CN105540593B - A kind of slagging agent living removes the method and its device of boron - Google Patents

A kind of slagging agent living removes the method and its device of boron Download PDF

Info

Publication number
CN105540593B
CN105540593B CN201511027460.4A CN201511027460A CN105540593B CN 105540593 B CN105540593 B CN 105540593B CN 201511027460 A CN201511027460 A CN 201511027460A CN 105540593 B CN105540593 B CN 105540593B
Authority
CN
China
Prior art keywords
agitator
silicon
boron
slag
frequency induction
Prior art date
Application number
CN201511027460.4A
Other languages
Chinese (zh)
Other versions
CN105540593A (en
Inventor
罗学涛
唐天宇
熊华平
甘传海
赖惠先
黄柳青
Original Assignee
厦门大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 厦门大学 filed Critical 厦门大学
Priority to CN201511027460.4A priority Critical patent/CN105540593B/en
Publication of CN105540593A publication Critical patent/CN105540593A/en
Application granted granted Critical
Publication of CN105540593B publication Critical patent/CN105540593B/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00Silicon; Compounds thereof
    • C01B33/02Silicon
    • C01B33/037Purification
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/80Compositional purity

Abstract

A kind of slagging agent living removes the method and its device of boron, belongs to semi-conducting material and field of metallurgy.Described device is provided with lobe pump, furnace base, Medium frequency induction coil, heat-insulation layer, graphite crucible, agitator and lowering or hoisting gear.Method:Raw silicon is put into graphite crucible from charging aperture, starts lobe pump and vacuumizes, starts medium frequency induction power supply heating, treats that temperature rises to 1500 DEG C, silico briquette is all melted;Inert gas is filled with into furnace chamber, keeps the temperature at 1550~1650 DEG C, adds slag agent, starts agitator, completes first time slag making;Medium frequency induction power supply power is improved, furnace chamber temperature is reached 1700~1800 DEG C, charging aperture is opened, puts into slag agent active component for the first time, vacuumize, start agitator, be passed through inert gas, complete second of slag making;After the completion for the treatment of slag making, silicon liquid is poured into and accepted in crucible, stand cooling, taken out silicon ingot, the low boron HIGH-PURITY SILICON after being purified, complete slagging agent living and remove boron.

Description

A kind of slagging agent living removes the method and its device of boron

Technical field

The invention belongs to semi-conducting material and field of metallurgy, more particularly, to a kind of slagging agent living except the method and its dress of boron Put.

Background technology

With fossil fuel price rise steadily and caused problem of environmental pollution is on the rise, clean energy resource It is developed into one of focus of concern.Wherein solar energy is a kind of important, new, effective renewable and clean energy resource, Its reserves is huge, without environmental pollution, is filled with tempting prospect.Crystalline silicon material is the main material of solar cell industry Material, compared with monocrystalline silicon, the cost of polysilicon is relatively low, and shared ratio is maximum.People use for reference conventional metallurgical method, have found out thing Manage the preparation method of metallurgy method purifying solar energy level polysilicon.

According to actual converted effect requirements, the purity rubric of the solar-grade polysilicon provided at present in industry is:P content < 0.5ppmw, B content < 0.3ppmw, elementary metal impurities total content < 0.1ppmw.

Research finds that blowing refining and slag making removal of impurities can substantially reduce B content.The advantages of blowing refining is equipment letter List, energy consumption are low, and in order to avoid the generation of bad products and security incident, throughput will be controlled strictly in industrial production, ensure Impurity and the abundant haptoreaction of gas.Cleaned for slag making, Japanese Suzuki and Sano (Suzuki, Sano.Thermodynamics for removal of boron from metallurgical silicon by flux treatment of molten silicon[C].The 10th European Photovoltaic Solar Energy Conference In Lisbon, Portugal 8-12 Apr.1991) more systematic research has been carried out to the slag making of Ca systems, with CaO-BaO-SiO2For slag agent, the slag for analyzing the silicon of silicon and equivalent heterogeneity different proportion mixes melting reaction.

