CN101602506A - A kind of production method of high purity polycrystalline silicon and production equipment - Google Patents
A kind of production method of high purity polycrystalline silicon and production equipment Download PDFInfo
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Abstract
The present invention relates to a kind of production method of high purity polycrystalline silicon and utilize this production method to produce the production equipment of high purity polycrystalline silicon, wherein said production method comprises the steps: that the preparation of silicon material, melting package, the melting of silicon material, slagging-off, molten silicon refining, silicon liquid pushing off the slag casting, the vacuum outgas of silicon liquid and directional freeze, silicon ingot come out of the stove and remove the peel cutting, wherein, employed silicon material is a metallurgical grade reduction silicon in the described silicon material preparation step, and the type of heating that adopts in described silicon material melting step comprises the chemical combustion heating.Described production equipment comprises the pack arrangement that is used for melting bag or refining bag identical more than at least three, and one of them bag is used for smelting operation, and a bag is used for refining operation, and a bag is used for repairing, preheating or loading operation.Adopt production method of the present invention and equipment, can produce high purity polycrystalline silicon on a large scale, at low cost.
Description
Technical field
The present invention relates to a kind of production method of high purity polycrystalline silicon and utilize this production method to produce the production equipment of high purity polycrystalline silicon.
Background technology
Fossil energy is Nonrenewable energy resources, and because fossil energy produces the increase that a large amount of carbonic acid gas causes global greenhouse effect in using, the continuous minimizing of fossil energy and use cause the increasing pressure to existent environment of people.Sun power has caused people's attention as green energy resource.Solar energy power generating is the technology of inventing as satellite power supply the earliest; wherein the gordian technique material of photovoltaic conversion is exactly a Pure Silicon Metal; breakthrough along with photovoltaic transition material and technology; the photovoltaic switch technology realizes civil nature; high pure metal silicon demand is also constantly enlarged; simultaneously people are seeking to satisfy the industrialization solution of the critical material polysilicon of photovoltaic conversion; wish to realize safety, environmental protection, low cost, less energy-consumption, high-level efficiency, large-scale production HIGH-PURITY SILICON, to reduce the cost of photovoltaic generation.
The main method that prior art is produced solar-grade high-purity silicon has trichlorosilane reduction method, silane decomposition, metallurgy method.
The trichlorosilane reduction method also claims Siemens Method, be with industrial reduction silicon and the synthetic preparation of HCl gas trichlorosilane, utilize the characteristic of muriatic low gasification point then, the fractionation of gasifying is purified, obtain high-purity trichlorosilane, trichlorosilane generates vapor deposited silicon and HCl gas with H-H reaction in hydrogen reduction furnace.This method Production Flow Chart comprises that silica reduction, the pre-treatment of silicon material, trichlorosilane synthesize, trichlorosilane distills purification, hydrogen reduction, silicon ingot casting or oriented growth and becomes polysilicon or silicon single crystal.The trichlorosilane reduction method is unique production method of present electronic-grade high purity polycrystalline silicon, also is the main production method of present solar-grade polysilicon.But this method Production Flow Chart length, complex process, control difficulty are big, and a large amount of severe corrosives and toxicity HCl gas are high to Equipment Requirement in the production, and is big to environmental influence; In addition because the key link in producing-hydrogen reduction trichlorosilane reaction transformation efficiency is low, speed of response is slow.These factors cause that this method production efficiency is low, the equipment cost have high input, produce dangerous high, the product cost height.
Silane decomposition and Siemens Method have similar part, not being both it adopts methods such as hydrogenation of silicon tetrachloride method, silicon alloy decomposition method, hydride reduction method and silicon direct hydrogenation to prepare silane (SiH4), silane is purified, and the silane after the purification carries out thermolysis and generates silicon and hydrogen.The advantage of this method is the production efficiency height, power consumption is low, cost is low, be fit to scale operation.But the having poor stability, easily blast of this method, and the purity of product is not high.This method is also used in solar-grade high-purity silicon is produced at present.
It is to make great efforts at present to conduct a research and the method for industrialization that metallurgy method is produced solar-grade high-purity silicon, and it has, and production security is good, environmental friendliness, Production Flow Chart is short, production efficiency is high, facility investment is little, be easy to realize advantage such as scale production.But it is also few to obtain to satisfy the solar-grade high-purity silicon that the photovoltaic conversion requires at present, and it mainly is limited by the source of raw material.Existing metallurgy method Technology is had relatively high expectations to raw material, and raw material mainly comes from the processing of semicon industry electronic-grade HIGH-PURITY SILICON and cuts clout.Because this part raw material limited amount can not satisfy the quantitative requirement of sun power industry to solar-grade high-purity polycrystalline silicon.Adopting metallurgy method to prepare solar-grade high-purity silicon from common reduction silicon is to satisfy solar-grade high-purity polycrystalline silicon quantitative requirement preferred plan in cost, scale.The more representational technical solution of metallurgy method has the electron beam of Japanese JFE company and plasma refining technology, the pyrorefining of Norway Elkem Sinle company, wet method acid immersion impurity removing technology.The implement scale of these methods is little, and the cost height can't solve the problem of mass-producing, serialization production.
Carried out many research work aspect the solar-grade high-purity silicon domestic the preparation in metallurgy method, and formed the partial monopoly technology.As Chinese patent application numbers 200610010654.8, " a kind of method for preparing solar-grade polysilicon " disclosed.This method is a raw material with the metallurgical grade silicon, adopts hydrochloric acid, nitric acid and hydrofluoric acid to carry out acidleach after the fragmentation respectively and handles, and needs with residual acid in a large amount of distilled water flush away silica flours.Silica flour after acidleach is handled divides two stages to carry out vacuum refinement at a vacuum oven, and the fs is vor refining, and with the fusing of silicon material, the argon gas that feeds moisture vapor then carries out oxidation refining to molten silicon by induction heating device.We know that argon gas is a rare gas element, and water is neutral, and two kinds of gases do not possess oxidisability, thus oxidation refining intensity very a little less than.Subordinate phase is vacuum distilling refining and vacuum outgas.After vacuum refinement is finished melt being carried out directional freeze handles.Adopt the mode of induction heating in this patent, because the restriction of induction heating technique condition, the power and the furnace capacity of induction heating are all very limited at present, and particularly for the higher silicon heating of resistivity, the direct induction efficiency of electromagnetism is very low.Therefore also there are little and some technological deficiencies of capacity scale in this patent, commercial scale production is used also have distance.
