CN103449448B - Equipment for purification trichlorosilane - Google Patents

Equipment for purification trichlorosilane Download PDF

Info

Publication number
CN103449448B
CN103449448B CN201310373760.2A CN201310373760A CN103449448B CN 103449448 B CN103449448 B CN 103449448B CN 201310373760 A CN201310373760 A CN 201310373760A CN 103449448 B CN103449448 B CN 103449448B
Authority
CN
China
Prior art keywords
gas
chlorine
synthetic reaction
trichlorosilane
rectification
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201310373760.2A
Other languages
Chinese (zh)
Other versions
CN103449448A (en
Inventor
万烨
张升学
严大洲
毋克力
肖荣辉
汤传斌
杨永亮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China ENFI Engineering Corp
Original Assignee
China ENFI Engineering Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China ENFI Engineering Corp filed Critical China ENFI Engineering Corp
Priority to CN201310373760.2A priority Critical patent/CN103449448B/en
Publication of CN103449448A publication Critical patent/CN103449448A/en
Application granted granted Critical
Publication of CN103449448B publication Critical patent/CN103449448B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention discloses a kind of equipment for purification trichlorosilane, this equipment is the first rectification purification devices, for trichlorosilane being carried out the first rectification purification process, to obtain purified trichlorosilane and the first distillation residual liquid, wherein said first rectification purification devices includes the first rectifying column of series connection, Second distillation column and the 3rd rectifying column, the rectification temperature of described first rectifying column is 60～100 degrees Celsius, and pressure is 0.2MPa, and reflux ratio is 10～50:1；The rectification temperature of described Second distillation column is 100～140 degrees Celsius, and pressure is 0.5MPa, and reflux ratio is 20～50:1；The rectification temperature of described 3rd rectifying column is 60～80 degrees Celsius, and pressure is 0.2MPa, and reflux ratio is 20～50:1.Utilize this equipment can purification trichlorosilane effectively, and the technique that this equipment relates to is simple, safety, energy-conserving and environment-protective, cost are low, and purified purity of trichlorosilane is high, it is possible to be effective to the production of polysilicon, and the waste liquid produced can continue to utilize.