The applicant Luo Xue great waves seminar (Ming Fang, Chenghao Lu, Liuqing Hui, Huixian Lai, Juan Chen,Jingtang Li,Wenhui Ma,Pengfei Xing and Xuetao Luo,Effect of calcium-based slag treatment on hydrometallurgical purification of metallurgical grade silicon,Industrial&Engineering Chemistry Research,2014, 53,972-979.) it have studied CaO-SiO2-CaF2Gone out for slag former the principle of the impurity such as B, P in silicon, while be investigated HCl Pickling effect of+HF the mixed acid for Si-Fe phases.

United States Patent (USP) US20050139148 (Fujiwara Hiroyasu et al, Silicon purifying Method, slag for purifying silicon, and purified silicon) use blowing refining and slag making simultaneously Carry out, reacting gas composition is the Ar that water vapour content is 30%, is blown into by rotary part central tube, using SiO2With For CaO to help slag agent, B content is down to 0.8ppmw from 7.4ppmw.The shortcomings that this patent, which is that water vapour content is too high, causes silicon ingot Middle stomata is more.

Chinese patent CN101555015A (boron-removing purification method and device of a kind of polysilicon) takes porous blade to rotate The mode of air blowing slag making.The shortcomings that this patent is that white residue ratio is larger after multiple slagging process, and installation cost is higher.

Chinese patent CN102040219A (a kind of to purify the method for preparing HIGH-PURITY SILICON by industrial silicon) combines industrial silicon production, External refining silicon melt is directly utilized, oxidative slagging is carried out in external refining equipment and removes boron, slag making dephosphorization is reduced after removing slag, will Silicon ingot removes slag top layer, crushes pickling drying, obtains HIGH-PURITY SILICON.Wherein B content < 0.5ppmw, P content < 1ppmw, metal are miscellaneous Matter content < 1ppmw.The shortcomings that this patent is SiO2It is bad with the control of CaO ratios, raw material is aoxidized serious.

In summary, noble gas component and Ventilation Rate are strictly controlled in blowing refining;During slagging boron removal Control slag agent component ratio.Slag agent excessively make it that waste residue quantitative change is big, and waste residue is difficult to degrade in natural environment, while can be dirty Surrounding soil and water source are contaminated, it is unfriendly to environment.By studying the active component for finding repeatedly to be added in slagging process in slag agent Instead of former slag agent, close effect can be played.

The content of the invention

It is an object of the invention to remove deficiency existing for the technique of boron impurity in silicon for existing repeatedly slag making, there is provided Low waste sludge discharge, technique is simple, a kind of efficient and suitable industrialized production slagging agent living removes boron device.

A kind of method for removing boron another object of the present invention is to provide slagging agent living.

The slagging agent living is except boron device is provided with lobe pump, furnace base, Medium frequency induction coil, heat-insulation layer, graphite crucible, stirs Device and lowering or hoisting gear are mixed, the lobe pump is connected with furnace base, and graphite crucible is located in furnace base, and heat-insulation layer is located at graphite crucible Periphery, Medium frequency induction coil are wound on heat-insulation layer periphery, and agitator is located in Medium frequency induction coil, and the top of furnace base is provided with charging Mouth and observation panel, the drive link lower port of agitator are provided with agitator gas outlet, and the drive link top of agitator is small provided with bar is passed Hole, the drive link top of agitator are provided with motor, and the top of agitator is provided with air chamber and air inlet, and the lowering or hoisting gear is located at Between at the top of the top of agitator and furnace base.

The method that the slagging agent living removes boron, comprises the following steps:

1) raw silicon is put into graphite crucible from charging aperture, starts lobe pump and vacuumize, started medium frequency induction power supply and add Heat, treat that temperature rises to 1500 DEG C, silico briquette is all melted, slag agent system is CaO-SiO2-CaCl2Or CaO-SiO2-CaF2

2) inert gas is filled with into furnace chamber, medium frequency induction power supply power is improved to 100~250kW, keeps the temperature at Between 1550~1650 DEG C, slag agent is added, starts agitator, completes first time slag making;

3) medium frequency induction power supply power is improved, furnace chamber temperature is reached 1700~1800 DEG C, opens charging aperture, for the first time Slag agent active component is put into, is vacuumized, starts agitator, while is passed through inert gas, completes second of slag making;

4) after the completion for the treatment of slag making, silicon liquid is poured into and accepted in crucible, stand cooling, silicon ingot is taken out, after being purified Low boron HIGH-PURITY SILICON, complete slagging agent living and remove boron.