Chinese invention patent application number 200710055601.2 discloses " novel process of preparation solar-grade polysilicon ".This patent proposed a kind of in electric arc furnace the reduction with carbon silica extract metalluragical silicon, in refining furnace, flocculate, solvent, oxidation refining, be cast into silicon ingot after the refining, silicon ingot carries out hydrochloric acid after fragmentation, hydrofluoric acid leaches, the silica flour that leaches carries out vacuum refinement in the 20kg vacuum induction furnace, adopt molybdenum bar condensation from silicon liquid of band water-cooled to extract silicon, extract out after weight reaches 1～5 kilogram and refill silicon liquid, then the silicon that melting is extracted in another vacuum oven and containing the argon gas of 1～5% water vapor and vacuum under refining, carry out directional freeze after refining is finished, obtain silicon ingot.This complex technical process need repeat melting, the energy consumption height.And furnace capacity is very little, 110 kilograms of electric arc furnace, 20 kilograms of refining furnaces.Adopt the condensation of band refrigerative molybdenum bar to extract silicon in the refining, have only 1～5 kilogram at every turn, need constantly come out of the stove, replenish silicon liquid, vacuum pumping, efficient is very low, is not suitable for the industrial-scale production high purity polycrystalline silicon.
Chinese invention patent application number 200810105851.7 open " metallurgy purification method of polysilicon ".This method proposes under 1000～1600 ℃ Pure Silicon Metal is being carried out the slag making processing under the protection of rare gas element argon gas, and treatment process is to add alkaline slag former.To wear into powder through the Pure Silicon Metal that slag making is handled then.Deoil respectively then and the acidleach processing.At first be the processing of deoiling, treatment process is to adopt weak ammonia or hydrogen peroxide to handle, and uses alcohol immersion then, uses deionized water wash again.The silica flour that deoils after handling carries out the acidleach processing again, and treatment step is to use the processing of (1) dilute hydrochloric acid, deionized water wash respectively; (2) chloroazotic acid, the vitriol oil, concentrated nitric acid are handled deionized water wash; (3) hydrofluoric acid treatment, deionized water wash; (4) concentrated hydrochloric acid processing, deionized water wash.Silica flour after at last acidleach being handled is smelted into silicon ingot with the method for directional freeze.There is multinomial deficiency in this method of purification.At first be under inert atmosphere, carry out the slag making treatment effect can be not fine, can only be with in the small amounts thing in the silicon liquid absorption slag input mutually.We know that the impurity element in the Pure Silicon Metal mostly is not that form with oxide compound exists, so simple slag making is handled and the impurity element in the silicon can not be gathered slag and go in mutually.In addition, this method needs a large amount of use inflammable ethanol, corrosive oxidation agent and strong acid, and is not only not easy to operate, and very big to the influence of environment, and needs a large amount of washed with de-ionized water, produces a large amount of sour waters, also is unfavorable for environment.If this method is used for the industrial production solar-grade polysilicon obviously, also need to solve a lot of practical problemss.
Chinese invention patent application number 200610046525.4 discloses " a kind of preparation method of used for solar batteries high purity polycrystalline silicon and device ".This patent provides a kind of device with melting, casting and directional freeze function.At first the silicon material is melted in the smelting zone, be cast into then in the directional freeze crucible, start the high-temperature zone of dragging ingot mechanism to make crucible slowly shift out directed district downwards, obtain directionally solidified silicon ingots.Above-mentioned silicon ingot is carried out secondary smelting purify, adopt plasma gun in the purification process and spray into oxidizing gas and purify, after purification is finished liquation is cast into die for molding, cooling, obtain high purity polycrystalline silicon.It is simple that this inventive method has a device structure, the advantage that flow process is short.But this method is difficult to be met the high purity polycrystalline silicon that solar cell needs obviously.At first be in melting once, in the directional freeze process, substantially do not remove the function of impurity in the silicon, though the directional freeze process can make the metallic impurity in the silicon gather to an end of directed base, but this patent of invention method does not have process and method that impurity is assembled in follow-up removal, in this external secondary oxidation refining process, after spraying into oxidizing gas, can be under the normal circumstances with impurity in the silicon liquid and silicon oxidation, form oxide compound, and the fusing point of oxide compound will be higher than the fusing point of silicon, and often the proportion of oxide compound is also very approaching or greater than the proportion of silicon in the silicon system, the layering of oxide compound and silicon is very difficult, therefore the removal of unfavorable oxide compound need carry out special processing to oxide compound, could keep the purpose that refining is purified that reaches of fusion process.This method reality does not possess the condition of purified silicon obviously, nor is fit to large-scale industrial production.
It is production method low-cost, safe, efficient, mass-producing that metallurgy method is produced solar-grade high-purity polycrystalline silicon; it also is the direction of high purity polycrystalline silicon production technology development; but the deficiency in view of prior art exists presses for a kind of industrial technology method and the equipment that can realize the industrial-scale production solar-grade high-purity polycrystalline silicon.
Summary of the invention
The objective of the invention is to, overcome the defective of above-mentioned prior art and provide a kind of and can realize that big furnace capacity produces the method and the equipment of high purity polycrystalline silicon.
For achieving the above object, the present invention takes following design:
A kind of production method of high purity polycrystalline silicon, described production method comprises the steps: that the preparation of silicon material, melting package, the melting of silicon material, slagging-off, molten silicon refining, silicon liquid pushing off the slag casting, the vacuum outgas of silicon liquid and directional freeze, silicon ingot come out of the stove and remove the peel cutting, wherein, employed silicon material is a metallurgical grade reduction silicon in the described silicon material preparation step, and the type of heating that adopts in described silicon material melting step comprises the chemical combustion heating.
Preferably, also comprised melting bag pre-heating step before described melting package step, the temperature of described melting bag preheating is 1000～1600 ℃.
Preferably, described silicon material melting step comprises that also adding light alkaline oxide compound 2～40%, carbonate 0～35%, fusing assistant 1～25% generate the step of low melting point, low density, low-viscosity silicate sludge with the silicon oxide with fusion process formation, wherein said light alkaline oxide compound comprises magnesium oxide, calcium oxide or barium oxide, and described fusing assistant is a fluorite.Further, the type of heating that adopts in described silicon material melting step comprises electrically heated and/or chemical combustion heating, wherein said electrically heated comprises induction heating, resistive heating or electron beam heating, described chemical combustion heating comprises blows coal oxygen burning heating, the heating of oxygen blast burning silicon, and the wherein said fuel that blows coal oxygen burning heating comprises heavy oil, coal dust, coal gas or Sweet natural gas.In addition, preferably, described silicon material melting step is carried out under antivacuum or subnormal ambient.
