CN105540593A - Boron removal method and device through activated slag agent - Google Patents
Boron removal method and device through activated slag agent Download PDFInfo
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- CN105540593A CN105540593A CN201511027460.4A CN201511027460A CN105540593A CN 105540593 A CN105540593 A CN 105540593A CN 201511027460 A CN201511027460 A CN 201511027460A CN 105540593 A CN105540593 A CN 105540593A
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- boron
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/037—Purification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a boron removal method and device through an activated slag agent, and belongs to the fields of semiconductor materials and metallurgy. The device is provided with a lobe pump, a furnace base, a medium-frequency induction coil, an insulating layer, a graphite crucible, a stirrer and a lifting device. The method comprises the steps that raw silicon is put into the graphite crucible from a feed port, the lobe pump is started to perform vacuumizing, a medium-frequency induction power supply is started to perform heating, and when the temperature is increased to 1500 DEG C, silicon blocks are completely molten; inert gas is charged into a furnace cavity to enable the temperature to be kept at 1550 DEG C-1650 DEG C, the slag agent is added, the stirrer is started, and first-time slagging is completed; the power of the medium-frequency induction power supply is increased to enable the temperature in the furnace cavity to reach 1700 DEG C-1800 DEG C, the feed port is opened, active components of the slag agent are put into the furnace cavity for the first time, vacuumizing is performed, the stirrer is started, the inert gas is introduced, and second-time slagging is completed; after slagging is completed, silicon liquid is poured into a receiving crucible, standing and cooling are performed, a silicon ingot is taken out, purified low-boron high-purity silicon is obtained, and then boron removal achieved through the activated slag agent is completed.
Description
Technical field
The invention belongs to semiconductor material and field of metallurgy, especially relate to method and device thereof that a kind of dissolving agent of living removes boron.
Background technology
Along with the problem of environmental pollution rising steadily and produce of fossil oil price is on the rise, one of the focus be developed to as people pay close attention to of clean energy.Wherein sun power is a kind of important, new, effective renewable and clean energy resource, and its reserves are huge, do not have environmental pollution, are filled with tempting prospect.Crystalline silicon material is the main raw of solar cell industry, and compared with silicon single crystal, the cost of polysilicon is lower, and shared ratio is maximum.People use for reference conventional metallurgical method, have found out the preparation method of physical metallurgy method purifying solar energy level polysilicon.
According to actual converted effect requirements, the purity rubric of the solar-grade polysilicon provided in current industry is: P content < 0.5ppmw, B content < 0.3ppmw, elementary metal impurities total content < 0.1ppmw.
Research finds, blowing refining and slag making removal of impurities can obviously reduce B content.The advantage of blowing refining is that equipment is simple, energy consumption is low, and in order to avoid the generation of bad product and security incident, air flow will strictly control when industrial production, ensures impurity and the abundant contact reacts of gas.For slag making removal of impurities, Suzuki and the Sano (Suzuki of Japan, Sano.Thermodynamicsforremovalofboronfrommetallurgicalsil iconbyfluxtreatmentofmoltensilicon [C] .The10thEuropeanPhotovoltaicSolarEnergyConferenceInLisbo n, Portugal8-12Apr.1991) comparatively systematic research has been carried out, with CaO-BaO-SiO to the slag making of Ca system
2for slag agent, analyze the slag mixing melting reaction of the silicon of silicon and equivalent heterogeneity different ratios.
The Luo Xue great waves seminar (MingFang of the applicant, ChenghaoLu, LiuqingHui, HuixianLai, JuanChen, JingtangLi, WenhuiMa, PengfeiXingandXuetaoLuo, Effectofcalcium-basedslagtreatmentonhydrometallurgicalpu rificationofmetallurgicalgradesilicon, Industrial & EngineeringChemistryResearch, 2014,53,972-979.) have studied CaO-SiO
2-CaF
2for the principle of the impurity such as B, P in silicon gone out by slag former, be investigated the pickling effect of HCl+HF mixing acid for Si-Fe phase simultaneously.
US Patent No. 20050139148 (FujiwaraHiroyasuetal, Siliconpurifyingmethod, slagforpurifyingsilicon, andpurifiedsilicon) adopt blowing refining and slag making to carry out simultaneously, reactant gases composition to be water vapour content be 30% Ar, be blown into by turning unit central duct, adopt SiO
2with CaO for helping slag agent, the content of B is down to 0.8ppmw from 7.4ppmw.To be that water vapour content is too high cause pore in silicon ingot more to the shortcoming of this patent.
