CN103466626B - A kind of production method of polysilicon - Google Patents
A kind of production method of polysilicon Download PDFInfo
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- CN103466626B CN103466626B CN201210188467.4A CN201210188467A CN103466626B CN 103466626 B CN103466626 B CN 103466626B CN 201210188467 A CN201210188467 A CN 201210188467A CN 103466626 B CN103466626 B CN 103466626B
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- trichlorosilane
- silicon tetrachloride
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Abstract
The production method that the invention provides a kind of polysilicon is that silicon ore and chlorine or hydrogenchloride, under reductive agent effect, chlorination reaction occurs, and obtains silicon tetrachloride; Described silicon tetrachloride is carried out hydrogenation, obtains trichlorosilane; By described trichlorosilane reduction, obtain polysilicon.The present invention directly makes silicon ore and chlorine or hydrogenchloride, under reductive agent effect, chlorination reaction occur, and obtains silicon tetrachloride; Described silicon tetrachloride is carried out hydrogenation and obtains trichlorosilane; By described trichlorosilane reduction, obtain polysilicon.First, direct in the present invention is that polysilicon prepared by raw material with silicon ore, without the need to preparing polysilicon again after quartz sand preparation is become industrial silicon by metallic silicon smelting operation, avoid the smelting industrial silicon operation of high energy consumption, because this reducing the energy consumption of whole method for preparing polysilicon.Secondly, operation of the present invention is few, work simplification, and all right recycle of tail gas that each operation produces, cost-saving.
Description
Technical field
The present invention relates to semiconductor applications, particularly the production method of polysilicon.
Background technology
Sun power is a kind of green energy resource, makes the exploitation of sun power become inexorable trend with the green new policies thought that " low-carbon (LC) " is feature.Polysilicon is as being the basic material of electric energy by solar energy converting, and its production technique is in continuous change, and production technology is gradually towards the future development of environmental protection, low power consuming.
The complex manufacturing of polysilicon, initial people mainly adopt metallurgy method, high-purity carbon hot reducing method or Solid State Electrotransport method.But because the product purity utilizing the methods such as metallurgy method, high-purity carbon hot reducing method and Solid State Electrotransport method to produce is low, energy consumption is high, waste of raw materials is large, so always can not enter into the production of mass-producing.
Current industrialized method for preparing polysilicon mainly contains silane thermal decomposition process and Siemens Method.Siemens Method is also called trichlorosilane gas phase hydrogen reduction method, and its principle is exactly reduce high-purity trichlorosilane by High Purity Hydrogen on the HIGH-PURITY SILICON core of about 1100 DEG C, generates polysilicon deposition on silicon core.The polysilicon purity that Siemens Method is produced meets the requirement of vertical pulling and Qu Rong completely, so become conventional production technology.Improved Siemens is the production of polysilicon technology developing formation on the basis of traditional Siemens process, possesses energy-conservation, consumption reduction simultaneously, recycles in production process a large amount of H supervened
2, HCl, SiCl
4deng the process matched therewith of by product and a large amount of by-product heat energy, the complete closed cycle of production-line technique technology and equipment system, quality product is high, and performance is more stable.Most producer all adopts improved Siemens to produce polysilicon in the world at present.
Improved Siemens schema is see Fig. 1, and its concrete technology is:
(I) hydrogen and hcl reaction, synthesising hydrogen, reaction formula is: H
2+ C1
2→ 2HCl.
(II) quartz sand smelting is purified to 98%, and generates industrial silicon by smelting.Chemical equation is: SiO
2+ C → Si+CO
2↑.
(III) described industrial silicon purity is lower, must purify further.Industrial silicon is pulverized rear and anhydrous hydrogen chloride Reactive Synthesis trichlorosilane, and reaction formula is: Si+HCl → SiHCl
3.The tail gas that reaction generates is the gaseous mixture of hydrogen, hydrogenchloride, trichlorosilane, silicon tetrachloride, silicon.
The tail gas that above-mentioned trichlorosilane building-up reactions produces obtains silica flour through purifying further, being separated, filter; Condensation obtains trichlorosilane and silicon tetrachloride, and after multistage rectification is purified, high-purity trichlorosilane enters trichlorosilane reduction operation and prepares polysilicon, and high-purity silicon tetrachloride enters hydrogenation process; Hydrogen is back to hydrogenation of silicon tetrachloride reaction; Hydrogenchloride is back to trichlorosilane building-up reactions again by absorption, rectifying, condensation, storage and gasification.The non-condensable gas produced in above tail gas separation operation and resistates are waste gas raffinate, carry out three-protection design.