Preferably, after described silicon material melting step is finished and reached 1430～1700 ℃, adopt slag scraper to be removed the gred in silicon liquid surface.
Preferably, described molten silicon refinement step comprises the refining purification process, and this refining purification process may further comprise the steps: be blown into argon gas, oxygen, water vapour gas mixture successively in silicon liquid, wherein to account for volume percent be 1～15% for oxygen, water vapour; Argon gas, oxygen mixture, wherein to account for volume percent be 1～15% to oxygen; Argon gas, hydrogen mixed gas, wherein to account for volume percent be 1～10% to hydrogen; Described refining purification process carries out under rough vacuum, and adopts vapor jet pump that the refining furnace that uses in the refining purification process is vacuumized.Further, adding total amount in described refining process is light alkaline oxide compound, carbonate, fusing assistant and the silicon-dioxide of silicon liquid weight 0.1～10%, weight part between them close be that the light alkaline oxide compound accounts for 5～35%, carbonate 1～35%, fusing assistant 5～20%, silica 1～10%, wherein said light alkaline oxide compound comprises magnesium oxide and/or calcium oxide, and described fusing assistant is a fluorite.In addition, described refining process comprises electrically heated and/or plasma gun heating to the temperature raising and the heat preserving mode of silicon liquid, outside preembedded graphite or the silicon-carbon piece resistance heating element energising heating of described electrically heated for adopting the refining ladle-lining, described plasma gun is heated to be plasma gun is inserted in the refining chamber from refining furnace top, and silicon liquid surface is heated.
Preferably, the silicon liquid that refining is finished is cast in the directional freeze bag, and sends into and carry out directional freeze in the directional solidification furnace, and described directional freeze is carried out thermal pretreatment before wrapping in and being cast into silicon liquid, and preheating temperature is 1400～1600 ℃.Further, after the directional freeze bag of the described silicon liquid of packing into is admitted in the directional solidification furnace, at first carry out silicon liquid vacuum outgas treatment step, the treatment time is that 0.5～10 hour, vacuum tightness are 10
-2～10
-3Pa, temperature are 1450～1600 ℃; Carry out the directional freeze step then, solidifying the speed of growth is 2～60mm/hr.
Preferably, also comprise with the silicon ingot after the directional freeze partly return the silicon material preparatory stage, again carry out fragmentation and with pretreated silicon material blended step, it is 5～30% that silicon ingot returns the ratio of carrying out melting again.
Preferably, the silicon ingot after the directional freeze is removed the peel cutting, and will cut clout and return the silicon material preparatory stage and carry out fragmentation and wet processing, carry out melting again.
Another object of the present invention provides a kind of production equipment that utilizes aforementioned production method to produce high purity polycrystalline silicon, comprise the pack arrangement that is used for melting bag or refining bag identical more than at least three, one of them bag is used for smelting operation, a bag is used for refining operation, and a bag is used for repairing, preheating or loading operation.Further comprise directional solidification furnace and a refining furnace coupling more than at least two, carry out directional freeze so that the silicon liquid that a bag refining is finished is cast into respectively in the described directional solidification furnace more than two.
Adopt production method of the present invention and equipment, can produce high purity polycrystalline silicon on a large scale, at low cost, the polysilicon of production not only can be directly used in produces the solar-energy photo-voltaic cell silicon chip, also can be used to produce other purpose silicon materials.Produce the solar-grade high-purity polycrystalline silicon preparation method with existing metallurgy method and compare with equipment, the present invention has many important advantages:
At first be to the invention provides a kind of technological line and the equipment that can realize the scale operation high purity polycrystalline silicon.The production line structural arrangement is clear and definite, compact construction, and it comprises the stages such as raw materials pretreatment, melting, refining, directional freeze, processing; The secondth,, smelting technique of the present invention adopts under antivacuum or the negative pressure and operates, and has avoided application high vacuum condition restriction furnace capacity, and the smelting furnace capacity among the present invention can be enlarged greatly; The 3rd, the coal oxygen burning that the silicon melting is adopted among the present invention, silicon oxidation burning type of heating have been avoided under the situation of big furnace capacity, and single Electric heating can not satisfy the needs of large vol heating; Simultaneously, the employing of chemical energy has not only enlarged furnace capacity, has also significantly reduced the consumption of electric energy, reaches energy saving purposes; The 4th, in the chemical combustion heating, realized the purpose of silicon deep oxidation removal of impurities, shorten the flow process that silicon is purified; The 5th, the present invention has finished the oxidation removal that major part is mingled with in smelt stage, reduced the refining load, making refining process only need finish influences the crucial tramp element B of photovoltaic efficiency of conversion, the removal of P, O in the high purity polycrystalline silicon, impurity elimination has clear and definite specific aim, has improved the efficient of impurity elimination; The 6th, the interchangeability of melting bag, refining bag or continuing property, making the stove bag remain on the condition of high temperature works continuously, not only can reduce thermosteresis, also avoided simultaneously " low temperature-high temperature " alternating temperature of stove bag to operate the shortening that causes lining life, reduce the loss of equipment and the consumption of material, reduce production costs; The 7th, production method of the present invention and equipment are easy to realize that the specific investment expense that production line is built is low, and industrial scale is big, low cost of manufacture, and purity height, product have very strong competitive power.
Production method of the present invention and equipment can be used for producing the production of solar-grade high-purity polycrystalline silicon, but are not restricted to the production of this rank polysilicon product.
Description of drawings
Fig. 1 is a production scheme of the present invention.
Embodiment
Referring to Fig. 1, the flow process of production method of the present invention comprises: the silicon material is prepared, the preheating of melting bag and charging, the melting of silicon material, slagging-off, molten silicon refining, silicon liquid pushing off the slag casting, the vacuum outgas of silicon liquid and directional freeze, silicon ingot are come out of the stove and remove the peel step such as cutting, wherein, employed silicon material is a metallurgical grade reduction silicon in the described silicon material preparation step, and the type of heating that adopts in described silicon material melting step comprises the chemical combustion heating.