Description

Equipment for purification trichlorosilane
Technical field
The present invention relates to photovoltaic industry technical field, in particular it relates to preparation is for the equipment of purification trichlorosilane.
Background technology
Solar energy receives the attention in the whole world as a kind of renewable and clean energy resource, utilizes the technology that solar energy resources generates electricity to have been considered to the new energy technology that the current whole world is the most promising.Thus, obtaining swift and violent development at the beginning of 21 century with the photovoltaic industry that solar energy generation technology is core.Polysilicon is as the main raw material(s) of photovoltaic industry, and along with the fast development of photovoltaic industry, its demand is significantly increased.And then, the demand of the primary raw material trichlorosilane producing polysilicon is consequently increased.But, present stage prepares the technique of trichlorosilane, and in its product, impurity is many, and purity of trichlorosilane is relatively low, it is then desired to be further purified.
But, the present stage Processes and apparatus of purification trichlorosilane still haves much room for improvement.
Summary of the invention
It is contemplated that at least solve one of technical problem of existence in prior art.For this, it is an object of the present invention to propose the equipment of the purification trichlorosilane of a kind of low-cost energy-saving environmental protection.
According to an aspect of the present invention, the present invention proposes a kind of equipment for purification trichlorosilane.According to embodiments of the invention, described equipment is the first rectification purification devices, for trichlorosilane being carried out the first rectification purification process, to obtain purified trichlorosilane and the first distillation residual liquid, wherein, the form that described trichlorosilane hydrogenates synthetic reaction product with chlorine provides, described first rectification purification devices includes the first rectifying column of series connection, Second distillation column and the 3rd rectifying column, wherein, each rectifying column is all respectively provided with charging aperture and discharging opening from bottom to top along the axial direction of described rectifying column, the rectification temperature of described first rectifying column is 60～100 degrees Celsius, pressure is 0.2MPa, reflux ratio is 10～50:1；The rectification temperature of described Second distillation column is 100～140 degrees Celsius, and pressure is 0.5MPa, and reflux ratio is 20～50:1；The rectification temperature of described 3rd rectifying column is 60～80 degrees Celsius, and pressure is 0.2MPa, and reflux ratio is 20～50:1.
It is surprisingly found by the inventors that, utilize this equipment can purification trichlorosilane effectively, and the technique that this equipment relates to is simple, safety, energy-conserving and environment-protective, cost are low, and purified purity of trichlorosilane is high, the production of polysilicon can be effective to, and the waste liquid produced can continue to utilize.
It addition, the equipment for purification trichlorosilane according to the above embodiment of the present invention can also have following additional technical characteristic:
According to embodiments of the invention, farther include: chlorine hydrogenation synthetic reaction device, described chlorine hydrogenation synthetic reaction device is connected with described first rectification purification devices, for making silica flour, hydrogen and at least one generation chlorine hydrogenation synthetic reaction selected from hydrogen chloride with Silicon chloride., in order to obtain described chlorine hydrogenation synthetic reaction product and supply to described first rectification purification devices.
According to embodiments of the invention, described chlorine hydrogenation synthetic reaction device is provided with nickel-base catalyst or copper-based catalysts, so that when there is nickel-base catalyst or copper-based catalysts, making to comprise Silicon chloride. and contacting with silica flour with the admixture of gas of hydrogen, described chlorine hydrogenation synthetic reaction occurs.Thereby, it is possible to be effectively improved the efficiency of chlorine hydrogenation synthetic reaction, subsequent step is conducive to carry out.
According to embodiments of the invention, described in comprise in the admixture of gas of Silicon chloride. and hydrogen, the mol ratio of Silicon chloride. and hydrogen is 1:2～5.Thus, the efficiency of chlorine hydrogenation synthetic reaction significantly improves, and is conducive to subsequent step to carry out.
According to embodiments of the invention, described chlorine hydrogenation synthetic reaction is to carry out at the temperature of 500～550 degrees Celsius.
According to embodiments of the invention, described chlorine hydrogenation synthetic reaction is at 500～550 degrees Celsius, carries out when 1.5～3.5MPa.Thus, the efficiency of chlorine hydrogenation synthetic reaction is high, is conducive to subsequent step to carry out.
According to embodiments of the invention, farther including: Liqiud-gas mixing device, described Liqiud-gas mixing device, for silicon tetrachloride liquid being mixed with hydrogen, obtains gas-liquid mixture；Heat-exchange device, described heat-exchange device hydrogenates synthetic reaction device with described Liqiud-gas mixing device and described chlorine respectively and is connected, for utilizing described chlorine hydrogenation synthetic reaction product that described gas-liquid mixture is carried out heat exchange process, in order to obtain through the gas-liquid mixture of preheating and hydrogenate synthetic reaction product through overcooled chlorine；And resistance heater, described resistance heater hydrogenates synthetic reaction device with described heat-exchange device and described chlorine respectively and is connected, for the gas-liquid mixture through preheating is heated, to comprise the admixture of gas of Silicon chloride. and hydrogen described in obtaining, and the described admixture of gas supply comprising Silicon chloride. and hydrogen is hydrogenated synthetic reaction device to described chlorine.Thus, can realize when consuming energy minimum chlorine being hydrogenated the cooling of synthetic reaction product and gas-liquid mixture being preheated simultaneously, and can effectively obtain the admixture of gas comprising Silicon chloride. and hydrogen, hydrogenate synthetic reaction to chlorine and provide raw material for chlorine hydrogenation synthetic reaction in circulation, it is thus possible to effectively realize energy-conserving and environment-protective, reduce the purpose of cost.
According to embodiments of the invention, farther including: dust arrester, described dust arrester is connected with described heat-exchange device, in order to carry out dust removal process by described through overcooled chlorine hydrogenation synthetic reaction product；And first condensing unit, described first condensing unit is connected with described dust arrester and the first rectification purification devices respectively, condense for the chlorine through dust removal process is hydrogenated synthetic reaction product, to be separately recovered hydrogen and chlorosilane liquid produced, described chlorosilane liquid produced comprises trichlorosilane and Silicon chloride., and to described first rectification purification devices, the supply of described chlorosilane liquid produced is used for described first rectification purification process.Thus, after overcooled chlorine hydrogenation synthetic reaction product is by above-mentioned process, chlorosilane liquid produced and hydrogen can be obtained, and the related device of the equipment that chlorosilane liquid produced and hydrogen can be respectively fed to for preparing polysilicon, again recycle, it is thus possible to effectively realize energy-conserving and environment-protective, reduce the purpose of cost.
According to embodiments of the invention, described first condensing unit hydrogenates synthetic reaction device with described chlorine and is connected, for by described hydrogen supply to described chlorine hydrogenation synthetic reaction device.Thereby, it is possible to hydrogen is recycled, hydrogenate the chlorine hydrogenation synthetic reaction carried out in synthetic reaction device for chlorine and raw material, energy-conserving and environment-protective are provided, and production cost can be reduced.
According to embodiments of the invention, the equipment of the present invention farther includes: dismutation reaction device, described dismutation reaction device is connected with described first rectification purification devices, for making described purified trichlorosilane generation dismutation reaction, in order to obtain the dismutation reaction product comprising Silicon chloride. and silane；Second rectification purification devices, described second rectification purification devices is connected with described dismutation reaction device, for described dismutation reaction product is carried out the second rectification purification process, in order to obtain silane gas and Silicon chloride.；And pyrolytic reaction device, described pyrolytic reaction device is connected with described second rectification purification devices, is used for making described silane gas generation pyrolytic reaction, in order to obtain polysilicon.Thus, the purified highly purified trichlorosilane that the present invention obtains can be effective to the production of electronic-grade polycrystalline silicon, thus based on above-mentioned various annexations, the equipment for purification trichlorosilane of the present invention can be effectively formed the equipment for preparing electronic-grade polycrystalline silicon with above-mentioned each device, and this is used for preparing that the equipment production cost of electronic-grade polycrystalline silicon is low, power consumption less, energy-conserving and environment-protective, the polysilicon purity of production is very high.
According to embodiments of the invention, in described dismutation reaction device, described dismutation reaction is at 50～80 degrees Celsius, carries out when 0.2～0.6MPa.Thus, production safety, and power consumption less, production cost is low, dismutation reaction efficiency is high, effective, is conducive to the carrying out of subsequent step.
According to embodiments of the invention, described dismutation reaction device is disproportionation reactor, described disproportionation reactor farther includes: disproportionation reactor body, this internal dismutation reaction space that limits of described disproportionation reactor, and is provided with catalyst layer in described dismutation reaction space；Trichlorosilane charging aperture, described trichlorosilane charging aperture is arranged on the lower section of described catalyst layer, for being fed past the trichlorosilane of purification in described dismutation reaction space；And dismutation reaction product discharge mouth, described dismutation reaction product discharge mouth is arranged on the top of described catalyst layer, discharges described disproportionation reactor for the dismutation reaction product comprising Silicon chloride. and silane that will be formed.Thus, dismutation reaction efficiency is high, effective, and production safety, power consumption less, cost is low, be conducive to the carrying out of subsequent step.
According to embodiments of the invention, described in comprise Silicon chloride. and hydrogen admixture of gas described in Silicon chloride. derive from described dismutation reaction device at least partially.Thus, recycled by the Silicon chloride. in dismutation reaction product such that it is able to realize energy-conserving and environment-protective, reduced the purpose of cost.
According to embodiments of the invention, described second rectification purification devices hydrogenates synthesizer with described chlorine and is connected, in order to the Silicon chloride. obtained in described second rectification purification devices is used for described chlorine hydrogenation synthetic reaction.Thus, the Silicon chloride. in the second rectification purification devices product has been recycled such that it is able to realize energy-conserving and environment-protective, reduced the purpose of cost.
According to embodiments of the invention, described second rectification purification devices is low-temperature fractionating tower, and wherein, the temperature in described low-temperature fractionating tower is-60～-80 degrees Celsius, and pressure is 0.6～1.0MPa, and reflux ratio is 5～20:1.Thus, production safety, and power consumption less, production cost is low, rectification purification efficiency is high, effective, is conducive to the carrying out of subsequent step.
According to embodiments of the invention, farther include vaporization process device, described vaporization process device is connected with described second rectification purification devices and described pyrolytic reaction device respectively, for, before pyrolytic reaction, in advance the silane gas stored in liquid form being vaporized process.Thus, the carrying out of pyrolytic reaction in pyrolytic reaction device is conducive to such that it is able to effectively prepare polysilicon, and cost is low, needing can be few, energy-conserving and environment-protective, and pyrolytic reaction efficiency is high.
According to embodiments of the invention, described pyrolytic reaction device is reduction furnace, is provided with the silicon core carrier as crystal deposition in described reduction furnace.Thus, pyrolytic reaction efficiency is high, effective, and the electronic-grade polycrystalline silicon purity prepared is high.
According to embodiments of the invention, described reduction furnace is bell-jar reduction furnace.Thus, pyrolytic reaction efficiency is high, effective.
According to embodiments of the invention, in described reduction furnace, it is provided with 12,24 or 36 pairs of silicon rods.Thus, adopt silicon core as carrier.Further, according to embodiments of the invention, the cooling jacket consistent with silicon core logarithm in reduction furnace, it is additionally provided with.Thus, be conducive to silane gas checking solution to deposit, prepare high-purity electronic-grade polycrystalline silicon.
According to embodiments of the invention, the temperature in described reduction furnace is 750～900 degrees Celsius, and pressure is 0.15～0.30MPa.Thus, pyrolytic reaction efficiency is high, effective, and reaction safety, and the electronic-grade polycrystalline silicon purity prepared is high.
According to embodiments of the invention, farther including: flash distillation processes device, described flash distillation processes device and is connected with described first rectification purification devices, for described first distillation residual liquid is carried out flash distillation process, in order to obtain Silicon chloride. gas and solid residue；Second condensing unit, described second condensing unit processes device with described flash distillation respectively and described Liqiud-gas mixing device is connected, for described Silicon chloride. gas is carried out condensation process, to obtain silicon tetrachloride liquid, and by the supply of described silicon tetrachloride liquid to described Liqiud-gas mixing device, hydrogenate synthetic reaction for described chlorine；And residue treatment device, described residue treatment device processes device with described flash distillation and is connected, and processes for described solid residue is sequentially carried out alkali liquor hydrolysis neutralisation treatment and filter pressing.Thereby, it is possible to effectively realize the cycling and reutilization of the first distillation residual liquid, thus reaching energy-conserving and environment-protective, reduce the purpose of cost.