(IV) trichlorosilane reduction adopts high temperature reduction technique, the HIGH-PURITY SILICON core of about 1100 DEG C reduces trichlorosilane by High Purity Hydrogen, generates polysilicon deposition on silicon core.The equation of chemical reaction is: SiHCl
3+ H
2→ Si+3HCl.Be separated reduction tail gas, condensation obtains trichlorosilane and silicon tetrachloride, and after multistage rectification is purified, the trichlorosilane obtained enters trichlorosilane reduction operation and prepares polysilicon, and the silicon tetrachloride obtained enters hydrogenation process.Be separated the hydrogen obtained and be back to hydrogenation of silicon tetrachloride reaction; Be separated the hydrogenchloride obtained to be reacted for hydrogenation of silicon tetrachloride by absorption, rectifying, condensation, storage and gasification.The non-condensable gas produced in above tail gas separation operation and resistates are waste gas raffinate, carry out three-protection design.
(V) hydrogenation of silicon tetrachloride generates trichlorosilane, is back to trichlorosilane reduction operation.Be separated hydrogenated tail gas, condensation obtains trichlorosilane and silicon tetrachloride, and after multistage rectification is purified, the trichlorosilane obtained enters trichlorosilane reduction operation and prepares polysilicon, and the silicon tetrachloride obtained enters hydrogenation process.Be separated the hydrogen obtained and be back to hydrogenation of silicon tetrachloride reaction; Be separated the hydrogenchloride obtained and be back to hydrogenation of silicon tetrachloride reaction again by absorption, rectifying, condensation, storage and gasification.The non-condensable gas produced in above tail gas separation operation and resistates are waste gas raffinate, carry out three-protection design.
But first through metallic silicon smelting operation, quartz sand preparation must be become industrial silicon in improved Siemens, be then that polysilicon prepared by raw material with industrial silicon.The energy needed due to smelting industrial silicon operation is higher, and is that polysilicon process complexity prepared by raw material with industrial silicon, and therefore the energy consumption of improved Siemens is high, cost is high.
Summary of the invention
It is low, cost-saving that the technical problem to be solved in the present invention is to provide a kind of polysilicon production process energy consumption.
The invention discloses a kind of production method of polysilicon, comprise the following steps:
(A) there is chlorination reaction in silicon ore and chlorine or hydrogenchloride under reductive agent effect, obtains silicon tetrachloride;
(B) silicon tetrachloride that described step (A) obtains is carried out hydrogenation, obtain trichlorosilane;
(C) by the trichlorosilane reduction that described step (B) obtains, polysilicon is obtained.
Preferably, described step (A) is specially:
There is chlorination reaction in silicon ore and chlorine or hydrogenchloride, obtain the tail gas comprising silicon tetrachloride and chlorine or hydrogenchloride under reductive agent effect, described chlorine or hydrogenchloride reclaimed.
Preferably, in described step (A), the SiO of described silicon ore
2content is greater than 60%.
Preferably, in described step (A), described reductive agent is charcoal, carbon or refinery coke.
Preferably, in described step (A), the mol ratio of described silicon ore and reductive agent is 0.1 ~ 5: 1.
Preferably, in described step (A), the purity of described chlorine or hydrogenchloride is greater than 99.9%.
Preferably, described steps A) in, the temperature of described chlorination reaction is 700 DEG C ~ 1500 DEG C, and the pressure of described chlorination reaction is 1 ~ 3MPa.
Preferably, described step (B) is specially:
The silicon tetrachloride obtained in described step (A) is carried out hydrogenation, obtains the tail gas comprising trichlorosilane and silicon tetrachloride, described silicon tetrachloride is reclaimed.
Preferably, in described step (B), described hydrogenation is cold hydrogenation, hot hydrogenation or chlorine hydrogenation.
Preferably, in described step (C), the temperature of described reduction is 1150 DEG C ~ 1250 DEG C.