The silicon material of the inventive method production HIGH-PURITY SILICON is a metallurgical grade reduction silicon, Pure Silicon Metal that the technology reduction of silica by various prior aries just obtains or the Pure Silicon Metal of handling through preliminary melting.Described silicon material preparation step comprises fragmentation, powder process, wet chemical process, cleaning, the oven dry of silicon material.Pure Silicon Metal is carried out graded crushing in crusher, and then make the silica flour of processing requirement granularity with the further fragmentation of airflow milling.The oxide compound and the part metals that adopt sour dissolution method to remove in the silicon then are mingled with, and through deionization washing back oven dry, take by weighing suitable weight by the smelting furnace capacity again, are placed on temporarily in the reinforced hopper, and preparation adds the melting bag.
Melting is carried out preheating before wrapping in dress silicon material, and preheating method can be chemical heat such as electrically heated, heavy oil or gas-fired, and melting bag preheating temperature reaches 1000～1600 ℃.Can certainly not preheating melting bag, the silicon material of directly packing into carries out melting.What particularly point out is that preheating temperature improves, and helps reducing the loss of silicon, shortens melting cycle.The preheating of melting bag is carried out on the special preheating worktable of production line, by reinforced hopper the silicon material is added in the melting bag after the preheating.
The melting bag that fills the silicon material is transported on the melting worktable of production line by crane or rail car, and the beginning smelting operation.The fusing of silicon material can be adopted electrically heated, and electrically heated comprises induction heating, resistive heating, electron beam heating.Induction heating is heated to be good with power frequency.By existing electromagnetic induction heating technology, the power frequency heating can obtain bigger furnace capacity.Resistive heating is at the embedding in advance resistance heating element of the liner skin of melting bag, and as graphite, silicon-carbon piece etc., for large vol melting bag, resistive heating is because power is limited, and heat-up time is longer, generally only does boosting or insulation effect.Great-power electronic Shu Jiare especially is fit to technology of the present invention, and not only rate of heating is fast for it, and clean, can reduce the secondary pollution of silicon liquid.But great-power electronic bundle heating installation price is very high.In heating means of the present invention, go back the special chemical combustion heating that proposes, comprise that blowing the burning of coal oxygen heats (fuel comprises heavy oil, coal dust, coal gas, liquefied gas etc.), the heating of oxygen blast burning silicon.This method is the surface that at first the incendiary coaloust-oxygen gun is placed the silicon material, the heat that produces by the burning of coal oxygen makes the silicon fusing, after the silicon of fusing forms the molten bath, close fuel feed, directly oxygen blast, make silicon under the high temperature dispensing heat that in oxygen, burns, continue the silicon material is heated, all melt up to the silicon material.In the fusion process of silicon material, in the melting bag, add simultaneously by the good light alkaline oxide compound of Process configuration, carbonate, fluorite etc., the silicon oxide that forms with fusion process generates the silicate sludge of low melting point, low density, low-viscosity, wherein the light alkaline oxide compound mainly comprises magnesium oxide, calcium oxide, barium oxide etc., and carbonate mainly comprises sodium bicarbonate, sodium carbonate etc.By making low-melting lightweight silicate sludge, make slag float over the surface of silicon liquid.Adopt the chemical combustion heating not only can save electric energy, and the metal inclusion oxidation in the silicon can be entered the slag phase, reach the purpose of purified silicon.Certainly, in melting mode of the present invention, when adopting electrically heated, also need oxygen blast and slag making, reach the purpose that is mingled with in the oxidation removal silicon.
Silicon material fusion process is to carry out under antivacuum or subnormal ambient among the present invention, does not need to set up huge vacuum system, makes furnace capacity that bigger extending space be arranged, and can reduce investment outlay, and reduces melting running cost.
" antivacuum " of the present invention environment is meant: atmospheric environment;
" negative pressure " of the present invention environment is meant: by the low pressure environment of exhaust blower or induced draft fan generation;
" rough vacuum " of the present invention is meant: vacuum tightness is 1～9000Pa.
When the melting of silicon material is finished, and after reaching 1430～1700 ℃, adopt slag scraper to remove the slag on silicon liquid surface.Molten silicon after the slagging-off is sent into the refining station and is carried out the refining purification.Melting bag and refining bag can be general in production line of the present invention, and just melting bag and refining bag are identical.The melting of silicon material is finished so, and directly handling of melting bag or track is transported to the refining platform after removing surperficial slag, carries out refining operation.Certainly, because the refining bag needs vacuum seal structure, also can adopt different bags.At this moment, needing in advance refining to be wrapped in the preheating worktable carries out molten silicon being cast in the refining bag after the preheating again.If certainly design rhythm of production, when a last bag silicon liquid refining is finished, and after being cast into directed stove, can directly accepting the silicon liquid that melting is finished, and not need to carry out the preheating of refining bag, can reduce energy consumption greatly, can realize staying simultaneously the silicon operation.
Silicon liquid refining purification process of the present invention is to divide three phases to carry out under rough vacuum, and main purpose is to remove nonmetal inclusions such as B, P in the silicon, O.Before beginning, refining at first adds special-purpose refining slag by Process configuration, the adding total amount of refining slag is a silicon liquid weight 0.1～3%, the main component of slag burden is light alkaline oxide compound, carbonate, fusing assistant, silicon-dioxide, the light alkaline oxide compound is that magnesium oxide, calcium oxide, carbonate are sodium bicarbonate etc., and fusing assistant is a fluorite.Fs is the tramp element B that removes in the silicon.Its process is the gas mixture that is blown into argon gas, oxygen, water vapour in silicon liquid, and wherein the per-cent 1～15% of oxygen and water vapour volume sum makes B generate volatile oxyhydroxide, overflows from silicon liquid and eliminating under vacuum.Subordinate phase is the tramp element P that removes in the silicon.Its process is to be blown into argon gas, oxygen mixture in silicon liquid, and wherein the oxygen volume percent 1～15%, and the P in the silicon is combined with dissolved oxygen, generates volatile phosphorus oxide, overflows from silicon liquid and eliminating under vacuum.Phase III is the dissolved oxygen that removes in the silicon.Its process is to be blown into argon gas, hydrogen mixed gas in silicon liquid, and wherein hydrogen volume per-cent 1～10%, and the oxygen in the silicon liquid is combined with hydrogen, generates H
2O overflows from silicon liquid and eliminating under vacuum.The refining purification process carries out under rough vacuum, adopts vapor jet pump that refining furnace is vacuumized.The squirt pump rate of air sucked in required is big, and does not have and to move back and forth parts, and is not easy to wear, is pumping equipment first-selected in present method refining unit.Can certainly select mechanical pump, mechanical booster pump, oil diffusion pump unit or mechanical pump, oily topping-up pump unit for use.