According to embodiments of the invention, farther including: the first compressor, described first compressor is connected with described pyrolytic reaction device, for the reduction tail gas of pyrolytic reaction is compressed to pressure be 6.0～10.0MPa；And the 3rd condensing unit, described 3rd condensing unit is connected with described first compressor, described Liqiud-gas mixing device and described vaporization process device, for being-100～-120 degrees Celsius by reduction tail gas condensing to the temperature through overcompression, silane gas is condensed into silane liquid and obtains hydrogen, and by described silane liquid supply to described vaporization process device, by the supply of described hydrogen to described Liqiud-gas mixing device, hydrogenate synthetic reaction for described chlorine.Thereby, it is possible to effectively the reduction tail gas produced in pyrolytic reaction device is processed, it is achieved non-pollution discharge, it is ensured that cleaning produces, and realizing the cycling and reutilization of reduction tail gas, thus reaching energy-conserving and environment-protective, reducing the purpose of cost.
According to embodiments of the invention, farther include: the second compressor, described second compressor for by each device produced containing chlorosilane but the tail gas of non-silane-containing be compressed to pressure be 0.25～0.50MPa；4th condensing unit, described 4th condensing unit is connected with described second compressor and described first rectification purification devices respectively, for by through overcompression containing chlorosilane but the tail gas of non-silane-containing is cooled to temperature is-15～-30 degrees Celsius, to obtain chlorosilane liquid produced and residual gas, and the supply of described chlorosilane liquid produced is used for described first rectification purification process to described first rectification purification devices；Elution device, described elution device is connected with described 4th condensing unit, for described residual gas is carried out drip washing, in order to obtain scrubbed gas and washing water；And drip washing water treatment facilities, described drip washing water treatment facilities is connected with described elution device, is used for utilizing alkali liquor that described washing water is neutralized, and liquid after neutralizing is carried out filter pressing, in order to obtain neutralizing water and filtering residue.Thereby, it is possible to effectively process containing chlorosilane but the tail gas of non-silane-containing produced in each device, it is achieved non-pollution discharge, it is ensured that cleaning produces, and realizing the cycling and reutilization of tail gas, thus reaching energy-conserving and environment-protective, reducing the purpose of cost.
According to embodiments of the invention, by the supply of described neutralization water to described elution device, for described residual gas is carried out drip washing.Thereby, it is possible to neutralization water is circulated utilization, thus reducing production cost, and realize non-pollution discharge, it is ensured that cleaning produces.
It should be noted that relative to prior art, the equipment for purification trichlorosilane of the present invention has the advantage that
1, the whole process system safety and stability related to, technique is simple, it may be achieved.
2, the purity of trichlorosilane that purification obtains is high, cost is low, energy saving technology environmental protection.
3, the equipment for purification trichlorosilane of the present invention can hydrogenate the effectively combination such as synthetic reaction device, dismutation reaction device, the second rectification purification devices and pyrolytic reaction device with aforesaid chlorine, thus constituting the new equipment for preparing electronic-grade polycrystalline silicon, and this equipment being used for preparing electronic-grade polycrystalline silicon can effectively realize trichlorosilane one stage disproportionation being silane gas；Silane gas is easily separated with chlorosilane, and after purification, purity is high, it is possible to reach more than 9N；The silane gas cracking temperature obtained is relatively low, and energy consumption is relatively low, and then produces the less costly of polysilicon；The polysilicon of preparation is electronic-grade polycrystalline silicon, and purity is high, it is possible to reach 9N-11N；Tail gas and the waste residue of discharge all meet environmental requirement, clean production equipment for polysilicon.
The additional aspect of the present invention and advantage will part provide in the following description, and part will become apparent from the description below, or is recognized by the practice of the present invention.
Accompanying drawing explanation
Above-mentioned and/or the additional aspect of the present invention and advantage are from conjunction with will be apparent from easy to understand the accompanying drawings below description to embodiment, wherein:
Fig. 1 shows the schematic flow sheet of the method preparing polysilicon according to an embodiment of the invention；
Fig. 2 shows the schematic flow sheet of the method preparing polysilicon according to an embodiment of the invention；
Fig. 3 shows according to an embodiment of the invention for preparing the structural representation of the equipment of polysilicon；
Fig. 4-Figure 11 respectively illustrates according to an embodiment of the invention for preparing the partial structurtes schematic diagram of the equipment of polysilicon,
Wherein, Fig. 5 shows the first rectification purification devices according to an embodiment of the invention, i.e. the structural representation of the equipment of the purification trichlorosilane of the present invention.
Detailed description of the invention
Being described below in detail embodiments of the invention, the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or has the element of same or like function from start to finish.The embodiment described below with reference to accompanying drawing is illustrative of, and is only used for explaining the present invention, and is not considered as limiting the invention.
In describing the invention, term " axially ", " on ", D score, " top ", the orientation of the instruction such as " end " or position relationship be based on orientation shown in the drawings or position relationship, it is for only for ease of the description present invention rather than requires that the present invention with specific azimuth configuration and operation, therefore must be not considered as limiting the invention.
In the present invention, unless otherwise clearly defined and limited, the term such as term " being connected ", " connection ", " fixing " should be interpreted broadly, for instance, it is possible to it is fixing connection, it is also possible to be removably connect, or connect integratedly；Can be mechanically connected, it is also possible to be electrical connection；Can be joined directly together, it is also possible to be indirectly connected to by intermediary, it is possible to be the connection of two element internals.For the ordinary skill in the art, it is possible to understand above-mentioned term concrete meaning in the present invention as the case may be.
In the present invention, unless otherwise clearly defined and limited, fisrt feature second feature it " on " or D score can include the first and second features and directly contact, it is also possible to include the first and second features and be not directly contact but by the other characterisation contact between them.And, fisrt feature second feature " on ", " top " and " above " include fisrt feature directly over second feature and oblique upper, or be merely representative of fisrt feature level height higher than second feature.Fisrt feature second feature " under ", " lower section " and " below " include fisrt feature immediately below second feature and obliquely downward, or be merely representative of fisrt feature level height less than second feature.
It should be noted that term " first ", " second " are only for descriptive purposes, and it is not intended that indicate or imply relative importance or the implicit quantity indicating indicated technical characteristic.Thus, define " first ", the feature of " second " can express or implicitly include one or more these features.
According to an aspect of the present invention, the present invention proposes a kind of equipment for purification trichlorosilane.According to embodiments of the invention, the equipment for purification trichlorosilane of the present invention is the first rectification purification devices, for trichlorosilane carries out the first rectification purification process, in order to obtain purified trichlorosilane and the first distillation residual liquid.Wherein, the form that described trichlorosilane hydrogenates synthetic reaction product with chlorine provides.According to some concrete examples of the present invention, with reference to Fig. 5, this the first rectification purification devices 2 includes the first rectifying column 21 of series connection, Second distillation column 22 and the 3rd rectifying column 23, wherein, each rectifying column is all respectively provided with charging aperture and discharging opening from bottom to top along the axial direction of described rectifying column, the rectification temperature of described first rectifying column 21 is 60～100 degrees Celsius, and pressure is 0.2MPa, and reflux ratio is 10～50:1；The rectification temperature of described Second distillation column 22 is 100～140 degrees Celsius, and pressure is 0.5MPa, and reflux ratio is 20～50:1；The rectification temperature of described 3rd rectifying column 23 is 60～80 degrees Celsius, and pressure is 0.2MPa, and reflux ratio is 20～50:1.
It is surprisingly found by the inventors that, utilize this equipment can purification trichlorosilane effectively, and the technique that this equipment relates to is simple, safety, energy-conserving and environment-protective, cost are low, and purified purity of trichlorosilane is high, the production of polysilicon can be effective to, and the waste liquid produced can continue to utilize.
In addition, according to embodiments of the invention, with reference to Fig. 3, the equipment 2 for purification trichlorosilane of the present invention may further include: chlorine hydrogenation synthetic reaction device 1, described chlorine hydrogenation synthetic reaction device 1 is connected with described first rectification purification devices 2, for making silica flour, hydrogen and at least one generation chlorine hydrogenation synthetic reaction selected from hydrogen chloride with Silicon chloride., in order to obtain described chlorine hydrogenation synthetic reaction product and supply to described first rectification purification devices 2.
Other embodiments according to the present invention, with reference to Fig. 3, the equipment 2 for purification trichlorosilane of the present invention can further include: dismutation reaction device the 3, second rectification purification devices 4 and pyrolytic reaction device 5.According to embodiments of the invention, dismutation reaction device 3 is connected with above-mentioned first rectification purification devices 2, is used for making described purified trichlorosilane generation dismutation reaction, in order to obtain the dismutation reaction product comprising Silicon chloride. and silane；Second rectification purification devices 4 is connected with dismutation reaction device 3, for described dismutation reaction product is carried out the second rectification purification process, in order to obtain silane gas and Silicon chloride.；Pyrolytic reaction device 5 is connected with the second rectification purification devices 4, is used for making described silane gas generation pyrolytic reaction, in order to obtain polysilicon.
Thus, the purified highly purified trichlorosilane that the present invention obtains can be effective to the production of electronic-grade polycrystalline silicon, and then based on above-mentioned various annexations, the equipment (i.e. the first rectification purification devices) for purification trichlorosilane of the present invention can hydrogenate synthetic reaction device with aforesaid chlorine, dismutation reaction device, second rectification purification devices and pyrolytic reaction device etc. effectively combine, thus constituting a kind of new equipment for preparing electronic-grade polycrystalline silicon, and this to be used for preparing the equipment production cost of electronic-grade polycrystalline silicon low, power consumption is few, energy-conserving and environment-protective, the polysilicon purity produced is very high.
Thus, according to a further aspect in the invention, the invention allows for a kind of equipment for preparing polysilicon.According to embodiments of the invention, with reference to Fig. 3, the equipment for preparing polysilicon of the present invention includes: chlorine hydrogenation synthetic reaction device the 1, first rectification purification devices 2, dismutation reaction device the 3, second rectification purification devices 4 and pyrolytic reaction device 5.According to some embodiments of the invention, described chlorine hydrogenation synthetic reaction device 1 is for making silica flour, hydrogen and at least one generation chlorine hydrogenation synthetic reaction selected from hydrogen chloride with Silicon chloride., in order to obtain the chlorine hydrogenation synthetic reaction product comprising trichlorosilane；Described first rectification purification devices 2 hydrogenates synthetic reaction device 1 with described chlorine and is connected, and carries out the first rectification purification process for the described chlorine comprising trichlorosilane is hydrogenated synthetic reaction product, in order to obtain purified trichlorosilane and the first distillation residual liquid；Described dismutation reaction device 3 is connected with described first rectification purification devices 2, is used for making described purified trichlorosilane generation dismutation reaction, in order to obtain the dismutation reaction product comprising Silicon chloride. and silane；Described second rectification purification devices 4 is connected with described dismutation reaction device 3, for described dismutation reaction product is carried out the second rectification purification process, in order to obtain silane gas and Silicon chloride.；Described pyrolytic reaction device 5 is connected with described second rectification purification devices 4, is used for making described silane gas generation pyrolytic reaction, in order to obtain polysilicon.It is surprisingly found by the inventors that, this equipment is utilized can effectively to prepare electronic-grade polycrystalline silicon, and the technique that this equipment relates to is simple, safety, energy-conserving and environment-protective, cost are low, and the polysilicon purity height produced, produce tail gas and waste residue can meet the requirement of environmental protection, for electronic-grade polycrystalline silicon process for cleanly preparing.
In order to make those skilled in the art that the method for preparing polysilicon of the present invention and applicable equipment thereof are more easily understood, below in conjunction with Fig. 3-Figure 11, overall and local the 26S Proteasome Structure and Function of the equipment for preparing polysilicon of the present invention is described in detail.
Wherein it is desired to illustrate, each accompanying drawing and " STC " specifically described herein refer to Silicon chloride., and " TCS " refers to trichlorosilane.
According to embodiments of the invention, in the chlorine hydrogenation synthetic reaction device 1 shown in Fig. 3, the condition of chlorine hydrogenation synthetic reaction is not particularly limited.Some concrete examples according to the present invention, chlorine hydrogenation synthetic reaction device 1 is provided with nickel-base catalyst or copper-based catalysts, so that when there is nickel-base catalyst or copper-based catalysts, making to comprise Silicon chloride. and contacting with silica flour with the admixture of gas of hydrogen, described chlorine hydrogenation synthetic reaction occurs.Wherein, the chemical reaction related generally to is: 3SiCl4+2H2+Si——4SiHCl3.Thereby, it is possible to be effectively improved the efficiency of chlorine hydrogenation synthetic reaction, subsequent step is conducive to carry out.Wherein, comprise the ratio of Silicon chloride. and hydrogen in the admixture of gas of Silicon chloride. and hydrogen to be not particularly limited.According to embodiments of the invention, described in comprise in the admixture of gas of Silicon chloride. and hydrogen, the mol ratio of Silicon chloride. and hydrogen is 1:2～5.Thus, the efficiency of chlorine hydrogenation synthetic reaction significantly improves, and is conducive to subsequent step to carry out.