Compared with prior art, the present invention directly makes silicon ore and chlorine or hydrogenchloride, under reductive agent effect, chlorination reaction occur, and obtains silicon tetrachloride; Described silicon tetrachloride is carried out hydrogenation and obtains trichlorosilane; By described trichlorosilane reduction, obtain polysilicon.First, direct in the present invention is that polysilicon prepared by raw material with silicon ore, without the need to preparing polysilicon again after quartz sand preparation is become industrial silicon by metallic silicon smelting operation, avoid the smelting industrial silicon operation of high energy consumption, because this reducing the energy consumption of whole method for preparing polysilicon.Secondly, operation of the present invention is few, work simplification, and all right recycle of tail gas that each operation produces, cost-saving.
Accompanying drawing explanation
Fig. 1 is the schema of improved Siemens;
Fig. 2 is the schema of the production method of polysilicon of the present invention.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The embodiment of the invention discloses a kind of method for preparing polysilicon, comprise the following steps:
(A) there is chlorination reaction in silicon ore and chlorine or hydrogenchloride under reductive agent effect, obtains silicon tetrachloride;
(B) silicon tetrachloride that described step (A) obtains is carried out hydrogenation, obtain trichlorosilane;
(C) by the trichlorosilane reduction that described step (B) obtains, polysilicon is obtained.
The present invention for raw material with silicon ore, chlorine or hydrogenchloride, makes silicon ore and chlorine or hydrogenchloride, under reductive agent effect, chlorination reaction occur, obtains silicon tetrachloride.Described silicon ore can be quartz sand, quartzite or natural quartz ore deposit, and described silicon ore is preferably SiO
2the silicon ore that content is greater than 60%; The form of the present invention to silicon ore is not particularly limited, and in order to ensure to react completely, preferably have physical structure that is fine, amorphous or open grain, its specific surface area is preferably greater than 3m
2/ g, its particle diameter is preferably 0.1 ~ 5mm, and water content is less than 1wt%.The purity of the present invention to described chlorine or hydrogenchloride is not particularly limited, and is preferably greater than 99.9%.The present invention is not particularly limited for described reductive agent, is preferably charcoal, carbon or refinery coke; The mol ratio of described silicon ore and reductive agent is preferably 0.1 ~ 5: 1, is more preferably 2 ~ 4: 1.
The temperature of described chlorination reaction is preferably 700 DEG C ~ 1500 DEG C, is more preferably 1000 DEG C ~ 1300 DEG C; The pressure of described chlorination reaction can be pressure-fired or mesohigh, is preferably 1 ~ 3MPa, is more preferably 1.5 ~ 2.5MPa.
After described chlorination reaction, not only comprise the silicon tetrachloride be obtained by reacting in the tail gas obtained and have neither part nor lot in chlorine or the hydrogenchloride of reaction, also comprise other non-condensable gas and resistates, as metal chloride, carbon monoxide, water etc.The present invention is separated described tail gas, obtains silicon tetrachloride.The present invention is not particularly limited tail gas separation method, carries out according to mode well known to those skilled in the art, can by tail gas through a series of compression and cooling, silicon tetrachloride and chlorine or HCl separation is come.The hydrogenation of silicon tetrachloride that described silicon tetrachloride can enter next step reacts; In order to cost-saving, the present invention more preferably has neither part nor lot in the chlorine of reaction or the recovery of hydrogenchloride by described.The chlorination reaction of silicon ore in step (A) can be reused for after described chlorine or hydrogenchloride reclaim, also separately can be used as him.Other non-condensable gas and resistates process according to method well known to those skilled in the art as the three wastes.
After obtaining silicon tetrachloride, described silicon tetrachloride is carried out hydrogenation by the present invention, obtains trichlorosilane.
The mode of the present invention to described hydrogenation is not particularly limited, and carries out according to mode well known to those skilled in the art, can be cold hydrogenation, hot hydrogenation or chlorine hydrogenation etc.To be silicon tetrachloride carry out hydrogenation under the effect of hydrogen and elementary silicon in described cold hydrogenation, and concrete reaction formula is: 3SiCl
4+ H
2+ Si → 4SiHCl
3;
Described hot hydrogenation is silicon tetrachloride hydrogenation under the effect of hydrogen, and concrete reaction formula is: SiCl
4+ H
2→ SiHCl
3+ HCl;
Described chlorine hydrogenation is silicon tetrachloride hydrogenation under the effect of hydrogenchloride elementary silicon, and concrete reaction formula is: SiCl
4+ 2HCl+Si → 2SiHCl
3.