Temperature raising and heat preserving mode to silicon liquid in the refining process adopt electrically heated or plasma gun heating, also can be both combinations.Electrically heated is to adopt the outside preembedded graphite of refining ladle-lining or silicon-carbon piece resistance heating element energising heating.The plasma gun heating is that it is inserted in the refining chamber from refining furnace top, and silicon liquid surface is heated.
After the refining of above-mentioned silicon liquid is finished, adopt the mode of pushing off the slag casting down antivacuum, the silicon liquid that refining is finished is cast in the directional freeze bag, and slag does not enter in the directional freeze bag, and sends into and carry out directional freeze in the directional solidification furnace.Directional freeze is preferably carried out thermal pretreatment, 1400～1600 ℃ of preheating temperatures before wrapping in and being cast into silicon liquid.
Directional freeze process of the present invention comprises vacuum outgas processing and two steps of silicon liquid, directional solidification.After the directional freeze bag of silicon liquid of will packing into is sent in the directional solidification furnace, at first carry out high vacuum degassing and handle 0.5～10 hour treatment time, vacuum tightness 10
-2～10
-31450～1600 ℃ of Pa, temperature are carried out directional freeze after vacuum outgas is finished dealing with, solidified the speed of growth 2～60mm/ hour.
In the method for the present invention, in order to reduce the purification load of silicon, the high-purity silicon ingot after can suitably a part being purified in the production returns the silicon material preparatory stage, and mix with pretreated silicon material broken again back.It is 5～30% that silicon ingot returns the ratio of handling again.
Silicon ingot after the directional freeze is removed the peel cutting processing, adopt scroll saw or slicing machine that silicon ingot is removed the peel processing, the epidermis of excision silicon ingot, and being mingled with under the enrichment end-grain cutting with silicon ingot after the directional freeze, the cutting clout returns the silicon material preparatory stage and carries out fragmentation and wet processing, carries out melting again.
Method according to high purity polycrystalline silicon of the present invention, in production equipment of the present invention, the furnace capacity of smelting furnace and refining furnace is big, and directional solidification furnace is because of being subjected to the restriction of silicon ingot following process condition, and the restriction of a silicon ingot directional freeze process temperature control, the furnace capacity of directional solidification furnace is much smaller than smelting furnace and refining furnace, therefore preferably have two or many directional solidification furnaces and a refining furnace coupling on the production line, the silicon liquid that one bag refining is finished is cast into respectively and carries out directional freeze in many directional solidification furnaces, to keep the moderate of silicon ingot size.
In high purity polycrystalline silicon production equipment of the present invention, melting bag, refining bag can be identical bags in the production, need in the production to be equipped with more than three, one of them bag is in the smelting operation, a bag is in the refining operation, a bag is in repairing, preheating and the charging, makes HIGH-PURITY SILICON production line compact construction, keeps operate continuously, reduces investment cost and production energy consumption.
Other devices and structure in the production equipment of the present invention can adopt production of polysilicon equipment various in the prior art, do not repeat them here.
Embodiment 1:
Referring to Fig. 1, the preferred embodiment of production method of the present invention shown in it.Be raw material at first, Pure Silicon Metal is carried out graded crushing in crusher, and then carry out further fragmentation with airflow milling and make 150～400 purpose silica flours with the carbon reduction Pure Silicon Metal.The oxide compound and the part metals that adopt sour dissolution method to remove in the silicon then are mingled with, and through deionization washing back oven dry, take by weighing 25 tons of silica flours by 25 tons of smelting furnace capacity again, place reinforced hopper, and preparation adds the melting bag.25 tons of meltings are carried out preheating before wrapping in dress silicon material, and preheating method heats with heavy oil combustion, and melting bag preheating temperature reaches 1500～1520 ℃.The preheating of melting bag is carried out on the special preheating worktable of production line, by reinforced hopper the silicon material is added in the melting bag after the preheating.
The melting bag that fills the silicon material is transported on the melting worktable of production line by rail car, and the beginning smelting operation.The melting type of heating is that coaloust-oxygen gun (fuel is coal dust) aids in the electron beam heating.At first the incendiary coaloust-oxygen gun is placed the surface of silicon material, the heat that produces by the burning of coal oxygen makes the silicon fusing, after the silicon of fusing forms the molten bath, closes fuel gas, and directly oxygen blast starts the electron beam gun boosting simultaneously.Make silicon under the high temperature release of heat of in oxygen, burning, continue the silicon material is heated, all melt up to the silicon material.In the fusion process of silicon material, in the melting bag, add by the good magnesium oxide of Process configuration, calcium oxide, fluorite, sodium bicarbonate etc. simultaneously, the ratio between them is magnesium oxide, calcium oxide 20%, sodium bicarbonate 10%, fluorite 5%.By making low-melting lightweight silicate sludge, make slag float over the surface of silicon liquid.Silicon material fusion process is to carry out antivacuum, and negative pressure is produced by air inducing equipment.The silicon material stops oxygen supply after melting clearly, adopts the electron beam gun insulation, and continues 2 hours.
After the melting of silicon material is finished, and temperature is adjusted to 1550 ℃, adopt slag scraper to remove the slag on silicon liquid surface.It is in 25 tons the refining bag that molten silicon after the slagging-off is cast into capacity, and sends into the refining station and carry out refining and purify.Before being cast into molten silicon, refining being wrapped in carry out on the preheating worktable again molten silicon being cast in the refining bag after the preheating in advance, 1520 ℃ of refining bag preheating temperatures, preheating method is identical with the melting bag.