According to embodiments of the invention, the temperature and pressure carrying out chlorine hydrogenation synthetic reaction in chlorine hydrogenation synthetic reaction device 1 is not particularly limited, as long as can effectively react, it is thus achieved that comprise the chlorine hydrogenation synthetic reaction product of trichlorosilane.According to some embodiments of the present invention, described chlorine hydrogenation synthetic reaction is to carry out at the temperature of 500～550 degrees Celsius.Other embodiments according to the present invention, described chlorine hydrogenation synthetic reaction is at 500～550 degrees Celsius, carries out when 1.5～3.5MPa.Thus, the efficiency of chlorine hydrogenation synthetic reaction is high, is conducive to subsequent step to carry out.
It addition, the source of the Silicon chloride. adopted in chlorine hydrogenation synthetic reaction device 1 is not particularly limited, it is straightforward to provide, it is also possible to separate from the product of subsequent step or waste liquid and obtain.According to embodiments of the invention, described Silicon chloride. derive from described dismutation reaction device 3 at least partially.Thus, recycled by the Silicon chloride. in dismutation reaction product such that it is able to realize energy-conserving and environment-protective, reduced the purpose of cost.
According to embodiments of the invention, described second rectification purification devices 4 and described chlorine hydrogenate synthesizer 1 and are connected (not shown), in order to the Silicon chloride. obtained in described second rectification purification devices is used for described chlorine hydrogenation synthetic reaction.Thereby, it is possible to Silicon chloride. produced in the second rectification purification devices is circulated utilization such that it is able to realize energy-conserving and environment-protective, reduce the purpose of cost.
According to embodiments of the invention, with reference to Fig. 4, the equipment for preparing polysilicon of the present invention may further include: Liqiud-gas mixing device 6, heat-exchange device 7 and resistance heater 8.According to embodiments of the invention, described Liqiud-gas mixing device 6, for silicon tetrachloride liquid being mixed with hydrogen, obtains gas-liquid mixture；Described heat-exchange device 7 hydrogenates synthetic reaction device 1 with described Liqiud-gas mixing device 6 and described chlorine respectively and is connected, for utilizing described chlorine hydrogenation synthetic reaction product that described gas-liquid mixture is carried out heat exchange process, in order to obtain through the gas-liquid mixture of preheating and hydrogenate synthetic reaction product through overcooled chlorine；Described resistance heater 8 hydrogenates synthetic reaction device 1 with described heat-exchange device 7 and described chlorine respectively and is connected, for the gas-liquid mixture through preheating is heated, to comprise the admixture of gas of Silicon chloride. and hydrogen described in obtaining, and the described admixture of gas supply comprising Silicon chloride. and hydrogen is hydrogenated synthetic reaction device 1 to described chlorine.Thus, can realize when consuming energy minimum chlorine being hydrogenated the cooling of synthetic reaction product and gas-liquid mixture being preheated simultaneously, and can effectively obtain the admixture of gas comprising Silicon chloride. and hydrogen, raw material is provided for chlorine hydrogenation synthetic reaction in following cycle, it is thus possible to effectively realize energy-conserving and environment-protective, reduce the purpose of cost.
According to embodiments of the invention, with reference to Fig. 4, the equipment for preparing polysilicon of the present invention may further include: dust arrester 9 and the first condensing unit 10.According to embodiments of the invention, dust arrester 9 is connected with heat-exchange device 7, in order to carry out dust removal process by described through overcooled chlorine hydrogenation synthetic reaction product；First condensing unit 10 is connected with dust arrester 9 and the first rectification purification devices 2 respectively, condense for the chlorine through dust removal process is hydrogenated synthetic reaction product, to be separately recovered hydrogen and chlorosilane liquid produced, described chlorosilane liquid produced comprises trichlorosilane and Silicon chloride., and to described first rectification purification devices 2, the supply of described chlorosilane liquid produced is used for described first rectification purification process.Thus, after overcooled chlorine hydrogenation synthetic reaction product is by above-mentioned process, chlorosilane liquid produced and hydrogen can be obtained, and chlorosilane liquid produced and hydrogen can be respectively fed to the related device of the equipment of the present invention, again recycle, it is thus possible to effectively realize energy-conserving and environment-protective, reduce the purpose of cost.
According to embodiments of the invention, described first condensing unit 10 hydrogenates synthetic reaction device 1 with described chlorine and is connected, for by described hydrogen supply to described chlorine hydrogenation synthetic reaction device 1.Thereby, it is possible to hydrogen is recycled, hydrogenate the chlorine hydrogenation synthetic reaction carried out in synthetic reaction device for chlorine and raw material, energy-conserving and environment-protective are provided, and production cost can be reduced.
Some concrete examples according to the present invention, with reference to Fig. 5, first rectification purification devices 2 includes the first rectifying column 21 of series connection, Second distillation column 22 and the 3rd rectifying column 23, and wherein, each rectifying column is all respectively provided with charging aperture and discharging opening from bottom to top along the axial direction of described rectifying column.Thereby, it is possible to ensure the production cost that is suitable for and higher rectification purification efficiency simultaneously, be conducive to the carrying out of subsequent step.Wherein, the reaction condition carried out in the first rectification purification devices 2 in the condition of the first rectification purification process and each rectifying column is not particularly limited, if can from the chlorine hydrogenation synthetic reaction product comprising trichlorosilane effectively purification obtain trichlorosilane.According to embodiments of the invention, the rectification temperature of described first rectifying column 21 is 60～100 degrees Celsius, and pressure is 0.2MPa, and reflux ratio is 10～50:1；The rectification temperature of described Second distillation column 22 is 100～140 degrees Celsius, and pressure is 0.5MPa, and reflux ratio is 20～50:1；The rectification temperature of described 3rd rectifying column 23 is 60～80 degrees Celsius, and pressure is 0.2MPa, and reflux ratio is 20～50:1.Thereby, it is possible to ensure safety in production, and power consumption less, production cost is low, rectification purification efficiency is high, effective, is conducive to the carrying out of subsequent step.
Wherein, the chemical reaction related in dismutation reaction device 3 is mainly: 4SiHCl3——SiH4+3SiCl4.And according to embodiments of the invention, the condition carrying out dismutation reaction in dismutation reaction device 3 is not particularly limited, as long as the dismutation reaction of trichlorosilane can be carried out safely, effectively obtain dismutation reaction product.Some concrete examples according to the present invention, in described dismutation reaction device 3, described dismutation reaction is at 50～80 degrees Celsius, carries out when 0.2～0.6MPa.Thus, production safety, and power consumption less, production cost is low, dismutation reaction efficiency is high, effective, is conducive to the carrying out of subsequent step.
According to embodiments of the invention, dismutation reaction device 3 is disproportionation reactor, and with reference to Fig. 6, described disproportionation reactor farther includes: disproportionation reactor body 31, trichlorosilane charging aperture 34 and dismutation reaction product discharge mouth 35.Wherein, according to embodiments of the invention, limit dismutation reaction space 32 in described disproportionation reactor body 31, and described dismutation reaction space 32 is provided with catalyst layer 33；Described trichlorosilane charging aperture 34 is arranged on the lower section of described catalyst layer 33, for supplying trichlorosilane in described dismutation reaction space 32；Described dismutation reaction product discharge mouth 35 is arranged on the top of described catalyst layer 33, discharges described disproportionation reactor for the dismutation reaction product comprising Silicon chloride. and silane that will be formed.Thus, dismutation reaction efficiency is high, effective, and production safety, power consumption less, cost is low, be conducive to the carrying out of subsequent step.
According to embodiments of the invention, the type of the second rectification purification devices 4 and the condition wherein carrying out processing are not particularly limited.Some concrete examples according to the present invention, with reference to Fig. 7, described second rectification purification devices 4 is low-temperature fractionating tower, and wherein, the temperature in described low-temperature fractionating tower is-60～-80 degrees Celsius, and pressure is 0.6～1.0MPa, and reflux ratio is 5～20:1.Thus, production safety, and power consumption less, production cost is low, rectification purification efficiency is high, effective, is conducive to the carrying out of subsequent step.
According to embodiments of the invention, with reference to Fig. 8, the equipment for preparing polysilicon of the present invention may further include vaporization process device 11, described vaporization process device 11 is connected with described second rectification purification devices 4 and described pyrolytic reaction device 5 respectively, for, before pyrolytic reaction, in advance the silane gas stored in liquid form being vaporized process.Thus, the carrying out of pyrolytic reaction in pyrolytic reaction device is conducive to such that it is able to effectively prepare polysilicon, and cost is low, needing can be few, energy-conserving and environment-protective, and pyrolytic reaction efficiency is high.
According to embodiments of the invention, the type of pyrolytic reaction device is not particularly limited.Some concrete examples according to the present invention, described pyrolytic reaction device 5 is reduction furnace, is provided with the silicon core carrier as crystal deposition in described reduction furnace.Thus, pyrolytic reaction efficiency is high, effective, and the electronic-grade polycrystalline silicon purity prepared is high.Other embodiments according to the present invention, with reference to Fig. 8, described reduction furnace is bell-jar reduction furnace.Thus, pyrolytic reaction efficiency is high, effective.It addition, the temperature in the quantity of silicon rod and reduction furnace, pressure condition are also not particularly limited in reduction furnace, as long as being conducive to pyrolytic reaction to carry out.According to embodiments of the invention, in described reduction furnace, it is provided with 12,24 or 36 pairs of silicon rods.Thus, it is possible to adopt silicon core as carrier.Further, according to embodiments of the invention, the cooling jacket consistent with silicon core logarithm in reduction furnace, it is additionally provided with.Thus, be conducive to silane gas checking solution to deposit, prepare high-purity electronic-grade polycrystalline silicon.Other embodiments according to the present invention, the temperature in described reduction furnace is 750～900 degrees Celsius, and pressure is 0.15～0.30MPa.Thus, pyrolytic reaction efficiency is high, effective, and reaction safety, and the electronic-grade polycrystalline silicon purity prepared is high.
According to embodiments of the invention, with reference to Fig. 9, the equipment for preparing polysilicon of the present invention can further include: flash distillation processes device the 12, second condensing unit 13 and residue treatment device 14.According to embodiments of the invention, it is connected as it is shown in figure 9, described flash distillation processes device 12 with described first rectification purification devices 2, for described first distillation residual liquid is carried out flash distillation process, in order to obtain Silicon chloride. gas and solid residue；Described second condensing unit 13 processes device 12 with described flash distillation respectively and described Liqiud-gas mixing device 6 is connected, for described Silicon chloride. gas is carried out condensation process, to obtain silicon tetrachloride liquid, and by the supply of described silicon tetrachloride liquid to described Liqiud-gas mixing device 6, hydrogenate synthetic reaction for described chlorine；Described residue treatment device 14 processes device 12 with described flash distillation and is connected, and processes for described solid residue is sequentially carried out alkali liquor hydrolysis neutralisation treatment and filter pressing.Thereby, it is possible to effectively realize the cycling and reutilization of the first distillation residual liquid, thus reaching energy-conserving and environment-protective, reduce the purpose of cost.Wherein it is desired to illustrate, when the first rectification purification devices 2 as it is shown in figure 5, when being the first rectifying column of series connection, Second distillation column and three rectifying columns, the first distillation residual liquid is the residual liquid discharged bottom Second distillation column.
According to embodiments of the invention, with reference to Figure 10, the equipment for preparing polysilicon of the present invention may further include: the first compressor 15 and the 3rd condensing unit 16, according to embodiments of the invention, described first compressor 15 is connected with described pyrolytic reaction device 5, for the reduction tail gas of pyrolytic reaction is compressed to pressure be 6.0～10.0MPa；Described 3rd condensing unit 16 is connected with described first compressor 15, described Liqiud-gas mixing device 6 and described vaporization process device 11, for being-100～-120 degrees Celsius by reduction tail gas condensing to the temperature through overcompression, silane gas is condensed into silane liquid and obtains hydrogen, and by described silane liquid supply to described vaporization process device 11, by the supply of described hydrogen to described Liqiud-gas mixing device 6, hydrogenate synthetic reaction for described chlorine.Thereby, it is possible to effectively the reduction tail gas produced in pyrolytic reaction device is processed, it is achieved non-pollution discharge, it is ensured that cleaning produces, and realizing the cycling and reutilization of reduction tail gas, thus reaching energy-conserving and environment-protective, reducing the purpose of cost.