Chinese patent CN101555015A (a kind of boron-removing purification method of polysilicon and device) takes the mode of porous blade rotary air blowing slag making.The shortcoming of this patent is that white residue ratio is comparatively large after repeatedly slagging process, and installation cost is higher.
The Chinese patent CN102040219A method of industrial silicon synthesis HIGH-PURITY SILICON (a kind of by) is in conjunction with industrial silicon production, directly utilize external refining silicon melt, oxidative slagging is carried out except boron in external refining equipment, slag making dephosphorization is reduced after removing slag, silicon ingot to be removed slag top layer, broken pickling is dried, and obtains HIGH-PURITY SILICON.Wherein B content < 0.5ppmw, P content < 1ppmw, metals content impurity < 1ppmw.The shortcoming of this patent is SiO
2not good with CaO ratio control, serious to material oxidation.
In sum, noble gas component and Ventilation Rate to strictly be controlled in blowing refining; Slag agent component proportions will be controlled in slagging boron removal process.Slag agent is excessive makes waste residue quantitative change large, and waste residue is difficult to degraded in physical environment, can pollute surrounding soil and water source simultaneously, unfriendly to environment.Find that in slagging process, the activeconstituents repeatedly added in slag agent replaces former slag agent, can play close effect by research.
Summary of the invention
The object of the invention is to the deficiency for the technique existence of boron impurity in existing repeatedly slag making removing silicon, dissolving agent removes boron device and one that is applicable suitability for industrialized production is lived to provide low waste sludge discharge, technique simple, efficient.
Another object of the present invention is to provide a kind of method of dissolving agent except boron of living.
Described dissolving agent alive removes boron device and is provided with lobe pump, furnace base, Medium frequency induction coil, thermal insulation layer, plumbago crucible, agitator and lifting device, described lobe pump is connected with furnace base, plumbago crucible is located in furnace base, thermal insulation layer is located at plumbago crucible periphery, Medium frequency induction coil is around thermal insulation layer periphery, agitator is located in Medium frequency induction coil, the top of furnace base is provided with opening for feed and porthole, the transmission rod lower port of agitator is provided with agitator air outlet, the transmission rod top of agitator is provided with and passes bar aperture, the transmission rod top of agitator is provided with electric motor, the top of agitator is provided with air chamber and inlet mouth, described lifting device is located between the top of agitator and furnace base top.
Described dissolving agent alive, except the method for boron, comprises the following steps:
1) drop into plumbago crucible by raw silicon from opening for feed, start lobe pump and vacuumize, start medium frequency induction power supply heating, treat that temperature rises to 1500 DEG C, silico briquette is all melted, slag agent system is CaO-SiO
2-CaCl
2or CaO-SiO
2-CaF
2;
2) in furnace chamber, be filled with rare gas element, improve medium frequency induction power supply power to 100 ~ 250kW, temperature is remained between 1550 ~ 1650 DEG C, adds slag agent, start agitator, complete first time slag making;
3) improve medium frequency induction power supply power, make furnace chamber temperature reach 1700 ~ 1800 DEG C, open opening for feed, first time drops into slag agent activeconstituents, vacuumizes, and starts agitator, passes into rare gas element simultaneously, completes second time slag making;
4) after slag making completes, silicon liquid is poured into and accepts in crucible, leave standstill cooling, take out silicon ingot, obtain the low boron HIGH-PURITY SILICON after purifying, complete dissolving agent alive except boron.
In step 1) in, described raw silicon can adopt metallurgical grade industrial silicon, described metallurgical grade industrial silicon can adopt purity be 99% ~ 99.9% metallurgical grade industrial silicon, Boron contents is at below 30ppmw; Described slag agent system CaO-SiO
2-CaCl
2mass ratio can be 1: 3: 1, slag agent system CaO-SiO
2-CaF
2mass ratio can be 1: 3: 1.
In step 2) and step 3) in, the rotating speed of described agitator can be 120 ~ 180r/min, and the time of stirring can be 30 ~ 45min, and in whole process, Ventilation Rate is 30 ~ 40L/min.