Silicon liquid refining purification process is to divide three phases to carry out under rough vacuum, and main purpose is to remove nonmetal inclusions such as B, P in the silicon, O.Before beginning, refining at first adds special-purpose refining slag by Process configuration, the adding total amount of refining slag is a silicon liquid weight 3%, the main component of slag burden is magnesium oxide, calcium oxide, silicon-dioxide, sodium bicarbonate etc., fusing assistant is a fluorite, weight part between them close be that magnesium oxide, calcium oxide account for 35%, carbonate 35%, fusing assistant 20%, silica 1 0%.Fs is the tramp element B that removes in the silicon.Its process is the gas mixture that is blown into argon gas, oxygen, water vapour in silicon liquid, and wherein oxygen, water vapour volume percent 8% make B generate volatile oxyhydroxide, overflows and eliminating 1.5 hours treatment times fs under vacuum from silicon liquid.Subordinate phase is the tramp element P that removes in the silicon.Its process is to be blown into argon gas, oxygen mixture in silicon liquid, and wherein the oxygen volume percent 5%, and the P in the silicon is combined with dissolved oxygen, generates volatile phosphorus oxide, overflows and eliminating 1 hour subordinate phase treatment time under vacuum from silicon liquid.Phase III is the dissolved oxygen that removes in the silicon.Its process is to be blown into argon gas, hydrogen mixed gas in silicon liquid, and wherein hydrogen volume per-cent 3%, and the oxygen in the silicon liquid is combined with hydrogen, generates H
2O overflows and eliminating 2 hours treatment times phase III from silicon liquid under vacuum.The refining purification process carries out under rough vacuum, more than the vacuum tightness 1000Pa, adopts vapor jet pump that refining furnace is vacuumized.
Temperature raising and heat preserving mode to silicon liquid in the refining process adopt electrically heated to aid in the plasma gun heating.Electrically heated is the outside preembedded graphite block resistance heating element energising heating of adopting the refining ladle-lining.The plasma gun heating is that plasma gun is inserted in the refining chamber from refining furnace top, and silicon liquid surface is heated.
After the refining of above-mentioned silicon liquid is finished, under antivacuum, adopt the mode of pushing off the slag casting, the silicon liquid that refining is finished is cast in the directional freeze bag, directional freeze bag list containing amount is 2.5 tons, once be cast in about 10 2.5 tons of directional solidification furnace bags, and slag does not enter in the directional solidification furnace bag, the directional solidification furnace bag is sent into by rail car and is carried out directional freeze in the directional solidification furnace.Directional solidification furnace carries out thermal pretreatment before wrapping in and being cast into silicon liquid, 1560 ℃ of preheating temperatures.
The directional freeze process comprises vacuum outgas processing and two steps of silicon liquid, directional solidification.After the directional freeze bag of silicon liquid of will packing into is sent in the directional solidification furnace, at first carry out high vacuum degassing and handle 2 hours treatment times, vacuum tightness 10
-2～10
-31520 ℃ of Pa, temperature are carried out directional freeze after vacuum outgas is finished dealing with, solidified speed of growth 0.3mm/ minute.
After directional freeze was finished, the silicon fixation is carried out stove in directed holding furnace cold.In order to reduce the purification load of silicon, in the production the high-purity silicon ingot after 16% purification is returned the silicon material preparatory stage, mix with pretreated silicon material broken again back.
Embodiment 2:
Referring to Fig. 1, be raw material equally, Pure Silicon Metal is carried out graded crushing in crusher, and then carry out further fragmentation with airflow milling and make 150～250 purpose silica flours with the carbon reduction Pure Silicon Metal.The oxide compound and the part metals that adopt sour dissolution method to remove in the silicon then are mingled with, and through deionization washing back oven dry, take by weighing 15 tons of silica flours by 15 tons of smelting furnace capacity again, place reinforced hopper, and preparation adds the melting bag.15 tons of meltings are carried out preheating before wrapping in dress silicon material, and preheating method heats with heavy oil combustion, and melting bag preheating temperature reaches 1500 ℃.The preheating of melting bag is carried out on the special preheating worktable of production line, by reinforced hopper the silicon material is added in the melting bag after the preheating.
The melting bag that fills the silicon material is transported on the melting worktable of production line by crane, and the beginning smelting operation.The fusing of silicon material can be adopted and blow coal oxygen burning heating (fuel is coal dust or coal gas), the heating of oxygen blast burning silicon, aids in the electron beam gun heating simultaneously.At first the incendiary coaloust-oxygen gun is placed the surface of silicon material, the heat that produces by the burning of coal oxygen makes the silicon fusing, after the silicon of fusing forms the molten bath, close coal gas, directly oxygen blast makes silicon under the high temperature release of heat of burning in oxygen, continuation is heated the silicon material, all melts up to the silicon material.In the fusion process of silicon material, in the melting bag, add simultaneously by good magnesium oxide, calcium oxide, barium oxide, sodium bicarbonate, sodium carbonate and the fluorite etc. of Process configuration.Silicon material fusion process is to carry out under subnormal ambient, and negative pressure is produced by induced draft fan.After the silicon material melts clearly, continue with the electron beam gun insulation, and continue to heat 3 hours.
After the melting of silicon material is finished, after adjusting pouring temperature and reaching 1560 ℃, adopt slag scraper to remove the slag on silicon liquid surface.Melting bag and refining bag can be general in the present embodiment, and just melting bag and refining bag are identical.The melting of silicon material is finished so, and directly handling of melting bag or track is transported to the refining platform after removing surperficial slag, carries out refining operation.
Silicon liquid refining purification process is to divide three phases to carry out under rough vacuum.At first add the special-purpose refining slag by Process configuration before refining begins, the adding total amount of refining slag is a silicon liquid weight 1.8%, and the main component of slag burden is magnesium oxide, calcium oxide, sodium bicarbonate, silicon-dioxide, and the fusing assistant fluorite.Fs is the tramp element B that removes in the silicon.Its process is the gas mixture that is blown into argon gas, oxygen, water vapour in silicon liquid, and wherein oxygen, water vapour volume percent 10% make B generate volatile oxyhydroxide, overflows from silicon liquid and eliminating under vacuum.Subordinate phase is the tramp element P that removes in the silicon.Its process is to be blown into argon gas, oxygen mixture in silicon liquid, and wherein the oxygen volume percent 6%, and the P in the silicon is combined with dissolved oxygen, generates volatile phosphorus oxide, overflows from silicon liquid and eliminating under vacuum.Phase III is the dissolved oxygen that removes in the silicon.Its process is to be blown into argon gas, hydrogen mixed gas in silicon liquid, and wherein hydrogen volume per-cent 3%, and the oxygen in the silicon liquid is combined with hydrogen, generates H
2O overflows from silicon liquid and eliminating under vacuum.The refining purification process carries out under rough vacuum, adopts vapor jet pump that refining furnace is vacuumized.