According to embodiments of the invention, with reference to Figure 11, the equipment for preparing polysilicon of the present invention can further include: the second compressor the 17, the 4th condensing unit 18, elution device 19 and drip washing water treatment facilities (not shown).Wherein, according to embodiments of the invention, described second compressor 17 for by each device produced containing chlorosilane but the tail gas of non-silane-containing be compressed to pressure be 0.25～0.50MPa；Described 4th condensing unit 18 is connected with described second compressor 17 and described first rectification purification devices 2 respectively, for by through overcompression containing chlorosilane but the tail gas of non-silane-containing is cooled to temperature is-15～-30 degrees Celsius, to obtain chlorosilane liquid produced and residual gas, and the supply of described chlorosilane liquid produced is used for described first rectification purification process to described first rectification purification devices 2；Described elution device 19 is connected with described 4th condensing unit 18, for described residual gas is carried out drip washing, in order to obtain scrubbed gas and washing water；Described drip washing water treatment facilities is connected with described elution device 19, is used for utilizing alkali liquor that described washing water is neutralized, and liquid after neutralizing is carried out filter pressing, in order to obtain neutralizing water and filtering residue.Thereby, it is possible to effectively process containing chlorosilane but the tail gas of non-silane-containing produced in each device, it is achieved non-pollution discharge, it is ensured that cleaning produces, and realizing the cycling and reutilization of tail gas, thus reaching energy-conserving and environment-protective, reducing the purpose of cost.
According to embodiments of the invention, it is also possible to by pipeline by the supply of described neutralization water to described elution device 19, for described residual gas is carried out drip washing.Thereby, it is possible to neutralization water is circulated utilization, thus reducing production cost, and realize non-pollution discharge, it is ensured that cleaning produces.
Above section is described in detail the equipment for preparing polysilicon of the present invention, in order to be more fully understood that this equipment, the method below this equipment being suitable for is described in detail again.According to an aspect of the present invention, the present invention proposes a kind of method preparing polysilicon.According to embodiments of the invention, seeing figures.1.and.2, the method comprises the following steps:
S100: chlorine hydrogenation synthetic reaction
First, silica flour, hydrogen and at least one generation chlorine hydrogenation synthetic reaction selected from hydrogen chloride with Silicon chloride. are made, in order to obtain the chlorine hydrogenation synthetic reaction product comprising trichlorosilane.Wherein, the chemical reaction that this step relates generally to is:
3SiCl4+2H2+Si——4SiHCl3。
According to embodiments of the invention, the condition of chlorine hydrogenation synthetic reaction is not particularly limited.Some concrete examples according to the present invention, it is possible to when there is nickel-base catalyst or copper-based catalysts, make to comprise Silicon chloride. and contact with silica flour with the admixture of gas of hydrogen, in order to described chlorine hydrogenation synthetic reaction occurs.Thereby, it is possible to be effectively improved the efficiency of chlorine hydrogenation synthetic reaction, trichlorosilane is conducive to generate, and the carrying out of following purification steps.Wherein, comprise the ratio of Silicon chloride. and hydrogen in the admixture of gas of Silicon chloride. and hydrogen to be not particularly limited.According to embodiments of the invention, described in comprise in the admixture of gas of Silicon chloride. and hydrogen, the mol ratio of Silicon chloride. and hydrogen is 1:2～5.Thus, the efficiency of chlorine hydrogenation synthetic reaction significantly improves, and is conducive to trichlorosilane to generate, and the carrying out of following purification steps.
According to embodiments of the invention, the preparation method of the admixture of gas comprising Silicon chloride. and hydrogen is not particularly limited.According to some embodiments of the present invention, this admixture of gas comprising Silicon chloride. and hydrogen can obtain through the following steps: silicon tetrachloride liquid is mixed with hydrogen, obtains gas-liquid mixture；Utilize described chlorine hydrogenation synthetic reaction product that described gas-liquid mixture is carried out heat exchange process, in order to obtain through the gas-liquid mixture of preheating and hydrogenate synthetic reaction product through overcooled chlorine；And utilize resistance heater, the gas-liquid mixture through preheating is heated, in order to described in acquisition, comprise the admixture of gas of Silicon chloride. and hydrogen.Thus, can realize when consuming energy minimum chlorine being hydrogenated the cooling of synthetic reaction product and gas-liquid mixture being preheated simultaneously, and can effectively obtain the admixture of gas comprising Silicon chloride. and hydrogen, hydrogenate synthetic reaction for the chlorine in following cycle and raw material is provided, it is thus possible to effectively realize energy-conserving and environment-protective, reduce the purpose of cost.
Additionally, hydrogenate synthetic reaction product for through overcooled chlorine, it is also possible to be further processed.According to embodiments of the invention, the method for the above-mentioned present invention may further include: carries out dust removal process by described through overcooled chlorine hydrogenation synthetic reaction product；Chlorine through dust removal process is hydrogenated synthetic reaction product condense, in order to being separately recovered hydrogen and chlorosilane liquid produced, described chlorosilane liquid produced comprises trichlorosilane and Silicon chloride.；And described chlorosilane liquid produced is used for described first rectification purification process.Thus, after overcooled chlorine hydrogenation synthetic reaction product is by above-mentioned process, chlorosilane liquid produced and hydrogen can be obtained, and chlorosilane liquid produced and hydrogen can by corresponding steps that to be respectively fed in polycrystalline silicon preparing process follow-up, again recycle, it is thus possible to effectively realize energy-conserving and environment-protective, reduce the purpose of cost.And for reclaiming the hydrogen obtained, according to embodiments of the invention, it is possible to described hydrogen is returned and is used for carrying out described chlorine hydrogenation synthetic reaction.Thereby, it is possible to hydrogen is recycled, hydrogenate synthetic reaction for chlorine and raw material, energy-conserving and environment-protective are provided, and production cost can be reduced.
According to embodiments of the invention, the temperature and pressure of chlorine hydrogenation synthetic reaction is not particularly limited, as long as can effectively react, it is thus achieved that comprise the chlorine hydrogenation synthetic reaction product of trichlorosilane.According to some embodiments of the present invention, described chlorine hydrogenation synthetic reaction is to carry out at the temperature of 500～550 degrees Celsius.Thus, the efficiency of chlorine hydrogenation synthetic reaction is high, is conducive to trichlorosilane to generate, and the carrying out of following purification steps.According to embodiments of the invention, described chlorine hydrogenation synthetic reaction is at 500～550 degrees Celsius, carries out when 1.5～3.5MPa.Thus, chlorine hydrogenation synthetic reaction safety, efficiency are high, are conducive to trichlorosilane to generate, and the carrying out of following purification steps.
It addition, the source that chlorine hydrogenates the Silicon chloride. that synthetic reaction adopts is not particularly limited, it is straightforward to provide, it is also possible to separate from the product of subsequent step or waste liquid and obtain.According to embodiments of the invention, obtaining by trichlorosilane is carried out dismutation reaction at least partially of described Silicon chloride..Thus, recycled by the Silicon chloride. in dismutation reaction product in polycrystalline silicon preparing process subsequent step such that it is able to realize energy-conserving and environment-protective, reduced the purpose of cost.Other embodiments according to the present invention, it is also possible to separate in the first distillation residual liquid comprising Silicon chloride. produced from follow-up first rectification purification step and obtain.Thereby, it is possible to effectively realize producing the cycling and reutilization of waste liquid, thus reaching energy-conserving and environment-protective, reduce the purpose of cost.
S200: the first rectification purification process
Secondly, the chlorine comprising trichlorosilane of above-mentioned acquisition is hydrogenated synthetic reaction product and carry out the first rectification purification process, in order to obtain purified trichlorosilane and the first distillation residual liquid.
According to embodiments of the invention, the device that the first rectification purification process adopts is not particularly limited, as long as can effectively realize the chlorine hydrogenation synthetic reaction product comprising trichlorosilane is purified processes.According to some embodiments of the present invention, described first rectification purification process is that the multiple rectifying columns utilizing series connection carry out, and wherein, in each rectifying column, the axial direction that the material for carrying out rectification process is along described rectifying column moves from bottom to top.Thereby, it is possible to be effectively improved the efficiency of rectification purification process such that it is able to obtain highly purified trichlorosilane, be conducive to the carrying out of subsequent step.According to some currently preferred embodiments of the present invention, described first rectification purification process is to utilize the first rectifying column of series connection, Second distillation column and the 3rd rectifying column to carry out.Thereby, it is possible to ensure the production cost that is suitable for and higher rectification purification efficiency simultaneously such that it is able to obtain highly purified trichlorosilane, be conducive to the carrying out of subsequent step.Wherein, the reaction condition in the condition of the first rectification purification process and each rectifying column is not particularly limited, as long as trichlorosilane can be obtained effective purification from the chlorine hydrogenation synthetic reaction product comprising trichlorosilane.According to embodiments of the invention, the rectification temperature of described first rectifying column is 60～100 degrees Celsius, and pressure is 0.2MPa, and reflux ratio is 10～50:1；The rectification temperature of described Second distillation column is 100～140 degrees Celsius, and pressure is 0.5MPa, and reflux ratio is 20～50:1；The rectification temperature of described 3rd rectifying column is 60～80 degrees Celsius, and pressure is 0.2MPa, and reflux ratio is 20～50:1.Thereby, it is possible to ensure safety in production, and power consumption less, production cost is low, rectification purification efficiency is high, effective, it is possible to purify obtain purity be the trichlorosilane of more than 99%.
Further, it is also possible to waste liquid i.e. the first distillation residual liquid that the first rectification purification process is produced is further processed.According to embodiments of the invention, farther include: described first distillation residual liquid is carried out flash distillation process, in order to obtain Silicon chloride. gas and solid residue；Described Silicon chloride. gas is carried out condensation process, in order to obtain silicon tetrachloride liquid；Described silicon tetrachloride liquid is used for described chlorine hydrogenation synthetic reaction；And described solid residue is sequentially carried out alkali liquor hydrolysis neutralisation treatment and filter pressing process.Thereby, it is possible to effectively realize the cycling and reutilization of the first distillation residual liquid, thus reaching energy-conserving and environment-protective, reduce the purpose of cost.Wherein, when the first rectification purification process is to utilize the first rectifying column of series connection recited above, Second distillation column and the 3rd rectifying column to carry out, the first distillation residual liquid is the residual liquid discharged bottom Second distillation column.
S300: dismutation reaction
Then, described purified trichlorosilane generation dismutation reaction is made, in order to obtain the dismutation reaction product comprising Silicon chloride. and silane.Wherein, the chemical reaction that this step relates generally to is: 4SiHCl3——SiH4+3SiCl4。
According to embodiments of the invention, the condition of dismutation reaction is not particularly limited, as long as the dismutation reaction of trichlorosilane can be carried out safely, effectively obtains above-mentioned dismutation reaction product.Some concrete examples according to the present invention, described dismutation reaction is at 50～80 degrees Celsius, carries out when 0.2～0.6MPa.Thus, production safety, and power consumption less, production cost is low, dismutation reaction efficiency is high, effective, is conducive to the carrying out of subsequent step.
It addition, the device carrying out dismutation reaction is also not particularly limited, as long as ensure that production safety, carrying out efficiently.According to embodiments of the invention, described dismutation reaction carries out in disproportionation reactor, and described disproportionation reactor may further include: disproportionation reactor body, trichlorosilane charging aperture and dismutation reaction product discharge mouth.Some concrete examples according to the present invention, this internal dismutation reaction space that limits of above-mentioned disproportionation reactor, and described dismutation reaction space is provided with catalyst layer；Described trichlorosilane charging aperture is arranged on the lower section of described catalyst layer, for supplying trichlorosilane in described dismutation reaction space；Described dismutation reaction product discharge mouth is arranged on the top of described catalyst layer, discharges described disproportionation reactor for the dismutation reaction product comprising Silicon chloride. and silane that will be formed.Thus, dismutation reaction efficiency is high, effective, and production safety, power consumption less, cost is low, be conducive to the carrying out of subsequent step.
S400: the second rectification purification process
It follows that described dismutation reaction product is carried out the second rectification purification process, in order to obtain silane gas and Silicon chloride..
According to embodiments of the invention, the device and the required condition that carry out the second rectification purification process are not particularly limited.Some concrete examples according to the present invention, described second rectification purification process carries out in low-temperature fractionating tower, and wherein, the temperature in described low-temperature fractionating tower is-60～-80 degrees Celsius, and pressure is 0.6～1.0MPa, and reflux ratio is 5～20:1.Thereby, it is possible to guarantee production safety, and power consumption less, production cost is low, rectification purification efficiency is high, effective, is conducive to the carrying out of subsequent step.
Wherein, for residual silicon tetrachloride liquor produced in the second rectification purification step, it is possible to be further processed.According to embodiments of the invention, residual silicon tetrachloride liquor is by processing, it is thus achieved that Silicon chloride. for described chlorine hydrogenation synthetic reaction.Thus, effectively achieve recycling of residual silicon tetrachloride liquor, and reduce the dispensing of chlorine hydrogenation synthetic reaction raw material such that it is able to realize energy-conserving and environment-protective, reduce the purpose of cost.