The parameter of the present invention to described hydrogenation process is not particularly limited, and those skilled in the art can adjust according to the hydrogenation process selected.
The tail gas of described hydrogenation, except comprising trichlorosilane, also comprises the silicon tetrachloride be not hydrogenated, different according to hydrogenation mode, and the tail gas of described hydrogenation also contains other compositions, as hydrogenchloride, hydrogen, non-condensable gas and resistates etc.In order to make next step trichlorosilane reduction carry out smoothly, described tail gas is preferably separated by the present invention, and described separation can be carried out according to mode well known to those skilled in the art.
When selecting cold hydrogenation, the present invention can by the tail gas after hydrogenation through series cooling, non-condensable gas and resistates etc. and trichlorosilane and silicon tetrachloride etc. are separated, described non-condensable gas comprises hydrogen and other non-condensable gases, in order to cost-saving, hydrogen is reclaimed, after recovery, can be used for silicon ore chlorination reaction, also can react with hydrogenation of silicon tetrachloride, also can separately for he uses; Other non-condensable gas and resistates process according to method well known to those skilled in the art as the three wastes.After the present invention obtains comprising the chlorosilane of trichlorosilane and silicon tetrachloride, described chlorosilane is preferably carried out rectification and purification by the present invention, trichlorosilane can be separated with silicon tetrachloride.The device of the present invention to rectification and purification is not particularly limited, and can select rectifying tower, and the pressure of described rectifying tower is preferably 0.3 ~ 0.7MPa, temperature is preferably 60 ~ 115 DEG C.The give up number of times of rectification and purification of the present invention is also not particularly limited, and carries out according to mode well known to those skilled in the art.In order to ensure the polysilicon purity of final preparation, the purity of the trichlorosilane therefore obtained through rectification and purification is preferably greater than 6N.Described trichlorosilane enters next step trichlorosilane reduction, and silicon tetrachloride rectification and purification obtained reclaims, and can be reused for hydrogenation of silicon tetrachloride reaction again, also can be separately his use.
When selecting hot hydrogenation, tail gas after hydrogenation can be entered series cooling by the present invention, non-condensable gas and resistates etc. and hydrogenchloride, trichlorosilane and silicon tetrachloride etc. are separated, described non-condensable gas comprises hydrogen and other non-condensable gases, in order to cost-saving, hydrogen is reclaimed, after recovery, can be used for silicon ore chlorination reaction, also can react with hydrogenation of silicon tetrachloride, also can separately for he uses; Other non-condensable gas and resistates process according to method well known to those skilled in the art as the three wastes.Again the mixture comprising hydrogenchloride, trichlorosilane and silicon tetrachloride is heated, hydrogenchloride is separated with tetrachloro silicane with trichlorosilicane; Described hydrogenchloride preferably reclaims by the present invention, is reused for silicon ore chlorination reaction and hydrogenation of silicon tetrachloride reaction; After obtaining comprising the chlorosilane of trichlorosilane and silicon tetrachloride, described chlorosilane is preferably carried out rectification and purification by the present invention, trichlorosilane can be separated with silicon tetrachloride.The device of the present invention to rectification and purification is not particularly limited, and can select rectifying tower, and the pressure of described rectifying tower is preferably 0.3 ~ 0.7MPa, temperature is preferably 60 ~ 115 DEG C.The give up number of times of rectification and purification of the present invention is also not particularly limited, and carries out according to mode well known to those skilled in the art.In order to ensure the polysilicon purity of final preparation, the purity of the trichlorosilane therefore obtained through rectification and purification is preferably greater than 6N.Described trichlorosilane enters next step trichlorosilane reduction, and silicon tetrachloride rectification and purification obtained reclaims, and can be reused for hydrogenation of silicon tetrachloride reaction again, also can be separately his use.