In step 2) in, described rare gas element can adopt O
2, water vapour and Ar oxygen mixture, by volume per-cent O in mixed gas
2content is 0.5% ~ 1%, and water vapour content is 0.5% ~ 1%, Ar Gas content is 98% ~ 99%; The biography bar of described agitator and blade material can adopt high-strength high temperature-resistant graphite; Be provided with air chamber below electric motor, rare gas element is entered by agitator arm top air plenum and passes bar inside; The biography masthead portion of described agitator is provided with 4 apertures, and rare gas element passes into stirrer bottom from 4 apertures, is smashed by rotating paddle, enters into silicon liquid.
In step 3) in, described slag agent activeconstituents is CaCl
2or CaF
2; The described vacuum tightness vacuumized can be 500 ~ 800Pa.
After Methods For Purification provided by the present invention, the highest 0.17ppmw that is reduced to of the content of boron impurity in silicon, meets the requirement for boron impurity content in solar-grade polysilicon.Select CaO and SiO
2effectively can improve the partition ratio of B, simultaneously CaCl
2can well react with B, generate stable material.
Feature of the present invention adopts multiple slag making mode to combine, and by repeatedly adding the activeconstituents in slag agent, under stirring and air blowing condition, making slag agent and B occur fully to react the object reaching and remove boron, reducing the white residue ratio in slagging process.
Feature of the present invention is integrated at agitator and ventpipe, gas can be smashed by blade in exit when air flow is lower, and then fully react with silicon liquid.
The present invention adopts blowing refining and slagging boron removal to combine repeatedly, adds slag former activeconstituents and reduces B content.Its advantage is the content that significantly can reduce detrimental impurity in silicon, especially Boron contents can be reduced to very low level, significantly reduces slag agent consumption simultaneously, reduces the harm of waste residue to environment from source.
The present invention is an improvement to traditional slagging process, adopts the mode combined in two ways, improves the removal effect of B.By adding repeatedly effective constituent, the effect of removing B can be reached, reducing slag agent consumption simultaneously, waste sludge discharge is reduced in source.Do not see similar manner in slag agent proportioning and agitator ventilation design, device is simple, is convenient to suitability for industrialized production, can meets suitability for industrialized production needs.
Accompanying drawing explanation
Fig. 1 is the structural representation of dissolving agent alive of the present invention except boron device embodiment.
Fig. 2 is the structural representation of vertical lift device in Fig. 1.
Embodiment
Below provide that of the present invention some (selected slag agent is CaO-SiO except boron purification example
2-CaCl
2):
As illustrated in fig. 1 and 2, described dissolving agent alive removes boron device embodiment and is provided with lobe pump 3, furnace base 4, Medium frequency induction coil 5, thermal insulation layer 6, plumbago crucible 7, agitator 8 and lifting device 14, described lobe pump 3 is connected with furnace base 4, plumbago crucible 7 is located in furnace base 4, thermal insulation layer 6 is located at plumbago crucible 7 periphery, Medium frequency induction coil 5 is around thermal insulation layer 6 periphery, agitator 8 is located in Medium frequency induction coil 5, the top of furnace base 4 is provided with opening for feed 1 and porthole 2, the transmission rod lower port of agitator 8 is provided with agitator air outlet 9, the transmission rod top of agitator 8 is provided with and passes bar aperture 11, the transmission rod top of agitator 8 is provided with electric motor 12, the top of agitator 8 is provided with air chamber 13 and inlet mouth 15, described lifting device 14 is located between the top of agitator 8 and furnace base 4 top.
In FIG, the agitating vane that 10 are agitator 8 is marked.
Described dissolving agent alive, except the method for boron, comprises the following steps:
1) drop into plumbago crucible by raw silicon from opening for feed, start lobe pump and vacuumize, start medium frequency induction power supply heating, treat that temperature rises to 1500 DEG C, silico briquette is all melted, slag agent system is CaO-SiO
2-CaCl
2or CaO-SiO
2-CaF
2; Described raw silicon can adopt metallurgical grade industrial silicon, described metallurgical grade industrial silicon can adopt purity be 99% ~ 99.9% metallurgical grade industrial silicon, Boron contents is at below 30ppmw; Described slag agent system CaO-SiO
2-CaCl
2mass ratio can be 1: 3: 1, slag agent system CaO-SiO
2-CaF
2mass ratio can be 1: 3: 1.