S500: pyrolytic reaction
Then, make the silane gas of above-mentioned acquisition that pyrolytic reaction to occur in reduction furnace, wherein, described reduction furnace is provided with the silicon core carrier as crystal deposition, in order to obtain polysilicon.Wherein, the chemical reaction that this step relates generally to is: SiH4——Si+2H2。
According to embodiments of the invention, the described silane gas obtained is gathered in liquid form storage, and occurs in entering reduction furnace before pyrolytic reaction, in advance the silane of described liquid form is vaporized process in carburator in previous step.Thus, it is simple to the transport of silane gas, and be conducive to pyrolytic reaction to carry out, and then can effectively prepare polysilicon, and cost is low, needing can be few, energy-conserving and environment-protective, and pyrolytic reaction efficiency is high.
According to embodiments of the invention, the type of the reduction furnace that pyrolytic reaction can adopt is not particularly limited.Some concrete examples according to the present invention, described reduction furnace is bell-jar reduction furnace.Thus, pyrolytic reaction efficiency is high, effective, and the electronic-grade polycrystalline silicon purity prepared is high.
It addition, the temperature in the quantity of silicon rod and reduction furnace, pressure condition are also not particularly limited in reduction furnace, as long as being conducive to pyrolytic reaction to carry out.According to embodiments of the invention, in described reduction furnace, it is provided with 12,24 or 36 pairs of silicon rods.Thus, it is possible to adopt silicon core as carrier.Further, according to embodiments of the invention, the cooling jacket consistent with silicon core logarithm in reduction furnace, it is additionally provided with.Thus, be conducive to silane gas checking solution to deposit, prepare high-purity electronic-grade polycrystalline silicon.Other embodiments according to the present invention, the temperature in described reduction furnace is 750～900 degrees Celsius, and pressure is 0.15～0.30MPa.Thus, pyrolytic reaction efficiency is high, effective, and reaction safety, and the electronic-grade polycrystalline silicon purity prepared is high.
Wherein, it is also possible to being further processed by reduction tail gas produced in pyrolytic reaction, in order to be circulated utilization, wherein, the method that reduction tail gas is processed is not particularly limited.According to embodiments of the invention, it is possible to farther include: the reduction tail gas of pyrolytic reaction is compressed to pressure be 6.0～10.0MPa；It it is-100～-120 degrees Celsius by reduction tail gas condensing to the temperature through overcompression, in order to silane gas is condensed into silane liquid, and obtains hydrogen；And described hydrogen is used for described chlorine hydrogenation synthetic reaction.Thereby, it is possible to effectively reduction tail gas is processed, it is achieved non-pollution discharge, it is ensured that cleaning produces, and realizing the cycling and reutilization of reduction tail gas, thus reaching energy-conserving and environment-protective, reducing the purpose of cost.
Additionally, can also be further processed containing chlorosilane but the tail gas of non-silane-containing produced in each step, in order to being circulated recycling, wherein, the method carrying out processing is not particularly limited.According to embodiments of the invention, may further include: by each step produced containing chlorosilane but the tail gas of non-silane-containing be compressed to pressure be 0.25～0.50MPa, and it is cooled further to the temperature of-15～-30 degrees Celsius, in order to obtain chlorosilane liquid produced and residual gas；Described chlorosilane liquid produced is carried out described first rectification purification process；Described residual gas is carried out drip washing, in order to obtain scrubbed gas and washing water；And utilize alkali liquor that described washing water is neutralized, liquid after neutralizing is carried out filter pressing, in order to obtain neutralizing water and filtering residue.Thereby, it is possible to effectively process containing chlorosilane but the tail gas of non-silane-containing produced in each step, it is achieved non-pollution discharge, it is ensured that cleaning produces, and realizing the cycling and reutilization of tail gas, thus reaching energy-conserving and environment-protective, reducing the purpose of cost.Wherein, above-mentioned neutralization water can also recycle, and according to embodiments of the invention, is used for described residual gas is carried out drip washing by described neutralization water.Thereby, it is possible to neutralization water is circulated utilization, thus reducing production cost, and realize non-pollution discharge, it is ensured that cleaning produces.
Other embodiments according to the present invention, the polysilicon method of preparing of the present invention can further include: the Silicon chloride. separating acquisition in intermediate steps returns S100(chlorine hydrogenation synthetic reaction), it is made to participate in chlorine hydrogenation synthetic reaction, and then enter in the processing step of the method preparing polysilicon of the present invention, carry out sequential loop.Thereby, it is possible to realize the production purpose of economy, environmental protection.
It is surprisingly found by the inventors that, utilize preparing polysilicon method and can effectively preparing electronic-grade polycrystalline silicon of the present invention, and the method technique is simple, safety, energy-conserving and environment-protective, cost are low, and the polysilicon purity height produced, produce tail gas and waste residue can meet the requirement of environmental protection, for electronic-grade polycrystalline silicon process for cleanly preparing.
Additionally, according to some embodiments of the present invention, with reference to Fig. 2, the present invention prepares polysilicon method and can also comprise the following steps:
(a) chlorine hydrogenation synthesis step: adopt silica flour, hydrogen and supplementary Silicon chloride. (or hydrogen chloride) and come from subsequent step (b), the Silicon chloride. of (c) is raw material, control temperature 500～550 degree, pressure 1.5～3.5MPa, Silicon chloride. and hydrogen proportioning 1:2～1:5, under Ni-based or copper-base catalyst effect, it is trichlorosilane by converting silicon tetrachloride in fixing bed (or fluid bed) hydrogenation reactor, provides trichlorosilane raw material for step (c).Primary response is: 3SiCl4+2H2+Si——4SiHCl3。
(b) trichlorosilane rectification and purification step: the chlorosilane mixed liquor coming from step (a) enters in three rectifying columns connected, and controls the first rectifying column temperature 60～100 DEG C, pressure 0.2MPa, reflux ratio 10:1～50:1；Control Second distillation column temperature 100～140 DEG C, pressure 0.5MPa, reflux ratio 20:1～50:1；Control the 3rd rectifying column temperature 60～80 DEG C, pressure 0.2MPa, reflux ratio 20:1～50:1.Obtaining the trichlorosilane that purity is more than 99%, Silicon chloride. returns step (a).
C () trichlorosilane disproportionation step: come from the trichlorosilane of step (b), passes in disproportionation reactor, under catalyst action, control reactor temperature 50～80 DEG C, pressure 0.2～0.6MPa, make trichlorosilane be converted into silane gas.Dominant response equation is: 4SiHCl3——SiH4+3SiCl4。
D () silane gas cryogenic rectification step: come from the silane gas containing impurity of step (c), enters in low-temperature fractionating tower, temperature-60～-80 DEG C in control tower, pressure 0.60～1.0MPa, reflux ratio 5:1～20:1.Thus, the silane purity of overhead extraction can reach 9N～11N, mainly eliminates the impurity compounds such as B, P, Al, C.This part silane gas with liquid mode extraction and stores.
E () silane gas Pintsch process prepares polysilicon step: the silane gas from step (d) enters in bell-jar reduction furnace, control internal temperature 750～900 DEG C, 0.15MPa～0.30MPa, makes silane gas cracking be deposited on silicon core, and the hydrogen of generation is back to step (a) and recycles.Silane gas once cracks transformation efficiency can reach more than 90%.Dominant response equation is: SiH4——Si+2H2。
(f) residual liquid recycling step: the residual liquid discharged bottom produced first distillation residual liquid and Second distillation column in step (b) is mainly rich in Silicon chloride. and a small amount of solid residue, after passing it through the process such as flash distillation, dedusting and condensation, Silicon chloride. is reclaimed, and solid residue drains into step (h) and processes.
(g) tail gas recycle step: main process two parts tail gas, the tail gas rich in chlorosilane that a part is discharged for step (a) and (b), (c), (f), after overcompression deep cooling, reclaim to step (b) after major part chlorosilane is separated, a small amount of tail gas containing chlorosilane is after tail gas eluting column hydrolysis process is qualified, discharge is to air, and is processed by hydrolysis residue to step (h)；Another part is the reduction tail gas from step (e), this partial tail gas contains hydrogen and silane gas, after overcompression deep cooling, hydrogen is separated and supplies to step (a) and recycle, and silane gas is condensed into liquid and recycles to step (e) after overflash.
(h) residue neutralization procedure: by the hydrolysis residue of the aforementioned solid residue coming from step (f) and step (g), interpolation nertralizer (calcium hydroxide alkali liquor) is neutralized, filter pressing processes, then qualified solid slag is carried out environment protection emission, and waste water is back to the tail gas eluting column described in step (g) recycles.
Below by specific embodiment, the present invention will be described, it is necessary to explanation is that these embodiments are merely to illustrate that purpose, and can not be construed to limitation of the present invention by any way.It addition, in the examples below that if not otherwise specified, then the equipment adopted and material are commercially available.
Embodiment 1
Utilizing the equipment shown in Fig. 3-Figure 11, see figures.1.and.2 shown flow process, the method for preparing polysilicon according to the present invention, according to the preparation of following process purification trichlorosilane, and then prepares polysilicon:
(1) chlorine hydrogenation synthesis step: from following step (2), step (3) Silicon chloride. with hydrogen after air and liquid mixer proportioning mixes, with hydrogenation reactor exit gas through heat exchange, enter resistive heater heats to uniform temperature, this mixing gas is directly entered in hydrogenation reactor, control temperature 500～550 degree, pressure 1.5～3.5MPa, Silicon chloride. and hydrogen proportioning 1:2～1:5, under Ni-based or copper-base catalyst effect, react with silica flour.Reacted gas after efficient gas-solid cleaner unit in gas-gas heat exchanger with from the gas converting heat of air and liquid mixer, reacting gas after cooling enters bubbling gas wash tower, integrated condenser will be entered after further for solid dust dedusting, chlorosilane condensate enters liquid collection tank, and Hydrogen Separation out enters air and liquid mixer through compressor and recycles.
(2) chlorosilane purification step: utilize trichlorosilane and the difference of Silicon chloride. boiling point, have the principle of different volatility at the same temperature, adopts three towers (i.e. rectifying column) to purify trichlorosilane.Residual liquid is discharged from Second distillation column, and through the TCS that purifies from the 3rd rectifying column top extraction, the STC of recovery discharges, from the 3rd rectifier bottoms, the air and liquid mixer being back to step (1).Obtain the trichlorosilane that purity is more than 99%.
(3), there is dismutation reaction in trichlorosilane disproportionation step: control the temperature 50～80 DEG C of disproportionation reactor, pressure 0.2～0.6MPa, under catalyst action, pass in reactor by the TCS of the 3rd rectifying column top extraction, produces silane gas.
(4) silane gas cryogenic rectification step: utilize the difference of the impurity such as B, P, C, chlorosilane and silane gas boiling point, has the principle of different volatility at the same temperature, adopts low-temperature fractionating tower to purify silane gas.The silane gas coming from step (3) enters low-temperature fractionating tower, temperature-60～-80 DEG C in control tower, pressure 0.60～1.0MPa, reflux ratio 5:1～20:1.9N-11N can be reached from the silane purity of overhead extraction, mainly eliminate the impurity compounds such as B, P, Al, C.Going step (5) from the high purity silane gas of overhead extraction, impurity etc. is discharged from the bottom of tower.
(5) silane gas high temperature pyrolysis step: the high purity silane gas from step (4) enters carburator, is vaporizated into gas and enters bell-jar reduction furnace, and inside arranges the silicon core carrier as crystal deposition, it is possible to be 12 pairs of rods, 24 pairs of rods or 36 pairs of excellent reduction furnaces.Controlling internal temperature 750～900 DEG C, under 0.15MPa～0.30MPa, silane gas cracking is deposited on silicon core, generates bar-shaped electronic-grade polycrystalline silicon.It is back to step (7) after the reduction tail gas recycle produced to process.Wherein, silane gas once cracks transformation efficiency and can reach more than 90%.
(6) residual liquid recycling step: the residual liquid discharged from step (2) the 3rd rectifier bottoms, rich in Silicon chloride. and a small amount of solid residue, evaporates through flash tank, flash tank is with agitating device, axle adopts mechanical seal with body, and it is outside is steam jacket, adopts steam heating.The Silicon chloride. gas being evaporated from flash tank enters follow-up water cooler condensation, and silicon tetrachloride liquid is back to air and liquid mixer in step (1).Solid residue through with alkali liquor hydrolysis neutralize after through filter pressing be harmless neutralization slag discharge.
(7) tail gas recycle step: whole system is divided into two strands of tail gas.Tail gas 1 is the tail gas containing chlorosilane, wherein not silane-containing gas.This partial tail gas is through compressor compresses to 0.25～0.50MPa, enter chiller, control cryogenic temperature-15～-30 DEG C, chlorosilane condensate gets off to be back to step (2), the uncooled gas got off enters in tail gas eluting column, the acceptable gas emptying after drip washing, washing water and alkali liquor and rear filter pressing, arranging outside filtering residue, neutralization water returns to eluting column and recycles；Tail gas 2 is the gas rich in hydrogen and a small amount of silane gas, namely from bell-jar reduction furnace reduction tail gas out, this portion gas is through compressor compresses to 6.0～10.0MPa, enter chiller condensation to-100～-120 DEG C, silane gas is condensed into liquid and enters carburator, and Hydrogen Separation exits into chlorine hydrogenation synthetic reaction device.
In the description of this specification, specific features, structure, material or feature that the description of reference term " embodiment ", " some embodiments ", " example ", " concrete example " or " some examples " etc. means in conjunction with this embodiment or example describe are contained at least one embodiment or the example of the present invention.In this manual, the schematic representation of above-mentioned term is not necessarily referring to identical embodiment or example.And, the specific features of description, structure, material or feature can combine in an appropriate manner in any one or more embodiments or example.
Although an embodiment of the present invention has been shown and described, it will be understood by those skilled in the art that: these embodiments can being carried out multiple change, amendment, replacement and modification when without departing from principles of the invention and objective, the scope of the present invention is limited by claim and equivalent thereof.