When selecting chlorine hydrogenation, the present invention can by the tail gas after hydrogenation through series cooling, non-condensable gas and resistates etc. and hydrogenchloride, trichlorosilane and silicon tetrachloride etc. are separated, other non-condensable gas and resistates process according to method well known to those skilled in the art as the three wastes; Again the mixture comprising hydrogenchloride, trichlorosilane and silicon tetrachloride is heated, hydrogenchloride is separated with tetrachloro silicane with trichlorosilicane; Described hydrogenchloride preferably reclaims by the present invention, is reused for silicon ore chlorination reaction and hydrogenation of silicon tetrachloride reaction; After obtaining comprising the chlorosilane of trichlorosilane and silicon tetrachloride, described chlorosilane is preferably carried out rectification and purification by the present invention, trichlorosilane can be separated with silicon tetrachloride.The device of the present invention to rectification and purification is not particularly limited, and can select rectifying tower, and the pressure of described rectifying tower is preferably 0.3 ~ 0.7MPa, temperature is preferably 60 ~ 115 DEG C.The give up number of times of rectification and purification of the present invention is also not particularly limited, and carries out according to mode well known to those skilled in the art.In order to ensure the polysilicon purity of final preparation, the purity of the trichlorosilane therefore obtained through rectification and purification is preferably greater than 6N.Described trichlorosilane enters next step trichlorosilane reduction, and silicon tetrachloride rectification and purification obtained reclaims, and can be reused for hydrogenation of silicon tetrachloride reaction again, also can be separately his use.
After the present invention obtains trichlorosilane, by described trichlorosilane reduction, obtain polysilicon.Described reduction is specially to reduce deposition and generates polysilicon in hydrogen atmosphere by described trichlorosilane.The mol ratio of described trichlorosilane and hydrogen is preferably 0.2 ~ 1: 1, is more preferably 0.5 ~ 0.8: 1.The present invention does not have particular requirement the time to trichlorosilane reduction, and polysilicon grows on silicon core, and silicon core diameter grows to 150 ~ 220 millimeters.The equipment of the present invention to trichlorosilane reduction does not have particular requirement, adopts equipment well known to those skilled in the art, can adopt polycrystalline silicon reducing furnace, and in described polycrystalline silicon reducing furnace, silicon core upper epidermis temperature is preferably 1150 DEG C ~ 1250 DEG C.After described trichlorosilane reduction, preferably also comprise tail gas recycle, described tail gas comprises Multiple components, as trichlorosilane, hydrogen, hydrogenchloride, silicon tetrachloride, dichlorosilane, other non-condensable gases and resistates, the present invention is not particularly limited described method for recovering tail gas, can carry out according to mode well known to those skilled in the art, as can by as described in tail gas through series cooling after, by non-condensable gas and resistates etc. and hydrogenchloride, trichlorosilane and silicon tetrachloride etc. are separated, described non-condensable gas comprises hydrogen and other non-condensable gases, in order to cost-saving, hydrogen is reclaimed, silicon ore chlorination reaction is can be used for after recovery, also can react with hydrogenation of silicon tetrachloride, also can separately for he uses, other non-condensable gas and resistates process according to method well known to those skilled in the art as the three wastes.Again the mixture comprising hydrogenchloride, dichlorosilane, trichlorosilane and silicon tetrachloride is heated, hydrogenchloride is separated with tetrachloro silicane with trichlorosilicane; Described hydrogenchloride preferably reclaims by the present invention, is reused for silicon ore chlorination reaction and hydrogenation of silicon tetrachloride reaction; After obtaining comprising the chlorosilane of dichlorosilane, trichlorosilane and silicon tetrachloride, described chlorosilane is preferably carried out rectification and purification by the present invention, dichlorosilane, trichlorosilane can be separated with silicon tetrachloride.Reclaiming being separated the described trichlorosilane obtained, can trichlorosilane reduction be reused for; Described silicon tetrachloride is reclaimed, after recovery, may be used for hydrogenation of silicon tetrachloride reaction, also can separately for he uses; Can carry out anti-disproportionation with silicon tetrachloride further to being separated the described dichlorosilane obtained, obtain chlorosilane, described chlorosilane can carry out rectification and purification according to technique scheme to it, obtains silicon tetrachloride and trichlorosilane.