In step 1), the raw silicon can use metallurgical grade industrial silicon, the metallurgical grade industrial silicon can use purity for 99%~99.9% metallurgical grade industrial silicon, Boron contents are in below 30ppmw;The slag agent system CaO-SiO2-CaCl2Quality Than that can be 1: 3: 1, slag agent system CaO-SiO2-CaF2Mass ratio can be 1: 3: 1.

In step 2) and step 3), the rotating speed of the agitator can be 120~180r/min, and the time of stirring can be 30 ~45min, Ventilation Rate is 30~40L/min in whole process.

In step 2), the inert gas can use O2, vapor and Ar oxygen mixtures, body is pressed in mixed gas Product percentage O2Content is 0.5%~1%, and water vapour content is that 0.5%~1%, Ar Gas contents are 98%~99%;It is described to stir The biography bar and blade material for mixing device can use high-strength high temperature-resistant graphite;Air chamber is provided with below motor, inert gas is by stirring Bar top air plenum, which enters, to be passed inside bar;4 apertures are provided with the top of the biography bar of the agitator, inert gas is passed through from 4 apertures Stirrer bottom, smashed, entered in silicon liquid by rotating vane.

In step 3), the slag agent active component is CaCl2Or CaF2;The vacuum vacuumized can be 500~ 800Pa。

After Methods For Purification provided by the present invention, the content highest of boron impurity can be reduced to 0.17ppmw in silicon, symbol Close the requirement for boron impurity content in solar-grade polysilicon.From CaO and SiO2B distribution coefficient can be effectively improved, CaCl simultaneously2It can be very good to react with B, generate stable material.

It is characteristic of the invention that be combined using a variety of slag making modes, by repeatedly adding the active component in slag agent, Slag agent is reached the purpose of removing boron with B generations fully reaction under the conditions of stirring and air blowing, reduce the white residue ratio in slagging process Rate.

It is characteristic of the invention that agitator and breather pipe are integrated, in the case where throughput is relatively low gas can be made to exist Exit is smashed by blade, is then fully reacted with silicon liquid again.

The present invention is combined repeatedly using blowing refining and slagging boron removal, and adding slag former active component reduces B content.Its Boron contents can especially be reduced to very low level by advantage in the content that objectionable impurities in silicon can be greatly lowered, Slag agent dosage is greatly reduced simultaneously, harm of the waste residue to environment is reduced from source.

The present invention is an improvement to traditional slagging process, by the way of two ways is combined, improves B removal Effect.By adding multiple active ingredient, the effect for removing B can be reached, while reduce slag agent dosage, reduced on source useless Slag discharges.Similar manner is had not seen in slag agent proportioning and agitator ventilation design method, device is simple, is easy to industrialized production, It disclosure satisfy that industrialized production needs.

Brief description of the drawings

Fig. 1 is the structural representation that slagging agent living of the present invention removes boron device embodiment.

Fig. 2 is the structural representation of vertical lift device in Fig. 1.

Embodiment

It is given below that of the present invention except boron purification example, some (selected slag agent is CaO-SiO2-CaCl2):

As illustrated in fig. 1 and 2, the slagging agent living is except boron device embodiment is provided with lobe pump 3, furnace base 4, Medium frequency induction line Circle 5, heat-insulation layer 6, graphite crucible 7, agitator 8 and lowering or hoisting gear 14, the lobe pump 3 are connected with furnace base 4, graphite crucible 7 It is located in furnace base 4, heat-insulation layer 6 is located at the periphery of graphite crucible 7, and Medium frequency induction coil 5 is wound on the periphery of heat-insulation layer 6, and agitator 8 is set In Medium frequency induction coil 5, the top of furnace base 4 is provided with charging aperture 1 and observation panel 2, and the drive link lower port of agitator 8 is provided with Agitator gas outlet 9, the drive link top of agitator 8, which is provided with, passes bar aperture 11, and motor is provided with the top of the drive link of agitator 8 12, the top of agitator 8 is provided with air chamber 13 and air inlet 15, and the lowering or hoisting gear 14 is located at top and the furnace base 4 of agitator 8 Between top.

In Fig. 1, mark 10 is the stirring vane of agitator 8.

