
| Raw silicon (ppmw) | After purification (ppmw) | Removal rate (%) | |
| P impurity | 235 | 0.52 | 99.78 |
Embodiment 6
2g silicon powder and 180g gallium block are placed in alumina crucible, 25g vanadium trichloride and the mixing of 55g calcium chloride is then added
Material, crucible is placed in resistance furnace, is at the uniform velocity warming up to 900 DEG C, constant temperature 2h, and centre is stirred once every 30min quartz pushrod, to
Silicon alloy and slag former are completely melt uniformly, to be then cooled to room temperature with 0.01 DEG C/min.By the sample diamond after solidification
Cutting machine is longitudinally splitted, and the slag former at top is mutually separated with the silicon alloy of lower part, then impregnates silicon alloy with hydrochloric acid solution,
Aluminum substrate is dissolved, large-sized silicon wafer is obtained, using filtering, washing and dry mode, by silicon chip drying.By the silicon after drying
Piece analyzes phosphorus content therein using the molten sample of ICP-OES, and acquired results are shown in Table 6.
Changes of contents before and after P slag making melting in 6. raw material of table
| Raw silicon (ppmw) | After purification (ppmw) | Removal rate (%) | |
| P impurity | 235 | 1.65 | 99.30 |
Embodiment 7
30g silicon powder and 70g aluminium block are placed in alumina crucible, the TiCl of 1000g is then added4, crucible is placed in electricity
It hinders in furnace, is at the uniform velocity warming up to 600 DEG C, constant temperature 4h, centre is stirred every 30min quartz pushrod once, to silicon alloy and additive
It is completely melt uniformly, to be then cooled to room temperature with 0.01 DEG C/min.Sample after solidification is longitudinally splitted with diamond custting machine,
The additive at top is mutually separated with the silicon alloy of lower part, then impregnates silicon alloy with hydrochloric acid solution, aluminum substrate is dissolved, obtains
Large-sized silicon wafer, using filtering, washing and dry mode, by silicon chip drying.Silicon wafer after drying is molten using ICP-OES
Sample analyzes phosphorus content therein, and acquired results are shown in Table 7.
Changes of contents before and after P slag making melting in 7. raw material of table
| Raw silicon (ppmw) | After purification (ppmw) | Removal rate (%) | |
| P impurity | 235 | 0.9 | 99.62 |
Embodiment 8
30g silicon powder and 70g iron block are placed in alumina crucible, the vanadium trichloride of 10g is then added, crucible is placed in electricity
It hinders in furnace, is at the uniform velocity warming up to 1000 DEG C, constant temperature 4h, centre is stirred every 30min quartz pushrod once, to silicon alloy and additive
It is completely melt uniformly, to be then cooled to room temperature with 0.01 DEG C/min.Sample after solidification is longitudinally splitted with diamond custting machine,
The additive at top is mutually separated with the silicon alloy of lower part, then impregnates silicon alloy with hydrochloric acid solution, iron matrix is dissolved, obtains
Large-sized silicon wafer, using filtering, washing and dry mode, by silicon chip drying.Silicon wafer after drying is molten using ICP-OES
Sample analyzes phosphorus content therein, and acquired results are shown in Table 8.
Changes of contents before and after P slag making melting in 8. raw material of table
| Raw silicon (ppmw) | After purification (ppmw) | Removal rate (%) | |
| P impurity | 235 | 1.1 | 99.53 |
Embodiment 9
1g silicon powder and 180g block tin are placed in alumina crucible, the sodium chloride of 100g is then added, crucible is placed in electricity
It hinders in furnace, is at the uniform velocity warming up to 1050 DEG C, constant temperature 3h, centre is stirred every 30min quartz pushrod once, to silicon alloy and additive
It is completely melt uniformly, to be then cooled to room temperature with 0.01 DEG C/min.Sample after solidification is longitudinally splitted with diamond custting machine,
The additive at top is mutually separated with the silicon alloy of lower part, then impregnates silicon alloy with hydrochloric acid solution, tin matrix is dissolved, obtains
Large-sized silicon wafer, using filtering, washing and dry mode, by silicon chip drying.Silicon wafer after drying is molten using ICP-OES
Sample analyzes phosphorus content therein, and acquired results are shown in Table 9.