The schema of method for preparing polysilicon of the present invention is see Fig. 2, and silicon ore and chlorine or hydrogenchloride, under reductive agent effect, chlorination reaction occurs, and is the synthesis of (A) silicon tetrachloride; Be separated chlorinated exhaust, obtain silicon tetrachloride, chlorine or hydrogenchloride and waste gas raffinate, described silicon tetrachloride enters the reaction of next step hydrogenation of silicon tetrachloride, described chlorine or hydrogenchloride is reclaimed, is reused for chlorination reaction; Described waste gas raffinate enters three-protection design.
The silicon tetrachloride obtained is carried out hydrogenation, is (B) hydrogenation of silicon tetrachloride, obtain the tail gas containing trichlorosilane, silicon tetrachloride and hydrogenchloride or hydrogen, hydrogenchloride or hydrogen are separated with chlorosilane, described chlorosilane backboard trichlorosilane and silicon tetrachloride; Hydrogenation of silicon tetrachloride is reused for after being separated the hydrogenchloride or hydrogen recovery obtained; Again by chlorosilane rectification and purification, trichlorosilane is separated with silicon tetrachloride, described silicon tetrachloride is reused for hydrogenation of silicon tetrachloride after reclaiming.Also containing waste gas raffinate in described tail gas, enter three-protection design.
The trichlorosilane obtained is reduced, obtains polysilicon, be (C) trichlorosilane reduction.After trichlorosilane reduces, be separated reacted tail gas, obtain chlorosilane, hydrogen, hydrogenchloride and waste gas raffinate respectively, described chlorosilane comprises trichlorosilane, silicon tetrachloride and dichlorosilane.Again trichlorosilane reduction or hydrogenation of silicon tetrachloride is applied to after hydrogen recovery; Hydrogenchloride is reused for hydrogenation of silicon tetrachloride after reclaiming; Waste gas raffinate, enters three-protection design.Again rectification and purification is carried out to chlorosilane, trichlorosilane, silicon tetrachloride and dichlorosilane are separated, trichlorosilane is reused for trichlorosilane reduction after reclaiming, silicon tetrachloride is reused for hydrogenation of silicon tetrachloride after reclaiming, after dichlorosilane reclaims and silicon tetrachloride carry out anti-disproportionation reaction and obtain chlorosilane, described chlorosilane can carry out rectification and purification according to technique scheme to it, obtains silicon tetrachloride and trichlorosilane.
Compared with prior art, the present invention directly makes silicon ore and chlorine or hydrogenchloride, under reductive agent effect, chlorination reaction occur, and obtains silicon tetrachloride; Described silicon tetrachloride is carried out hydrogenation and obtains trichlorosilane; By described trichlorosilane reduction, obtain polysilicon.First, direct in the present invention is that polysilicon prepared by raw material with silicon ore, without the need to preparing polysilicon again after quartz sand preparation is become industrial silicon by metallic silicon smelting operation, avoid the smelting industrial silicon operation of high energy consumption, because this reducing the energy consumption of whole method for preparing polysilicon.Secondly, operation of the present invention is few, work simplification, all right recycle of the tail gas that each operation produces, cost-saving.
In order to understand the present invention further, be described method for preparing polysilicon provided by the invention below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Silicon ore and 3 times of refinery cokes to silicon ore molar weight are added in reactor, is heated to about 1200 DEG C, after passing into emptying three times of argon gas, switch to chlorine to pass into reactor, in reaction process, keep reaction system to be slight positive pressure state.Detect tail gas to learn in tail gas containing a large amount of silicon tetrachloride, other metal chloride, CO, Cl
2deng;
By tail gas through a series of compression and cooling, silicon tetrachloride is separated, chlorine gets back to chlorination reaction, and other non-condensable gas and resistates go three-protection design operation.
Be under the condition of 1200 DEG C in temperature, in silicon tetrachloride, pass into H
2, be trichlorosilane by hydrogenation of silicon tetrachloride, by the tail gas after hydrogenation by after a series of cooling, the hydrogenchloride in tail gas and chlorosilane condensate are separated, non-condensable gas is mainly hydrogen; After again the chlorosilane being dissolved with hydrogenchloride being heated, hydrogenchloride is resolved, thus chlorosilane and HCl separation are opened; Then the chlorosilane after parsing is gone rectification and purification operation, hydrogenchloride gets back to hydrogenation apparatus, and hydrogen removes rectifying or hydrogenation process after purifying, and the recovery completing each material uses.