The method that the slagging agent living removes boron, comprises the following steps:

1) raw silicon is put into graphite crucible from charging aperture, starts lobe pump and vacuumize, started medium frequency induction power supply and add Heat, treat that temperature rises to 1500 DEG C, silico briquette is all melted, slag agent system is CaO-SiO2-CaCl2Or CaO-SiO2-CaF2;Institute Metallurgical grade industrial silicon can be used by stating raw silicon, the metallurgical grade industrial silicon can use purity for 99%~99.9% metallurgical grade work Industry silicon, Boron contents are in below 30ppmw;The slag agent system CaO-SiO2-CaCl2Mass ratio can be 1: 3: 1, slag agent system CaO-SiO2-CaF2Mass ratio can be 1: 3: 1.

2) inert gas is filled with into furnace chamber, medium frequency induction power supply power is improved to 100~250kW, keeps the temperature at Between 1550~1650 DEG C, slag agent is added, starts agitator, completes first time slag making;The rotating speed of the agitator can be 120~ 180r/min, time of stirring can be 30~45min, and Ventilation Rate is 30~40L/min in whole process.The inert gas O can be used2, vapor and Ar oxygen mixtures, percent by volume O is pressed in mixed gas2Content is 0.5%~1%, and water steams Gas content is that 0.5%~1%, Ar Gas contents are 98%~99%;The biography bar and blade material of the agitator can use high-strength Spend high temperature resistant graphite;Air chamber is provided with below motor, inert gas is entered by puddler top air plenum to be passed inside bar;The stirring 4 apertures are provided with the top of the biography bar of device, inert gas is passed through stirrer bottom from 4 apertures, is smashed, enter by rotating vane In silicon liquid.

3) medium frequency induction power supply power is improved, furnace chamber temperature is reached 1700~1800 DEG C, opens charging aperture, for the first time Slag agent active component is put into, is vacuumized, starts agitator, while is passed through inert gas, completes second of slag making;The agitator Rotating speed can be 120~180r/min, time of stirring can be 30~45min, and Ventilation Rate is 30~40L/ in whole process min.The slag agent active component is CaCl2Or CaF2;The vacuum vacuumized can be 500~800Pa.

4) after the completion for the treatment of slag making, silicon liquid is poured into and accepted in crucible, stand cooling, silicon ingot is taken out, after being purified Low boron HIGH-PURITY SILICON, complete slagging agent living and remove boron.

Active slag of the present invention is removed in boron purifying plant, starts lowering or hoisting gear and agitator is risen into top, silico briquette leads to Cross in charging aperture input graphite crucible, start lobe pump and smelting furnace is vacuumized, when vacuum reaches 500~800Pa, beat Induction power supply is opened, Medium frequency induction coil starts to heat the silico briquette inside crucible, and temperature rises to 1500 DEG C, and insulation treats that silico briquette melts Change, be passed through inert gas, gas enters air inlet chamber from air inlet, is full of whole furnace chamber by passing bar aperture, increases induction coil work( Rate, elevate the temperature to 1600 DEG C, proportionally preparing slag agent, put into slag former from charging aperture, now lowering or hoisting gear will stir Mix device to be down to below white residue liquid level, inner case is observed by observation ward, starts motor, starts agitator, treat to make for the first time After the completion of slag, rise temperature is to 1700 DEG C, motor stall, and lowering or hoisting gear makes agitator rise to top, slag agent activity into Divide after charging aperture addition, agitator is fallen, and stirring, which is blown, continues second of slag making, can so carry out multiple slag making.Treat slag making After the completion of, stop stirring ventilation, lowering or hoisting gear rises to top, opens bell, and white residue is poured into old slag together and accepted in crucible, cold But the first part is cut off after standing, slag making terminates.