Changes of contents before and after P slag making melting in 9. raw material of table
| Raw silicon (ppmw) | After purification (ppmw) | Removal rate (%) | |
| P impurity | 235 | 1.0 | 99.57 |
Embodiment 10
693g silicon powder and 7g copper billet are placed in alumina crucible, the aluminum fluoride of 200g is then added, crucible is placed in electricity
It hinders in furnace, is at the uniform velocity warming up to 1300 DEG C, constant temperature 3h, centre is stirred every 30min quartz pushrod once, to silicon alloy and additive
It is completely melt uniformly, to be then cooled to room temperature with 0.01 DEG C/min.Sample after solidification is longitudinally splitted with diamond custting machine,
The additive at top is mutually separated with the silicon alloy of lower part, then impregnates silicon alloy with hydrochloric acid solution, Copper substrate is dissolved, obtains
Large-sized silicon wafer, using filtering, washing and dry mode, by silicon chip drying.Silicon wafer after drying is molten using ICP-OES
Sample analyzes phosphorus content therein, and acquired results are shown in Table 10.
Changes of contents before and after P slag making melting in 10. raw material of table
| Raw silicon (ppmw) | After purification (ppmw) | Removal rate (%) | |
| P impurity | 235 | 1.2 | 99.49 |
The above is only section Examples of the present invention, while can illustrate through the foregoing embodiment: when additive is by raw material ice
Spar, containing titanium halide, vanadium containing brine compound, alkali halide, alkaline-earth halide, in aluminum fluoride when any composition,
The low temperature slag making melting dephosphorization of silicon raw material may be implemented.Certainly, due to ice crystal, containing titanium halide, vanadium containing brine compound, alkali gold
It is close to belong to halide, alkaline-earth halide, aluminum fluoride these types raw material physicochemical property, so taking two or more original
Material carries out mixing as additive using arbitrary proportion, and the low temperature slag making melting dephosphorization of silicon raw material also may be implemented.
Claims (10)
1. a kind of silicon materials dephosphorization purifies additive, it is characterised in that: the additive by raw material ice crystal, containing titanium halide, contain
One or more of vanadium halide, alkali halide, alkaline-earth halide, aluminum fluoride are mixed in any proportion.
2. additive as described in claim 1, it is characterised in that: described containing titanium halide is TiClx, TiBrx, TiIx,
One or more of TiFx, wherein x value is 1~10.
3. additive as described in claim 1, it is characterised in that: the vanadium containing brine compound is VClx, VBrx, VIx, in VFx
One kind, wherein x value be 1~10.
4. additive as described in claim 1, it is characterised in that: the alkali halide includes the alkali metal member by IA race
One or more of compounds that element F, Cl, Br, I of plain Li, Na, K, Rb and VIIA race are formed.
5. additive as described in claim 1, it is characterised in that: the alkaline-earth halide includes the alkali gold by Group IIA
Belong to element Be, one or more of compounds that element F, Cl, Br, I of Mg, Ca, Sr, Ba and VIIA race are formed.
6. additive as described in claim 1, it is characterised in that: the vanadium containing brine compound is vanadium trichloride, the alkaline earth gold
Category halide is calcium halide.
7. a kind of method of purification that using additive as described in any one of claims 1 to 6 silicon materials are carried out with dephosphorization, special
Sign be the following steps are included:
Step 1, silicon raw material, metal medium and the additive are all heated to fusing, stirred evenly, and 600~1300
It is carried out slag refining 2~6 hours at DEG C；
Step 2, after slag refining, it is cooling again after the slag phase of acquisition is separated with silicon alloy or by the slag phase of acquisition with
It is separated again after silicon alloy is cooling；
Step 3, the silicon alloy obtained after separation is placed in acid solution and is impregnated, the metal medium in dissolution removal silicon alloy, it
The silicon material of acquisition is subjected to drying and processing afterwards；
Step 4, step 1~step 3 is repeated 1~4 time, until phosphorus content meets purity requirement in silicon material.
8. the method for purification of additive as claimed in claim 7, it is characterised in that: in the step 1 additive usage amount with
The silicon raw material, the ratio of metal medium total amount are 0.1~10.
9. the method for purification of additive as claimed in claim 7, it is characterised in that: silicon alloy is sial, silicon in the step 2
One or more of iron, silico-calcium, silicon gallium, silicon titanium, silicomanganese, silicon tin, SiGe, silicon vanadium, copper silicon, silicon zinc, silicozirconium, silicon alloy
The ratio of middle silicon is 0.1%~99%.
10. the method for purification of additive as claimed in claim 7, it is characterised in that: acid solution is that hydrochloric acid is molten in the step 3
One or more of liquid, nitric acid solution, sulfuric acid solution, hydrofluoric acid solution, phosphoric acid solution.
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| CN201910850909.9A CN110467185B (en) | 2019-09-10 | 2019-09-10 | Silicon material dephosphorization purification additive and purification method |
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