Ensure that Rectification column pressure is under 0.5MPa, temperature are 90 DEG C of conditions, through 3 repeated isolation, isolate trichlorosilane and be purified to 6N from chlorosilane, then to trichlorosilane reduction operation, hydrogenation process got back to by silicon tetrachloride.
In polycrystalline silicon reducing furnace, make high-purity SiHCl
3at H
2in atmosphere, reduction deposition generates polysilicon, SiHCl
3with H
2mol ratio be 0.5: 1; Described polycrystalline silicon reducing furnace is multipair excellent reduction reactor, adopts silicon core to be electrode, and with electrically heated silicon core, ensure that silicon rod upper epidermis temperature is 1200 DEG C, polysilicon grows on silicon core, and silicon core diameter grows to 150 ~ 220 millimeters.The same Н of remaining trichlorosilane
2, Н С l, Si Н С 1
3, SiCl
4discharge as tail gas from reaction vessel together, after being separated by reduction device for recovering tail gas, getting back in each corresponding operation and recycle.
Embodiment 2
Silicon ore and 4 times of refinery cokes to silicon ore molar weight are added in reactor, is heated to about 1300 DEG C, after passing into emptying three times of argon gas, switch to chlorine to pass into reactor, in reaction process, keep reaction system to be slight positive pressure state.Detect tail gas to learn in tail gas containing a large amount of silicon tetrachloride, other metal chloride, CO, Cl
2deng;
By tail gas through a series of compression and cooling, silicon tetrachloride is separated, chlorine gets back to chlorination reaction, and other non-condensable gas and resistates go three-protection design operation.
Be under the condition of 550 DEG C in temperature, in silicon tetrachloride, pass into H
2(reaction formula is 3SiCl with 1/3 times of silica flour to silicon tetrachloride mole number
4+ 2H
2+ Si=4SiHCl
3), be trichlorosilane by hydrogenation of silicon tetrachloride, by the tail gas after hydrogenation by after a series of cooling, the hydrogenchloride in tail gas and chlorosilane condensate are separated, non-condensable gas is mainly hydrogen; After again the chlorosilane being dissolved with hydrogenchloride being heated, hydrogenchloride is resolved, thus chlorosilane and HCl separation are opened; Then the chlorosilane after parsing is gone rectification and purification operation, hydrogenchloride gets back to hydrogenation apparatus, and hydrogen removes rectifying or hydrogenation process after purifying, and the recovery completing each material uses.
Ensure that Rectification column pressure is under 0.5MPa, temperature are 90 DEG C of conditions, through 3 repeated isolation, isolate trichlorosilane and be purified to 6N from chlorosilane, then to trichlorosilane reduction operation, hydrogenation process got back to by silicon tetrachloride.
In polycrystalline silicon reducing furnace, make high-purity SiHCl
3at H
2in atmosphere, reduction deposition generates polysilicon, SiHCl
3with H
2mol ratio be 0.5: 1; Described polycrystalline silicon reducing furnace is multipair excellent reduction reactor, adopts silicon core to be electrode, and with electrically heated silicon core, ensure that silicon rod upper epidermis temperature is 1220 DEG C, polysilicon grows on silicon core, and silicon core diameter grows to 150 ~ 220 millimeters.The same Н of remaining trichlorosilane
2, Н С l, Si Н С 1
3, SiCl
4discharge as tail gas from reaction vessel together, after being separated by reduction device for recovering tail gas, getting back in each corresponding operation and recycle.
Embodiment 3
Silicon ore and 2 times of refinery cokes to silicon ore molar weight are added in reactor, is heated to about 900 DEG C, after passing into emptying three times of argon gas, switch to chlorine to pass into reactor, in reaction process, keep reaction system to be slight positive pressure state.Detect tail gas to learn in tail gas containing a large amount of silicon tetrachloride, other metal chloride, CO, Cl
2deng;
By tail gas through a series of compression and cooling, silicon tetrachloride is separated, chlorine gets back to chlorination reaction, and other non-condensable gas and resistates go three-protection design operation.