Specific embodiment given below:

Embodiment 1

1) industrial silicon 100kg is weighed;Boron concentration is about 22ppmw;

2) CaO, SiO are weighed for 1: 3: 1 in mass ratio2、CaCl2, gross mass 20kg;

3) industrial silicon is put into graphite crucible, vacuumized, when vacuum reaches 600Pa, open induction power supply heating, temperature 1500 DEG C are risen to, heats 30min, silico briquette fusing;

4) inert gas is passed through, temperature is improved to 1600 DEG C, adds slag agent, vertical lift device is started and falls agitator, side Stir side ventilation;

5) stop stirring ventilation after 45min, open charging aperture, put into 4kg CaCl2, charging aperture is closed, is vacuumized, very When reciprocal of duty cycle is to 600Pa, continue stirring ventilation;

6) whole process stir speed (S.S.) is 150r/min, and Ventilation Rate is 35L/min during stirring;

7) stop stirring ventilation after 45min, after the completion for the treatment of slag making, silicon liquid is poured into and accepted in crucible, after standing 120min, Take out silicon ingot, remove the 1/5 of 1/10 and the afterbody on head, obtain low boron high purity silicon ingot, by ICP-AES (inductive etc. from Daughter atom emission spectrometry) content that measures B in silicon ingot is 2.49ppmw.

Embodiment 2

1) industrial silicon 100kg is weighed;Boron concentration is about 22ppmw;

2) CaO, SiO are weighed for 1: 3: 1 in mass ratio2、CaCl2, gross mass 20kg;

3) industrial silicon is put into graphite crucible, vacuumized, when vacuum reaches 600Pa, open induction power supply heating, temperature 1500 DEG C are risen to, heats 30min, silico briquette fusing;

4) inert gas is passed through, temperature is improved to 1700 DEG C, adds slag agent, vertical lift device is started and falls agitator, side Stir side ventilation;

5) stop stirring ventilation after 45min, open charging aperture, put into active component for the first time, put into 8kg CaCl2, close Charging aperture is closed, is vacuumized, when vacuum is to 600Pa, continues stirring ventilation, whole process ensures temperature more than 1600 DEG C;

6) whole process stir speed (S.S.) is 150r/min, and Ventilation Rate is 35L/min during stirring;

7) stop stirring ventilation after 45min, after the completion for the treatment of slag making, silicon liquid is poured into and accepted in crucible, after standing 120min, Silicon ingot is taken out, afterbody clearance 3/10, after obtaining low boron high purity silicon ingot, (inductively coupled plasma atom is sent out by ICP-AES Penetrate spectroscopic methodology) B content is 0.52ppmw in the silicon ingot surveyed.

Embodiment 3

1) industrial silicon 100kg is weighed;Boron concentration is about 22ppmw;

2) CaO, SiO are weighed for 1: 3: 1 in mass ratio2、CaCl2, gross mass 20kg;

3) industrial silicon is put into graphite crucible, vacuumized, when vacuum reaches 600Pa, open induction power supply heating, temperature 1500 DEG C are risen to, heats 30min, silico briquette fusing;

4) inert gas is passed through, temperature is improved to 1600 DEG C, adds slag agent, vertical lift device is started and falls agitator, side Stir side ventilation;

5) stop stirring ventilation after 45min, open charging aperture, put into active component for the first time, put into 4kg CaCl2, close Charging aperture is closed, is vacuumized, when vacuum is to 600Pa, continues stirring ventilation, whole process ensures temperature more than 1600 DEG C;

6) stop stirring ventilation after 45min, open charging aperture, put into active component for the second time, put into 4kg CaCl2, close Charging aperture is closed, vacuumizing makes the near 600Pa of air pressure, continues stirring ventilation, and whole process ensures temperature more than 1600 DEG C;

7) whole process stir speed (S.S.) is 150r/min, and Ventilation Rate is 35L/min during stirring;

8) stop stirring ventilation after 45min, after the completion for the treatment of slag making, silicon liquid is poured into and accepted in crucible, after standing 120min, Silicon ingot is taken out, the 1/5 of 1/10 and the afterbody on head is removed, the polycrystal silicon ingot after being purified, passes through ICP-AES (inductives Plasma atomic emission spectrometry) content that measures B in silicon ingot is 0.38ppmw.