Temperature raising and heat preserving mode to silicon liquid in the refining process adopt the graphite heating element energising heating that is embedded in the furnace lining outside, aid in the plasma gun heating simultaneously.The plasma gun heating is that plasma gun is inserted in the refining chamber from refining furnace top, and silicon liquid surface is heated.
After the refining of silicon liquid is finished, adopt the mode of pushing off the slag casting down antivacuum, the silicon liquid that refining is finished is cast in the directional freeze bag, and slag does not enter in the directional freeze bag, and sends into and carry out directional freeze in the directional freeze bag.15 tons of refining bags dock 10 1.5 tons of directional freeze bags.Directional freeze must be carried out thermal pretreatment before wrapping in and being cast into silicon liquid, and preheating temperature is more than 1530 ℃.
The directional freeze process comprises vacuum outgas processing and two steps of silicon liquid, directional solidification.After the directional freeze bag of silicon liquid of will packing into is sent in the directional solidification furnace, at first carry out high vacuum degassing and handle 2 hours treatment times, vacuum tightness 10
-2～10
-31530 ℃ of Pa, temperature are carried out directional freeze after vacuum outgas is finished dealing with, solidified speed of growth 0.5mm/ minute.After directional freeze is finished the orientation bag is transported in the holding furnace, makes the silicon ingot slow cooling, reduce internal stress.
In the production, in order to reduce the purification load of silicon, the high-purity silicon ingot after can suitably a part being purified returns the silicon material preparatory stage, and mix with pretreated silicon material broken again back, and it is 12% that silicon ingot returns the ratio of handling again.
Silicon ingot after the directional freeze is removed the peel cutting processing, adopt scroll saw or slicing machine that silicon ingot is removed the peel processing, the epidermis of excision silicon ingot, and being mingled with under the enrichment end-grain cutting with silicon ingot after the directional freeze, the cutting clout returns the silicon material preparatory stage and carries out fragmentation and wet processing, carries out melting again.
Embodiment 3:
Referring to Fig. 1, be raw material with the carbon reduction Pure Silicon Metal, Pure Silicon Metal is carried out graded crushing in crusher, and then carry out further fragmentation with airflow milling, make 150～250 purpose silica flours.The oxide compound and the part metals that adopt sour dissolution method to remove in the silicon then are mingled with, and through deionization washing back oven dry, take by weighing 5 tons of silica flours again, add in 5 tons of power frequency smelting furnaces.
Start the line-frequency induction heating, and aid in and blow coal oxygen burning heating (fuel is liquefied gas etc.), oxygen blast burning heating.The incendiary coaloust-oxygen gun is placed the surface of silicon material, and the heat that produces by the burning of coal oxygen makes the silicon fusing, after the silicon of fusing forms the molten bath, close coal gas, directly oxygen blast makes silicon under the high temperature release of heat of burning in oxygen, continuation is heated the silicon material, all melts up to the silicon material.In the fusion process of silicon material, in the melting bag, add simultaneously by good magnesium oxide, calcium oxide, barium oxide, sodium bicarbonate, sodium carbonate and the fluorite etc. of Process configuration.Silicon material fusion process is to carry out antivacuum, and negative pressure is produced by induced draft fan.After the silicon material melts clearly, continue with main-frequency electromagnetic induction insulation heating 1 hour.
After the melting of silicon material is finished, after adjusting pouring temperature and reaching 1540 ℃, adopt slag scraper to remove the slag on silicon liquid surface.Then silicon liquid is cast in 5 tons the refining bag.Refining is preheating to 1600 ℃ before wrapping in casting silicon in advance, and the handling of melting bag to the refining platform, is carried out refining operation.
Silicon liquid refining purification process is to divide three phases to carry out under rough vacuum.Before refining begins, at first add the special-purpose refining slag by Process configuration, the adding total amount of refining slag is 1.0% of a silicon liquid weight, and the main component of slag burden is magnesium oxide, calcium oxide, sodium bicarbonate, silicon-dioxide, and the fusing assistant fluorite.Fs is the tramp element B that removes in the silicon.Its process is the gas mixture that is blown into argon gas, oxygen, water vapour in silicon liquid, and wherein oxygen, water vapour volume percent 12% make B generate volatile oxyhydroxide, overflows from silicon liquid and eliminating under vacuum.Subordinate phase is the tramp element P that removes in the silicon.Its process is to be blown into argon gas, oxygen mixture in silicon liquid, and wherein the oxygen volume percent 10%, and the P in the silicon is combined with dissolved oxygen, generates volatile phosphorus oxide, overflows from silicon liquid and eliminating under vacuum.Phase III is the dissolved oxygen that removes in the silicon.Its process is to be blown into argon gas, hydrogen mixed gas in silicon liquid, and wherein hydrogen volume per-cent 6%, and the oxygen in the silicon liquid is combined with hydrogen, generates H
2O overflows from silicon liquid and eliminating under vacuum.The refining purification process carries out under rough vacuum, adopts vapor jet pump that refining furnace is vacuumized.
In the refining process, the graphite heating element energising heating that is embedded in the furnace lining outside is adopted in the temperature raising of silicon liquid and heat preserving mode, aided in the plasma gun heating simultaneously.Plasma gun inserts in the refining chamber from refining furnace top, and silicon liquid surface is heated.
After the refining of silicon liquid is finished, adopt the mode of pushing off the slag casting down antivacuum, the silicon liquid that refining is finished is cast in the directional freeze bag, and slag does not enter in the directional freeze bag, and the directional freeze bag is admitted to and carries out directional freeze in the directional solidification furnace.One 5 tons refining furnace docks five 1 ton directional solidification furnace.Directional freeze must be carried out thermal pretreatment before wrapping in and being cast into silicon liquid, and preheating temperature is more than 1500 ℃.
The directional freeze process comprises vacuum outgas processing and two steps of silicon liquid, directional solidification.After the directional freeze bag of silicon liquid of will packing into is sent in the directional solidification furnace, at first carry out high vacuum degassing and handle 2 hours treatment times, vacuum tightness 10
-2～10
-31500 ℃ of Pa, temperature are carried out directional freeze after vacuum outgas is finished dealing with, solidified speed of growth 1mm/ minute.After directional freeze is finished, the orientation bag is transported in the holding furnace, makes the silicon ingot slow cooling, reduce internal stress and hold facility.