Be under the condition of 600 DEG C in temperature, in silicon tetrachloride, pass into hydrogen chloride gas and (reaction formula is SiCl with the silica flour of the mole numbers such as silicon tetrachloride
4+ 2HCl+Si=2SiHCl
3), be trichlorosilane by hydrogenation of silicon tetrachloride, by the tail gas after hydrogenation by after a series of cooling, the hydrogenchloride in tail gas and chlorosilane condensate separated; After again the chlorosilane being dissolved with hydrogenchloride being heated, hydrogenchloride is resolved, thus chlorosilane and HCl separation are opened; Then the chlorosilane after parsing is gone rectification and purification operation, hydrogenchloride gets back to hydrogenation apparatus, and the recovery completing each material uses.
Ensure that Rectification column pressure is under 0.5MPa, temperature are 90 DEG C of conditions, through 3 repeated isolation, isolate trichlorosilane and be purified to 6N from chlorosilane, then to trichlorosilane reduction operation, hydrogenation process got back to by silicon tetrachloride.
In polycrystalline silicon reducing furnace, make high-purity SiHCl
3at H
2in atmosphere, reduction deposition generates polysilicon, SiHCl
3with H
2mol ratio be 0.5: 1; Described polycrystalline silicon reducing furnace is multipair excellent reduction reactor, adopts silicon core to be electrode, and with electrically heated silicon core, ensure that silicon rod upper epidermis temperature is 1200 DEG C, polysilicon grows on silicon core, and silicon core diameter grows to 150 ~ 220 millimeters.The same Н of trichlorosilane that unreacted is complete
2, Н С l, Si Н С 1
3, SiCl
4discharge as tail gas from reaction vessel together, after being separated by reduction device for recovering tail gas, getting back in each corresponding operation and recycle.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (6)
1. a production method for polysilicon, comprises the following steps:
(A) there is chlorination reaction in silicon ore and chlorine or hydrogenchloride under reductive agent effect, obtains silicon tetrachloride; The temperature of described chlorination reaction is 700 DEG C ~ 1500 DEG C, and the pressure of described chlorination reaction is 1 ~ 3MPa; Described reductive agent is charcoal; The mol ratio of described silicon ore and reductive agent is 0.1 ~ 5:1; The purity of described chlorine or hydrogenchloride is greater than 99.9%; The SiO of described silicon ore
2content is greater than 60%;
(B) silicon tetrachloride that described step (A) obtains is carried out hydrogenation, obtain trichlorosilane;
(C) by the trichlorosilane reduction that described step (B) obtains, polysilicon is obtained.
2. production method according to claim 1, is characterized in that, described step (A) is specially:
There is chlorination reaction in silicon ore and chlorine or hydrogenchloride, obtain the tail gas comprising silicon tetrachloride and chlorine or hydrogenchloride under reductive agent effect, described chlorine or hydrogenchloride reclaimed.
3. production method according to claim 1, is characterized in that, in described step (A), described reductive agent is refinery coke.
4. production method according to claim 1, is characterized in that, described step (B) is specially:
The silicon tetrachloride obtained in described step (A) is carried out hydrogenation, obtains the tail gas comprising trichlorosilane and silicon tetrachloride, described silicon tetrachloride is reclaimed.
5. production method according to claim 1, is characterized in that, in described step (B), described hydrogenation is cold hydrogenation, hot hydrogenation or chlorine hydrogenation.
6. production method according to claim 1, is characterized in that, in described step (C), the temperature of described reduction is 1150 DEG C ~ 1250 DEG C.
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| CN106145120B (en) * | 2015-03-10 | 2018-11-13 | 周正平 | Original system method for recovering tail gas is gone back in a kind of production of polysilicon |
| KR102303581B1 (en) * | 2016-06-23 | 2021-09-16 | 미쓰비시 마테리알 가부시키가이샤 | Polycrystalline silicon rod and manufacturing method thereof |
| CN106629739A (en) * | 2016-12-07 | 2017-05-10 | 安徽爱森能源有限公司 | Method for producing polysilicon for solar panels |
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| CN101186299A (en) * | 2007-09-19 | 2008-05-28 | 宁波杉杉尤利卡太阳能科技发展有限公司 | Technique for producing high purity silicon by fluidized bed device |
| CN102030329A (en) * | 2009-09-29 | 2011-04-27 | 重庆大全新能源有限公司 | Polycrystalline silicon producing device and process |
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| CN102030329A (en) * | 2009-09-29 | 2011-04-27 | 重庆大全新能源有限公司 | Polycrystalline silicon producing device and process |
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