Embodiment 4

Weigh industrial silicon 100kg;Boron concentration is about 22ppmw;

1) CaO, SiO are weighed for 1: 3: 1 in mass ratio2、CaCl2, gross mass 20kg;

2) industrial silicon is put into graphite crucible, vacuumized, when vacuum reaches below 300Pa, open induction power supply heating, Temperature rises to 1500 DEG C, heats 30min, silico briquette fusing;

3) inert gas is passed through, temperature is improved to 1600 DEG C, adds slag agent, vertical lift device is started and falls agitator, side Stir side ventilation;

4) stop stirring ventilation after 45min, open charging aperture, put into 8kg CaCl2, charging aperture is closed, is vacuumized, very When reciprocal of duty cycle is to 600Pa, continue stirring ventilation, whole process ensures temperature more than 1600 DEG C;

5) whole process stir speed (S.S.) is 150r/min, and Ventilation Rate is 35L/min during stirring;

6) stop stirring ventilation after 45min, after the completion for the treatment of slag making, silicon liquid is poured into and accepted in crucible, after standing 120min, Silicon ingot is taken out, the 1/5 of 1/10 and the afterbody on head is removed, the polycrystal silicon ingot after being purified, passes through ICP-AES (inductives Plasma atomic emission spectrometry) content that measures B in silicon ingot is 0.26ppmw.

Embodiment 5

Weigh industrial silicon 100kg;Boron concentration is about 22ppmw;

1) CaO, SiO are weighed for 1: 3: 1 in mass ratio2、CaCl2, gross mass 20kg;

2) industrial silicon is put into graphite crucible, vacuumized, when vacuum reaches 600Pa, open induction power supply heating, temperature 1500 DEG C are risen to, heats 30min, silico briquette fusing;

3) inert gas is passed through, temperature is improved to 1600 DEG C, adds slag agent, vertical lift device is started and falls agitator, side Stir side ventilation;

4) stop stirring ventilation after 45min, open charging aperture, put into active component for the first time, put into 8kg CaCl2, close Charging aperture is closed, is vacuumized, when vacuum is to 600Pa, continues stirring ventilation, whole process ensures temperature more than 1600 DEG C;

5) stop stirring ventilation after 45min, open charging aperture, put into active component for the second time, put into 4kg CaCl2, close Charging aperture is closed, is vacuumized, when vacuum is to 600Pa, continues stirring ventilation, whole process ensures temperature more than 1600 DEG C;

6) whole process stir speed (S.S.) is 150r/min, and Ventilation Rate is 35L/min during stirring;

7) stop stirring ventilation after 45min, after the completion for the treatment of slag making, silicon liquid is poured into and accepted in crucible, after standing 120min, Silicon ingot is taken out, the 1/5 of 1/10 and the afterbody on head is removed, the polycrystal silicon ingot after being purified, passes through ICP-AES (inductives Plasma atomic emission spectrometry) content that measures B in silicon ingot is 0.17ppmw.

The present invention is a kind of method except boron purifying silicon materials, and the recycling of slag agent can be achieved, and cost is low, operation letter It is single, it is easy to accomplish industrial-scale production.The technical grade metalluragical silicon of selection is raw material, and raw silicon is put into graphite crucible, taken out Vacuum, start medium frequency induction power supply heating.After silicon melts, inert gas is passed through into solution, improves solution temperature, adds slag Agent and silicon solution reaction, after reaction terminates, silicon liquid temperature is improved again, a kind of effective active composition added in slag agent, is continued Slag making.Treat to stand after the completion of slag making, silicon liquid is poured into old slag and accepted in crucible.During secondary or multiple slag making, by old slag and work Property group adds according to a certain percentage, slag liquid is removed after the completion of slag making, the silicon liquid after refining pours into undertaking crucible, and silicon is taken out after cooling Ingot, obtain the HIGH-PURITY SILICON after low boron purification.According to the present invention, the content highest of boron impurity can be reduced to 0.17ppmw in silicon.

Claims (6)