2) in furnace chamber, be filled with rare gas element, improve medium frequency induction power supply power to 100 ~ 250kW, temperature is remained between 1550 ~ 1650 DEG C, adds slag agent, start agitator, complete first time slag making; The rotating speed of described agitator can be 120 ~ 180r/min, and the time of stirring can be 30 ~ 45min, and in whole process, Ventilation Rate is 30 ~ 40L/min.Described rare gas element can adopt O
2, water vapour and Ar oxygen mixture, by volume per-cent O in mixed gas
2content is 0.5% ~ 1%, and water vapour content is 0.5% ~ 1%, Ar Gas content is 98% ~ 99%; The biography bar of described agitator and blade material can adopt high-strength high temperature-resistant graphite; Be provided with air chamber below electric motor, rare gas element is entered by agitator arm top air plenum and passes bar inside; The biography masthead portion of described agitator is provided with 4 apertures, and rare gas element passes into stirrer bottom from 4 apertures, is smashed by rotating paddle, enters into silicon liquid.
3) improve medium frequency induction power supply power, make furnace chamber temperature reach 1700 ~ 1800 DEG C, open opening for feed, first time drops into slag agent activeconstituents, vacuumizes, and starts agitator, passes into rare gas element simultaneously, completes second time slag making; The rotating speed of described agitator can be 120 ~ 180r/min, and the time of stirring can be 30 ~ 45min, and in whole process, Ventilation Rate is 30 ~ 40L/min.Described slag agent activeconstituents is CaCl
2or CaF
2; The described vacuum tightness vacuumized can be 500 ~ 800Pa.
4) after slag making completes, silicon liquid is poured into and accepts in crucible, leave standstill cooling, take out silicon ingot, obtain the low boron HIGH-PURITY SILICON after purifying, complete dissolving agent alive except boron.
Active slag of the present invention is except in boron purifying plant, start lifting device and agitator is risen to top, silico briquette drops in plumbago crucible by opening for feed, start lobe pump to vacuumize smelting furnace, when vacuum tightness arrives 500 ~ 800Pa, open induction power supply, Medium frequency induction coil starts the silico briquette heating inside to crucible, temperature rises to 1500 DEG C, insulation treats that silico briquette melts, pass into rare gas element, gas enters air chamber from inlet mouth, whole furnace chamber is full of by passing bar aperture, strengthen ruhmkorff coil power, elevate the temperature to 1600 DEG C, proportionally preparing slag agent, slag former is dropped into from opening for feed, now agitator is down to below white residue liquid level by lifting device, inner case is observed by observation ward, start electric motor, start agitator, after first time slag making completes, raised temperature to 1700 DEG C, motor stall, lifting device makes agitator rise to top, after slag agent activeconstituents adds from opening for feed, agitator is fallen, stirring blows continues second time slag making, so repeatedly slag making can be carried out.After slag making completes, stop stirring ventilation, lifting device rises to top, opens bell, white residue is poured together into old slag and accepts in crucible, and the first part of excision after cooling leaves standstill, slag making terminates.
Below provide specific embodiment:
Embodiment 1
1) industrial silicon 100kg is taken; Boron concentration is about 22ppmw;
2) be take CaO, SiO at 1: 3: 1 in mass ratio
2, CaCl
2, total mass is 20kg;
3) drop in plumbago crucible by industrial silicon, vacuumize, when vacuum tightness reaches 600Pa, open induction power supply heating, temperature rises to 1500 DEG C, heating 30min, and silico briquette melts;
4) pass into rare gas element, improve temperature to 1600 DEG C, add slag agent, start VTOL (vertical take off and landing) device and fall agitator, ventilate while stirring;
5) stop after 45min stirring ventilation, open opening for feed, drop into the CaCl of 4kg
2, close opening for feed, vacuumize, when vacuum tightness is to 600Pa, continue to stir ventilation;
6) whole process stir speed (S.S.) is 150r/min, and during stirring, Ventilation Rate is 35L/min;
7) stop after 45min stirring ventilation, after slag making completes, silicon liquid is poured into and accepts in crucible, after leaving standstill 120min, take out silicon ingot, removing 1/10 of head and 1/5 of afterbody, obtain low boron high purity silicon ingot, the content being recorded B in silicon ingot by ICP-AES (inductively coupled plasma atomic emission spectrometry) is 2.49ppmw.