Claims (21)

1. the equipment for purification trichlorosilane, it is characterised in that including:
First rectification purification devices, for carrying out the first rectification purification process, in order to obtain purified trichlorosilane and the first distillation residual liquid to trichlorosilane；
Chlorine hydrogenation synthetic reaction device, described chlorine hydrogenation synthetic reaction device is connected with described first rectification purification devices, for making silica flour, hydrogen and at least one generation chlorine hydrogenation synthetic reaction selected from hydrogen chloride with Silicon chloride., to obtain described chlorine hydrogenation synthetic reaction product and to supply to described first rectification purification devices, and described chlorine hydrogenation synthetic reaction device is provided with nickel-base catalyst or copper-based catalysts, so that when there is nickel-base catalyst or copper-based catalysts, make to comprise Silicon chloride. to contact with silica flour with the admixture of gas of hydrogen, there is described chlorine hydrogenation synthetic reaction；
Liqiud-gas mixing device, described Liqiud-gas mixing device, for silicon tetrachloride liquid being mixed with hydrogen, obtains gas-liquid mixture；
Heat-exchange device, described heat-exchange device hydrogenates synthetic reaction device with described Liqiud-gas mixing device and described chlorine respectively and is connected, for utilizing described chlorine hydrogenation synthetic reaction product that described gas-liquid mixture is carried out heat exchange process, in order to obtain through the gas-liquid mixture of preheating and hydrogenate synthetic reaction product through overcooled chlorine；And
Resistance heater, described resistance heater hydrogenates synthetic reaction device with described heat-exchange device and described chlorine respectively and is connected, for the gas-liquid mixture through preheating is heated, to comprise the admixture of gas of Silicon chloride. and hydrogen described in obtaining, and the described admixture of gas supply comprising Silicon chloride. and hydrogen is hydrogenated synthetic reaction device to described chlorine
Wherein,
The form that described trichlorosilane hydrogenates synthetic reaction product with chlorine provides,
Described first rectification purification devices includes the first rectifying column of series connection, Second distillation column and the 3rd rectifying column, and the rectification temperature of described first rectifying column is 60～100 degrees Celsius, and pressure is 0.2MPa, and reflux ratio is 10～50:1；The rectification temperature of described Second distillation column is 100～140 degrees Celsius, and pressure is 0.5MPa, and reflux ratio is 20～50:1；The rectification temperature of described 3rd rectifying column is 60～80 degrees Celsius, and pressure is 0.2MPa, and reflux ratio is 20～50:1,
Wherein, each rectifying column is all respectively provided with charging aperture and discharging opening from bottom to top along the axial direction of described rectifying column.
2. equipment according to claim 1, it is characterised in that described in comprise in the admixture of gas of Silicon chloride. and hydrogen, the mol ratio of Silicon chloride. and hydrogen is 1:2～5.
3. equipment according to claim 1, it is characterised in that described chlorine hydrogenation synthetic reaction is to carry out at the temperature of 500～550 degrees Celsius.
4. equipment according to claim 3, it is characterised in that described chlorine hydrogenation synthetic reaction is at 500～550 degrees Celsius, carries out when 1.5～3.5MPa.
5. equipment according to claim 1, it is characterised in that farther include:
Dust arrester, described dust arrester is connected with described heat-exchange device, in order to carry out dust removal process by described through overcooled chlorine hydrogenation synthetic reaction product；And
First condensing unit, described first condensing unit is connected with described dust arrester and the first rectification purification devices respectively, condense for the chlorine through dust removal process is hydrogenated synthetic reaction product, to be separately recovered hydrogen and chlorosilane liquid produced, described chlorosilane liquid produced comprises trichlorosilane and Silicon chloride., and to described first rectification purification devices, the supply of described chlorosilane liquid produced is used for described first rectification purification process.
6. equipment according to claim 5, it is characterised in that described first condensing unit hydrogenates synthetic reaction device with described chlorine and is connected, for by described hydrogen supply to described chlorine hydrogenation synthetic reaction device.
7. equipment according to claim 1, it is characterised in that farther include:
Dismutation reaction device, described dismutation reaction device is connected with described first rectification purification devices, is used for making described purified trichlorosilane generation dismutation reaction, in order to obtain the dismutation reaction product comprising Silicon chloride. and silane；
Second rectification purification devices, described second rectification purification devices is connected with described dismutation reaction device, for described dismutation reaction product is carried out the second rectification purification process, in order to obtain silane gas and Silicon chloride.；And
Pyrolytic reaction device, described pyrolytic reaction device is connected with described second rectification purification devices, is used for making described silane gas generation pyrolytic reaction, in order to obtain polysilicon.
8. equipment according to claim 7, it is characterised in that in described dismutation reaction device, described dismutation reaction is at 50～80 degrees Celsius, carries out when 0.2～0.6MPa.
9. equipment according to claim 7, it is characterised in that described dismutation reaction device is disproportionation reactor, and described disproportionation reactor farther includes:
Disproportionation reactor body, this internal dismutation reaction space that limits of described disproportionation reactor, and described dismutation reaction space is provided with catalyst layer；
Trichlorosilane charging aperture, described trichlorosilane charging aperture is arranged on the lower section of described catalyst layer, for supplying described purified trichlorosilane in described dismutation reaction space；And
Dismutation reaction product discharge mouth, described dismutation reaction product discharge mouth is arranged on the top of described catalyst layer, discharges described disproportionation reactor for the dismutation reaction product comprising Silicon chloride. and silane that will be formed.
10. equipment according to claim 7, it is characterised in that described in comprise Silicon chloride. and hydrogen admixture of gas described in Silicon chloride. derive from described dismutation reaction device at least partially.
11. equipment according to claim 7, it is characterised in that described second rectification purification devices hydrogenates synthesizer with described chlorine and is connected, in order to the Silicon chloride. obtained in described second rectification purification devices is used for described chlorine hydrogenation synthetic reaction.
12. equipment according to claim 7, it is characterised in that described second rectification purification devices is low-temperature fractionating tower, wherein, the temperature in described low-temperature fractionating tower is-60～-80 degrees Celsius, and pressure is 0.6～1.0MPa, and reflux ratio is 5～20:1.
13. equipment according to claim 7, it is characterized in that, farther include vaporization process device, described vaporization process device is connected with described second rectification purification devices and described pyrolytic reaction device respectively, for, before pyrolytic reaction, in advance the silane gas stored in liquid form being vaporized process.
14. equipment according to claim 7, it is characterised in that described pyrolytic reaction device is reduction furnace, described reduction furnace is provided with the silicon core carrier as crystal deposition.
15. equipment according to claim 14, it is characterised in that described reduction furnace is bell-jar reduction furnace.
16. equipment according to claim 15, it is characterised in that be provided with 12,24 or 36 pairs of silicon rods in described reduction furnace.
17. equipment according to claim 15, it is characterised in that the temperature in described reduction furnace is 750～900 degrees Celsius, pressure is 0.15～0.30MPa.
18. equipment according to claim 1, it is characterised in that farther include:
Flash distillation processes device, and described flash distillation processes device and is connected with described first rectification purification devices, for described first distillation residual liquid is carried out flash distillation process, in order to obtain Silicon chloride. gas and solid residue；
Second condensing unit, described second condensing unit processes device with described flash distillation respectively and described Liqiud-gas mixing device is connected, for described Silicon chloride. gas is carried out condensation process, to obtain silicon tetrachloride liquid, and by the supply of described silicon tetrachloride liquid to described Liqiud-gas mixing device, hydrogenate synthetic reaction for described chlorine；And
Residue treatment device, described residue treatment device processes device with described flash distillation and is connected, and processes for described solid residue is sequentially carried out alkali liquor hydrolysis neutralisation treatment and filter pressing.
19. equipment according to claim 13, it is characterised in that farther include:
First compressor, described first compressor is connected with described pyrolytic reaction device, for the reduction tail gas of pyrolytic reaction is compressed to pressure be 6.0～10.0MPa；And
3rd condensing unit, described 3rd condensing unit is connected with described first compressor, described Liqiud-gas mixing device and described vaporization process device, for being-100～-120 degrees Celsius by reduction tail gas condensing to the temperature through overcompression, silane gas is condensed into silane liquid and obtains hydrogen, and by described silane liquid supply to described vaporization process device, by the supply of described hydrogen to described Liqiud-gas mixing device, hydrogenate synthetic reaction for described chlorine.
20. equipment according to claim 7, it is characterised in that farther include:
Second compressor, described second compressor for by each device produced containing chlorosilane but the tail gas of non-silane-containing be compressed to pressure be 0.25～0.50MPa；
4th condensing unit, described 4th condensing unit is connected with described second compressor and described first rectification purification devices respectively, for by through overcompression containing chlorosilane but the tail gas of non-silane-containing is cooled to temperature is-15～-30 degrees Celsius, to obtain chlorosilane liquid produced and residual gas, and the supply of described chlorosilane liquid produced is used for described first rectification purification process to described first rectification purification devices；
Elution device, described elution device is connected with described 4th condensing unit, for described residual gas is carried out drip washing, in order to obtain scrubbed gas and washing water；And
Drip washing water treatment facilities, described drip washing water treatment facilities is connected with described elution device, is used for utilizing alkali liquor that described washing water is neutralized, and liquid after neutralizing is carried out filter pressing, in order to obtain neutralizing water and filtering residue.
21. equipment according to claim 20, it is characterised in that by the supply of described neutralization water to described elution device, for described residual gas is carried out drip washing.
CN201310373760.2A 2013-08-23 2013-08-23 Equipment for purification trichlorosilane Active CN103449448B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310373760.2A CN103449448B (en) 2013-08-23 2013-08-23 Equipment for purification trichlorosilane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310373760.2A CN103449448B (en) 2013-08-23 2013-08-23 Equipment for purification trichlorosilane