1. the method that slagging agent removes boron of living, it is characterised in that boron device is removed using slagging agent living, the slagging agent living removes boron device Provided with lobe pump, furnace base, Medium frequency induction coil, heat-insulation layer, graphite crucible, agitator and lowering or hoisting gear, the lobe pump with Furnace base is connected, and graphite crucible is located in furnace base, and heat-insulation layer is located at graphite crucible periphery, and Medium frequency induction coil is wound on heat-insulation layer Periphery, agitator are located in Medium frequency induction coil, and the top of furnace base is provided with charging aperture and observation panel, under the drive link of agitator Port is provided with agitator gas outlet, and the drive link top of agitator, which is provided with, passes bar aperture, and electricity is provided with the top of the drive link of agitator Motivation, the top of agitator are provided with air chamber and air inlet, and the lowering or hoisting gear is located at the top and furnace base top of agitator Between;
It the described method comprises the following steps:
1) raw silicon is put into graphite crucible from charging aperture, starts lobe pump and vacuumize, started medium frequency induction power supply heating, treat Temperature rises to 1500 DEG C, silico briquette is all melted, slag agent system is CaO-SiO2-CaCl2Or CaO-SiO2-CaF2
The slag agent system CaO-SiO2-CaCl2Mass ratio be 1: 3: 1, slag agent system CaO-SiO2-CaF2Mass ratio be 1: 3∶1;
2) inert gas is filled with into furnace chamber, medium frequency induction power supply power is improved to 100~250kW, keeps the temperature at 1550 Between~1650 DEG C, slag agent is added, starts agitator, completes first time slag making;
The inert gas uses O2, vapor and Ar oxygen mixtures, percent by volume O is pressed in mixed gas2Content is 0.5%~1%, water vapour content is that 0.5%~1%, Ar Gas contents are 98%~99%;
3) medium frequency induction power supply power is improved, furnace chamber temperature is reached 1700~1800 DEG C, charging aperture is opened, puts into for the first time Slag agent active component, is vacuumized, and starts agitator, while is passed through inert gas, completes second of slag making;
4) after the completion for the treatment of slag making, silicon liquid is poured into and accepted in crucible, stand cooling, take out silicon ingot, the low boron after being purified HIGH-PURITY SILICON, complete slagging agent living and remove boron.
2. the method that slagging agent living removes boron as claimed in claim 1, it is characterised in that in step 1), the raw silicon uses smelting Golden level industrial silicon.
3. the method that slagging agent living removes boron as claimed in claim 2, it is characterised in that the metallurgical grade industrial silicon use purity for 99%~99.9% metallurgical grade industrial silicon, Boron contents are in below 30ppmw.
4. the method that slagging agent living removes boron as claimed in claim 1, it is characterised in that in step 2) and step 3), the stirring The rotating speed of device is 120~180r/min, and time of stirring is 30~45min, and Ventilation Rate is 30~40L/ in whole process min;Air chamber is provided with below motor, inert gas is entered by puddler top air plenum to be passed inside bar;The biography bar of the agitator Top is provided with 4 apertures, and inert gas is passed through stirrer bottom from 4 apertures, is smashed, entered in silicon liquid by rotating vane.
5. the method that slagging agent living removes boron as claimed in claim 1, it is characterised in that in step 3), the slag agent active component For CaCl2Or CaF2
6. the method that slagging agent living removes boron as claimed in claim 1, it is characterised in that in step 3), the vacuum vacuumized Spend for 500~800Pa.
CN201511027460.4A 2015-12-31 2015-12-31 A kind of slagging agent living removes the method and its device of boron CN105540593B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201511027460.4A CN105540593B (en) 2015-12-31 2015-12-31 A kind of slagging agent living removes the method and its device of boron

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201511027460.4A CN105540593B (en) 2015-12-31 2015-12-31 A kind of slagging agent living removes the method and its device of boron

Publications (2)

Publication Number Publication Date
CN105540593A CN105540593A (en) 2016-05-04
CN105540593B true CN105540593B (en) 2017-12-19

Family

ID=55820229

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201511027460.4A CN105540593B (en) 2015-12-31 2015-12-31 A kind of slagging agent living removes the method and its device of boron

Country Status (1)

Country Link
CN (1) CN105540593B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106012007B (en) * 2016-07-22 2018-03-13 天合光能股份有限公司 A kind of method and its device of forced convertion growth crystalline silicon
CN108059167A (en) * 2017-12-26 2018-05-22 中国科学院过程工程研究所 Cut the method and device that silica flour slag prepares HIGH-PURITY SILICON
CN109354024A (en) * 2018-11-19 2019-02-19 成都斯力康科技股份有限公司 A kind of device and method of infant industry silicon separation, impurity removal