Embodiment 2
1) industrial silicon 100kg is taken; Boron concentration is about 22ppmw;
2) be take CaO, SiO at 1: 3: 1 in mass ratio
2, CaCl
2, total mass is 20kg;
3) drop in plumbago crucible by industrial silicon, vacuumize, when vacuum tightness reaches 600Pa, open induction power supply heating, temperature rises to 1500 DEG C, heating 30min, and silico briquette melts;
4) pass into rare gas element, improve temperature to 1700 DEG C, add slag agent, start VTOL (vertical take off and landing) device and fall agitator, ventilate while stirring;
5) stop after 45min stirring ventilation, open opening for feed, first time drops into activeconstituents, drops into the CaCl of 8kg
2, close opening for feed, vacuumize, when vacuum tightness is to 600Pa, continue to stir ventilation, whole process ensures temperature more than 1600 DEG C;
6) whole process stir speed (S.S.) is 150r/min, and during stirring, Ventilation Rate is 35L/min;
7) stop after 45min stirring ventilation, after slag making completes, silicon liquid is poured into and accepts in crucible, after leaving standstill 120min, take out silicon ingot, afterbody clearance 3/10, after obtaining low boron high purity silicon ingot, in the silicon ingot surveyed by ICP-AES (inductively coupled plasma atomic emission spectrometry), the content of B is 0.52ppmw.
Embodiment 3
1) industrial silicon 100kg is taken; Boron concentration is about 22ppmw;
2) be take CaO, SiO at 1: 3: 1 in mass ratio
2, CaCl
2, total mass is 20kg;
3) drop in plumbago crucible by industrial silicon, vacuumize, when vacuum tightness reaches 600Pa, open induction power supply heating, temperature rises to 1500 DEG C, heating 30min, and silico briquette melts;
4) pass into rare gas element, improve temperature to 1600 DEG C, add slag agent, start VTOL (vertical take off and landing) device and fall agitator, ventilate while stirring;
5) stop after 45min stirring ventilation, open opening for feed, first time drops into activeconstituents, drops into the CaCl of 4kg
2, close opening for feed, vacuumize, when vacuum tightness is to 600Pa, continue to stir ventilation, whole process ensures temperature more than 1600 DEG C;
6) stop after 45min stirring ventilation, open opening for feed, second time drops into activeconstituents, drops into the CaCl of 4kg
2, close opening for feed, vacuumize and make the near 600Pa of air pressure, continue to stir ventilation, whole process ensures temperature more than 1600 DEG C;
7) whole process stir speed (S.S.) is 150r/min, and during stirring, Ventilation Rate is 35L/min;
8) stop after 45min stirring ventilation, after slag making completes, silicon liquid is poured into and accepts in crucible, after leaving standstill 120min, take out silicon ingot, removing 1/10 of head and 1/5 of afterbody, obtain the polycrystal silicon ingot after purifying, the content being recorded B in silicon ingot by ICP-AES (inductively coupled plasma atomic emission spectrometry) is 0.38ppmw.
Embodiment 4
Take industrial silicon 100kg; Boron concentration is about 22ppmw;
1) be take CaO, SiO at 1: 3: 1 in mass ratio
2, CaCl
2, total mass is 20kg;
2) drop in plumbago crucible by industrial silicon, vacuumize, when vacuum tightness reaches below 300Pa, open induction power supply heating, temperature rises to 1500 DEG C, heating 30min, and silico briquette melts;
3) pass into rare gas element, improve temperature to 1600 DEG C, add slag agent, start VTOL (vertical take off and landing) device and fall agitator, ventilate while stirring;
4) stop after 45min stirring ventilation, open opening for feed, drop into the CaCl of 8kg
2, close opening for feed, vacuumize, when vacuum tightness is to 600Pa, continue to stir ventilation, whole process ensures temperature more than 1600 DEG C;
5) whole process stir speed (S.S.) is 150r/min, and during stirring, Ventilation Rate is 35L/min;
6) stop after 45min stirring ventilation, after slag making completes, silicon liquid is poured into and accepts in crucible, after leaving standstill 120min, take out silicon ingot, removing 1/10 of head and 1/5 of afterbody, obtain the polycrystal silicon ingot after purifying, the content being recorded B in silicon ingot by ICP-AES (inductively coupled plasma atomic emission spectrometry) is 0.26ppmw.