In the production, in order to reduce the purification load of silicon, the high-purity silicon ingot after a part is purified returns the silicon material preparatory stage, and mix with pretreated silicon material broken again back, and silicon ingot returns the ratio of handling again and is about 10%.
Silicon ingot after the directional freeze is removed the peel cutting processing, adopt scroll saw or slicing machine that silicon ingot is removed the peel processing, the epidermis of excision silicon ingot, and being mingled with under the enrichment end-grain cutting with silicon ingot after the directional freeze, the cutting clout returns the silicon material preparatory stage and carries out fragmentation and wet processing, carries out melting again.
Obviously, those of ordinary skill in the art can equip with the production method of a kind of high purity polycrystalline silicon of the present invention and the production that utilizes this production method to produce high purity polycrystalline silicon, constitutes various types of method for preparing polysilicon and produces equipment.
The foregoing description is only for the usefulness that the present invention is described; and be not to be limitation of the present invention; without departing from the present invention; the those of ordinary skill in relevant technologies field can also be made various variations and modification; therefore all technical schemes that are equal to also should belong to category of the present invention, and scope of patent protection of the present invention is limited by each claim.
Claims (15)
1, a kind of production method of high purity polycrystalline silicon, described production method comprises the steps: that the preparation of silicon material, melting package, the melting of silicon material, slagging-off, molten silicon refining, silicon liquid pushing off the slag casting, the vacuum outgas of silicon liquid and directional freeze, silicon ingot come out of the stove and remove the peel cutting, wherein, employed silicon material is a metallurgical grade reduction silicon in the described silicon material preparation step, and the type of heating that adopts in described silicon material melting step comprises the chemical combustion heating.
2, production method according to claim 1 is characterized in that: also comprised melting bag pre-heating step before described melting package step, the temperature of described melting bag preheating is 1000～1600 ℃.
3, production method according to claim 1, it is characterized in that: described silicon material melting step comprises that also adding light alkaline oxide compound 2～40%, carbonate 0～35%, fusing assistant 1～25% generate the step of low melting point, low density, low-viscosity silicate sludge with the silicon oxide with fusion process formation, wherein said light alkaline oxide compound comprises magnesium oxide, calcium oxide or barium oxide, and described fusing assistant is a fluorite.
4, production method according to claim 1, it is characterized in that: the type of heating that adopts in described silicon material melting step also comprises electrically heated, described electrically heated comprises induction heating, resistive heating or electron beam heating, and described chemical combustion adds the fuel of pining for that blows coal oxygen burning heating and comprises heavy oil, coal dust, coal gas or Sweet natural gas.
5, according to claim 3 or 4 described production methods, it is characterized in that: described silicon material melting step is carried out under antivacuum or subnormal ambient.
6, production method according to claim 1 is characterized in that: after described silicon material melting step is finished and reached 1430～1700 ℃, adopt slag scraper to be removed the gred in silicon liquid surface.
7, production method according to claim 1, it is characterized in that: described molten silicon refinement step comprises the refining purification process, this refining purification process may further comprise the steps: be blown into argon gas, oxygen, water vapour gas mixture successively in silicon liquid, wherein to account for volume percent be 1～15% for oxygen and water vapour sum; Argon gas, oxygen mixture, wherein to account for volume percent be 1～15% to oxygen; Argon gas, hydrogen mixed gas, wherein to account for volume percent be 1～10% to hydrogen; Described refining purification process carries out under rough vacuum, and adopts vapor jet pump that the refining furnace that uses in the refining purification process is vacuumized.
8, production method according to claim 7, it is characterized in that: adding total amount in described refining process is light alkaline oxide compound, carbonate, fusing assistant and the silicon-dioxide of silicon liquid weight 0.1～10%, weight part between them close be that the light alkaline oxide compound accounts for 5～35%, carbonate 1～35%, fusing assistant 5～20%, silica 1～10%, wherein said light alkaline oxide compound comprises magnesium oxide and/or calcium oxide, and described fusing assistant is a fluorite.
9, production method according to claim 7, it is characterized in that: described refining process comprises electrically heated and/or plasma gun heating to the temperature raising and the heat preserving mode of silicon liquid, outside preembedded graphite or the silicon-carbon piece resistance heating element energising heating of described electrically heated for adopting the refining ladle-lining, described plasma gun is heated to be plasma gun is inserted in the refining chamber from refining furnace top, and silicon liquid surface is heated.
10, production method according to claim 1, it is characterized in that: the silicon liquid that refining is finished is cast in the directional freeze bag, and send into and carry out directional freeze in the directional solidification furnace, described directional freeze is carried out thermal pretreatment before wrapping in and being cast into silicon liquid, and preheating temperature is 1400～1600 ℃.
11, production method according to claim 10 is characterized in that: after the directional freeze bag of the described silicon liquid of packing into is admitted in the directional solidification furnace, at first carry out silicon liquid vacuum outgas treatment step, the treatment time is that 0.5～10 hour, vacuum tightness are 10
-2～10
-3Pa, temperature are 1450～1600 ℃; Carry out the directional freeze step then, solidifying the speed of growth is 2～60mm/ hour.
12, production method according to claim 1, it is characterized in that: also comprise with the silicon ingot after the directional freeze partly return the silicon material preparatory stage, again carry out fragmentation and with pretreated silicon material blended step, it is 5～30% that silicon ingot returns the ratio of carrying out melting again.
13, production method according to claim 1 is characterized in that: the silicon ingot after the directional freeze is removed the peel cutting, and will cut clout and return the silicon material preparatory stage and carry out fragmentation and wet processing, carry out melting again.
14, a kind of production equipment that utilizes the described production method of claim 1-13 to produce high purity polycrystalline silicon, it is characterized in that: comprise the pack arrangement that is used for melting bag or refining bag identical more than at least three, one of them bag is used for smelting operation, a bag is used for refining operation, and a bag is used for repairing, preheating or loading operation.
15, production equipment according to claim 14, it is characterized in that: also comprise directional solidification furnace and a refining furnace coupling more than at least two, carry out directional freeze so that the silicon liquid that a bag refining is finished is cast into respectively in the described directional solidification furnace more than two.
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| CN102021645A (en) * | 2010-12-28 | 2011-04-20 | 哈尔滨工业大学 | Method for preparing polycrystalline silicon ingot with directional solidification microstructure |
| CN102712482A (en) * | 2010-02-09 | 2012-10-03 | 金子恭二郎 | Silicon vacuum melting method |
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