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1431289A (en) * 2003-02-18 2003-07-23 王晓军 Integral oxygen supply and agitation equip
JP2003277040A (en) * 2002-03-19 2003-10-02 Sharp Corp Method of purifying silicon and solar cell manufactured by using silicon purified by method thereof
JP2004217473A (en) * 2003-01-15 2004-08-05 Sharp Corp Apparatus and method for purifying silicon and silicon purified using the same
WO2006006487A1 (en) * 2004-07-13 2006-01-19 Sharp Kabushiki Kaisha Method for purification of silicon and silicon purified by said method
WO2006061944A1 (en) * 2004-12-09 2006-06-15 Sharp Kabushiki Kaisha Method for purification of silicon and silicon
CN101555015A (en) * 2009-05-19 2009-10-14 厦门大学 Purifying method and device for removing boron from polysilicon

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003277040A (en) * 2002-03-19 2003-10-02 Sharp Corp Method of purifying silicon and solar cell manufactured by using silicon purified by method thereof
JP2004217473A (en) * 2003-01-15 2004-08-05 Sharp Corp Apparatus and method for purifying silicon and silicon purified using the same
CN1431289A (en) * 2003-02-18 2003-07-23 王晓军 Integral oxygen supply and agitation equip
WO2006006487A1 (en) * 2004-07-13 2006-01-19 Sharp Kabushiki Kaisha Method for purification of silicon and silicon purified by said method
WO2006061944A1 (en) * 2004-12-09 2006-06-15 Sharp Kabushiki Kaisha Method for purification of silicon and silicon
CN101555015A (en) * 2009-05-19 2009-10-14 厦门大学 Purifying method and device for removing boron from polysilicon

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Effects of Slag Refining on Boron Removal from Metallurgical-Grade Silicon Using Recycled Slag with Active Component;Chenghao Lu, et al;《Separation Science and Technology》;20150701(第50期);第2760页实验部分、表1和图1 *

Also Published As

Publication number Publication date
CN105540593A (en) 2016-05-04

Similar Documents

Publication Publication Date Title
JP4159994B2 (en) Method for purifying silicon, slag for silicon purification, and purified silicon
ES2357501T3 (en) High purity metallurgical silicon and elaboration procedure.
Alemany et al. Refining of metallurgical-grade silicon by inductive plasma
CN101704687B (en) Method for producing potassium sulphate by decomposing potassium feldspar at low temperature
CN101113029B (en) Treatment recovery method for monocrystalline silicon cutting waste liquor
CN102120583B (en) Crucible for electronic industry and method for purifying high-purity quartz sand as lining material
CN101122047B (en) Method for manufacturing polycrystalline silicon used for solar battery
JP2010503596A (en) Method and apparatus for refining low grade silicon material
CN102925722B (en) Method for smelting vanadium-aluminum alloy by electro-aluminothermic process
CN101343699B (en) Aluminum-silicon alloy refining agent and preparation thereof
CN101357765B (en) Method for preparing solar-grade silicon
ES2718777T3 (en) Production process of ferromanganese with ultra low phosphorus and carbon content through the use of ferromanganese slag
BRPI0709288A2 (en) method for producing high purity silicon, method for preparing high purity silicon, method for preparing high purity silica and method for purifying low grade silicon for high grade silicon
CN102498064A (en) Polycrystalline silicon mass and process for producing polycrystalline silicon mass
CN102173424B (en) Method and equipment for removing phosphorus and metal impurities in ganister sand through vacuum induction melting
CN101343063A (en) Purification apparatus and method for solar energy level polysilicon
CN101475174B (en) Method for purifying industrial silicon for preparing solar grade silicon
CN107651691B (en) A kind of method of crystalline silicon cutting waste material preparation high-quality silicon carbide
JP4856738B2 (en) Manufacturing method of high purity silicon material
CN101920960B (en) Method for preparing solar grade polysilicon by metallurgy method and polysilicon prepared thereby
CN101844768B (en) Method for removing phosphorus and boron from metallurgical-grade silicon
CN100410400C (en) Method for preparation of aluminum scandium alloy by alumino-thermic reduction method
Einhaus et al. Photosil–simplified production of solar silicon from metallurgical silicon
WO2006006487A1 (en) Method for purification of silicon and silicon purified by said method
JP2012508154A (en) Method and apparatus for producing solar grade silicon by refining metallurgical grade silicon

Legal Events

Date Code Title Description
PB01 Publication
C06 Publication
SE01 Entry into force of request for substantive examination
C10 Entry into substantive examination
GR01 Patent grant
GR01 Patent grant