Embodiment 5
Take industrial silicon 100kg; Boron concentration is about 22ppmw;
1) be take CaO, SiO at 1: 3: 1 in mass ratio
2, CaCl
2, total mass is 20kg;
2) drop in plumbago crucible by industrial silicon, vacuumize, when vacuum tightness reaches 600Pa, open induction power supply heating, temperature rises to 1500 DEG C, heating 30min, and silico briquette melts;
3) pass into rare gas element, improve temperature to 1600 DEG C, add slag agent, start VTOL (vertical take off and landing) device and fall agitator, ventilate while stirring;
4) stop after 45min stirring ventilation, open opening for feed, first time drops into activeconstituents, drops into the CaCl of 8kg
2, close opening for feed, vacuumize, when vacuum tightness is to 600Pa, continue to stir ventilation, whole process ensures temperature more than 1600 DEG C;
5) stop after 45min stirring ventilation, open opening for feed, second time drops into activeconstituents, drops into the CaCl of 4kg
2, close opening for feed, vacuumize, when vacuum tightness is to 600Pa, continue to stir ventilation, whole process ensures temperature more than 1600 DEG C;
6) whole process stir speed (S.S.) is 150r/min, and during stirring, Ventilation Rate is 35L/min;
7) stop after 45min stirring ventilation, after slag making completes, silicon liquid is poured into and accepts in crucible, after leaving standstill 120min, take out silicon ingot, removing 1/10 of head and 1/5 of afterbody, obtain the polycrystal silicon ingot after purifying, the content being recorded B in silicon ingot by ICP-AES (inductively coupled plasma atomic emission spectrometry) is 0.17ppmw.
The present invention is a kind of method except boron purifying silicon materials, and can realize the recycling of slag agent, cost is low, simple to operate, is easy to realize commercial scale production.The technical grade metalluragical silicon selected is raw material, raw silicon is put into plumbago crucible, vacuumizes, and starts medium frequency induction power supply heating.After silicon melts, in solution, pass into rare gas element, improve solution temperature, add slag agent and silicon solution reaction, after reaction terminates, again improve silicon liquid temp, add a kind of effective active composition in slag agent, continue slag making.Leave standstill after slag making completes, silicon liquid is poured into old slag and accept in crucible.When secondary or repeatedly slag making, old slag and active group are added according to a certain percentage, removal slag liquid after slag making completes, the silicon liquid after refining pours undertaking crucible into, takes out silicon ingot after cooling, obtains the HIGH-PURITY SILICON after the purification of low boron.According to the present invention, in silicon, the content of boron impurity is the highest is reduced to 0.17ppmw.
Claims (10)
1. dissolving agent of living is except boron device, it is characterized in that being provided with lobe pump, furnace base, Medium frequency induction coil, thermal insulation layer, plumbago crucible, agitator and lifting device, described lobe pump is connected with furnace base, plumbago crucible is located in furnace base, thermal insulation layer is located at plumbago crucible periphery, Medium frequency induction coil is around thermal insulation layer periphery, agitator is located in Medium frequency induction coil, the top of furnace base is provided with opening for feed and porthole, the transmission rod lower port of agitator is provided with agitator air outlet, the transmission rod top of agitator is provided with and passes bar aperture, the transmission rod top of agitator is provided with electric motor, the top of agitator is provided with air chamber and inlet mouth, described lifting device is located between the top of agitator and furnace base top.
2. dissolving agent of living, except the method for boron, is characterized in that comprising the following steps:
1) drop into plumbago crucible by raw silicon from opening for feed, start lobe pump and vacuumize, start medium frequency induction power supply heating, treat that temperature rises to 1500 DEG C, silico briquette is all melted, slag agent system is CaO-SiO
2-CaCl
2or CaO-SiO
2-CaF
2;
2) in furnace chamber, be filled with rare gas element, improve medium frequency induction power supply power to 100 ~ 250kW, temperature is remained between 1550 ~ 1650 DEG C, adds slag agent, start agitator, complete first time slag making;
3) improve medium frequency induction power supply power, make furnace chamber temperature reach 1700 ~ 1800 DEG C, open opening for feed, first time drops into slag agent activeconstituents, vacuumizes, and starts agitator, passes into rare gas element simultaneously, completes second time slag making;
4) after slag making completes, silicon liquid is poured into and accepts in crucible, leave standstill cooling, take out silicon ingot, obtain the low boron HIGH-PURITY SILICON after purifying, complete dissolving agent alive except boron.
3. dissolving agent of living as claimed in claim 2 removes the method for boron, it is characterized in that in step 1) in, described raw silicon adopts metallurgical grade industrial silicon.
4. dissolving agent of living as claimed in claim 3 removes the method for boron, and it is characterized in that described metallurgical grade industrial silicon employing purity is the metallurgical grade industrial silicon of 99% ~ 99.9%, Boron contents is at below 30ppmw.
5. dissolving agent of living as claimed in claim 2 removes the method for boron, it is characterized in that in step 1) in, described slag agent system CaO-SiO
2-CaCl
2mass ratio be 1: 3: 1, slag agent system CaO-SiO
2-CaF
2mass ratio be 1: 3: 1.
6. dissolving agent of living as claimed in claim 2 removes the method for boron, it is characterized in that in step 2) and step 3) in, the rotating speed of described agitator is 120 ~ 180r/min, and the time of stirring is 30 ~ 45min, and in whole process, Ventilation Rate is 30 ~ 40L/min.
7. dissolving agent of living as claimed in claim 2 removes the method for boron, it is characterized in that in step 2) in, described rare gas element adopts O
2, water vapour and Ar oxygen mixture, by volume per-cent O in mixed gas
2content is 0.5% ~ 1%, and water vapour content is 0.5% ~ 1%, Ar Gas content is 98% ~ 99%.
8. dissolving agent of living as claimed in claim 2 removes the method for boron, it is characterized in that in step 2) in, be provided with air chamber below described electric motor, rare gas element is entered by agitator arm top air plenum and passes bar inside; The biography masthead portion of described agitator is provided with 4 apertures, and rare gas element passes into stirrer bottom from 4 apertures, is smashed by rotating paddle, enters into silicon liquid.
9. dissolving agent of living as claimed in claim 2 removes the method for boron, it is characterized in that in step 3) in, described slag agent activeconstituents is CaCl
2or CaF
2.
10. live dissolving agent as claimed in claim 2 except the method for boron, it is characterized in that in step 3) in, described in the vacuum tightness that vacuumizes be 500 ~ 800Pa.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106012007A (en) * | 2016-07-22 | 2016-10-12 | 常州天合光能有限公司 | Method and device for growing crystalline silicone by aid of forced convection |
| 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 |
| CN110156023A (en) * | 2019-06-14 | 2019-08-23 | 宝兴易达光伏刃料有限公司 | A kind of environmentally protective smelting high-purity silicon method |
| CN111498852A (en) * | 2020-04-23 | 2020-08-07 | 北方民族大学 | Device for producing high-purity industrial silicon and preparation method thereof |
| CN114212795A (en) * | 2021-12-21 | 2022-03-22 | 湖南立新硅材料科技有限公司 | Device and method for refining silicon sludge |
Citations (6)
| 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 |
-
2015
- 2015-12-31 CN CN201511027460.4A patent/CN105540593B/en active Active
Patent Citations (7)
| 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 |
| CN1984842A (en) * | 2004-07-13 | 2007-06-20 | 夏普株式会社 | 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)
| Title |
|---|
| CHENGHAO LU, ET AL: "Effects of Slag Refining on Boron Removal from Metallurgical-Grade Silicon Using Recycled Slag with Active Component", 《SEPARATION SCIENCE AND TECHNOLOGY》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106012007A (en) * | 2016-07-22 | 2016-10-12 | 常州天合光能有限公司 | Method and device for growing crystalline silicone by aid of forced convection |
| 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 |
| CN110156023A (en) * | 2019-06-14 | 2019-08-23 | 宝兴易达光伏刃料有限公司 | A kind of environmentally protective smelting high-purity silicon method |
| CN111498852A (en) * | 2020-04-23 | 2020-08-07 | 北方民族大学 | Device for producing high-purity industrial silicon and preparation method thereof |
| CN114212795A (en) * | 2021-12-21 | 2022-03-22 | 湖南立新硅材料科技有限公司 | Device and method for refining silicon sludge |
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