Publications (2)

Publication Number Publication Date
CN103449448A CN103449448A (en) 2013-12-18
CN103449448B true CN103449448B (en) 2016-07-06

Family

ID=49732352

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310373760.2A Active CN103449448B (en) 2013-08-23 2013-08-23 Equipment for purification trichlorosilane

Country Status (1)

Country Link
CN (1) CN103449448B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103434013B (en) * 2013-08-29 2016-03-23 昆山达功电子有限公司 Magnet ring burr remover
CN103950933B (en) * 2014-03-31 2016-08-17 中国恩菲工程技术有限公司 The method preparing polysilicon
CN103950937B (en) * 2014-03-31 2016-03-30 中国恩菲工程技术有限公司 Chlorosilane method of purification
CN103950938B (en) * 2014-03-31 2016-01-27 中国恩菲工程技术有限公司 Chlorosilane purification system
CN108516555A (en) * 2018-07-10 2018-09-11 天津科技大学 A kind of preparation method and equipment of dichlororosilane eiectronic grade

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101486727A (en) * 2009-02-13 2009-07-22 李明成 High purity silane gas continuous preparation and apparatus thereof
CN101618874A (en) * 2009-08-13 2010-01-06 洛阳世纪新源硅业科技有限公司 Method for producing trichlorosilane by coldly hydrogenating silicon tetrachloride
CN103260716A (en) * 2010-12-20 2013-08-21 Memc电子材料有限公司 Production of polycrystalline silicon in substantially closed-oop processes that involve disproportionation operations
CN203498101U (en) * 2013-08-23 2014-03-26 中国恩菲工程技术有限公司 Equipment for purifying trichlorosilane

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101786630B (en) * 2010-01-29 2013-02-13 天津大学 Trichlorosilane three-tower differential pressure coupling energy-saving rectifying and purifying system and operating method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101486727A (en) * 2009-02-13 2009-07-22 李明成 High purity silane gas continuous preparation and apparatus thereof
CN101618874A (en) * 2009-08-13 2010-01-06 洛阳世纪新源硅业科技有限公司 Method for producing trichlorosilane by coldly hydrogenating silicon tetrachloride
CN103260716A (en) * 2010-12-20 2013-08-21 Memc电子材料有限公司 Production of polycrystalline silicon in substantially closed-oop processes that involve disproportionation operations
CN203498101U (en) * 2013-08-23 2014-03-26 中国恩菲工程技术有限公司 Equipment for purifying trichlorosilane

Also Published As

Publication number Publication date
CN103449448A (en) 2013-12-18

Similar Documents

Publication Publication Date Title
CN103449448B (en) Equipment for purification trichlorosilane
CN101143723B (en) Modified method and device for preparing trichlorosilane and multicrystal silicon
CN103449446B (en) Method for preparing trichlorosilane
CN101279735A (en) Production method and apparatus for trichlorosilane
CN105060298B (en) High-boiling components prepare the treating method and apparatus of organosilicon in a kind of production of polysilicon
CN102442672B (en) Method for purifying and recycling impurity-containing chlorosilane and application of method in polysilicon production
CN103449440B (en) Equipment for preparing polycrystalline silicon
CN102838121B (en) Method and device for recycling tail gas in production of polycrystalline silicon
CN204058313U (en) A kind of apparatus system recycling chlorosilane slag slurry raffinate
CN103482630B (en) Prepare the method for polysilicon
CN103382032A (en) Preparation method for trichlorosilane from silicon tetrachloride
CN206188406U (en) A device for handling polycrystalline silicon by -product sediment thick liquid
CN103553057B (en) A kind of method utilizing reaction rectification technique process chlorosilane waste gas
CN103449447B (en) Prepare the equipment of trichlorosilane
CN102786055A (en) Method and device for heat utilization in polycrystalline silicon production process
CN103466633B (en) The method of purification trichlorosilane
CN204057977U (en) For the apparatus system of halogen silicon polymer cracking for halosilanes
CN102020282A (en) Method for producing trichlorosilane by using silicon tetrachloride
CN104072530A (en) Device system and method for recycling chlorosilane residual slurry liquid
CN203498101U (en) Equipment for purifying trichlorosilane
CN203498100U (en) Equipment for preparing trichlorosilane
CN105565322B (en) A kind for the treatment of method and apparatus by silicon, hydrogen and silicon tetrachloride gas/solid mixture obtained by the reaction
CN107720755A (en) A kind of production of polysilicon raw material and method for preparing polysilicon
CN103449444B (en) The method of purifying silane
CN201136791Y (en) Device for conversing silicon tetrachloride to be trichlorosilane by hydrochlorination process

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant