CN102530951A - Method and device for producing granular polysilicon - Google Patents
Method and device for producing granular polysilicon Download PDFInfo
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- CN102530951A CN102530951A CN2010106032385A CN201010603238A CN102530951A CN 102530951 A CN102530951 A CN 102530951A CN 2010106032385 A CN2010106032385 A CN 2010106032385A CN 201010603238 A CN201010603238 A CN 201010603238A CN 102530951 A CN102530951 A CN 102530951A
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Abstract
The invention discloses a method and a device for producing granular polysilicon by utilizing the fluidized-bed process. Hydrogen chloride is fed into a fluidized-bed reactor from an expanding section of the top of a fluidized bed and is reacted with fine silicon powder generated in the process of producing granular silicon to generate chloro-silicane gas so that risks of harm to a system due to the fact that the fine silicon powder enters a pipeline at the rear end of the fluidized bed are eliminated, fine silicon powder entrainment is eliminated simultaneously, gas inlet flow of the fluidized bed is improved so as to improve unit capacity of the rector, and production cost is lowered. Besides, the hydrogen chloride fed into the fluidized-bed reactor from the top is reacted with the fine silicon powder to generate chloro-silicane so that circulation of a certain amount of chloride in the reactor is achieved.
Description
Technical field
The present invention relates to a kind of method and device of producing the high purity granular polysilicon, relate more specifically to method and device that a kind of fluidized-bed process is produced granular polycrystalline silicon.
Background technology
Production of polysilicon technology also has fluidized bed process, physics method etc. except traditional improvement Siemens Method.Because the fluidized-bed process energy consumption is lower, it also is counted as the strongest the substituting of improvement Siemens process polycrystalline silicon production technique.Fluidized-bed process is that the polycrysalline silcon after the heating is transported to reaction zone as seed crystal; Feed silicon-containing gas or/and hydrogen at reaction zone; Silicon-containing gas produces elemental silicon and is deposited on particle surface or/and hydrogen on the polycrysalline silcon surface thermolysis or reduction takes place; Is that the polycrysalline silcon of 0.1～10mm takes out as product at reactor lower part with the part particle diameter; On reaction zone top, the polysilicon fine particle that adds diameter as crystal seed and be 0.01～1.0mm is to keep the amount of polycrysalline silcon in the reactor drum.This invention technology has the reactor drum operate continuously and the cycle of operation is long, low power consumption and other advantages.
(particle diameter is less than 10 μ m but common fluidized-bed process can produce the superfine silica flour of particle diameter in the process of producing granular polycrystalline silicon.In fluidized-bed based on the halogenated silanes reactive system; Fine silica powder is prone to the absorption halogenated silanes and discharges with the product granular polycrystalline silicon, causes that halogen impurities exceeds standard in the finished product, simultaneously because the generation of fine silica powder; Air input in the palpus controlling flow fluidized bed reactor; Reduce the harm that is caused in the fluidized-bed rear end pipeline that fine silica powder carried secretly by tail gas, this causes the median size of product granular polycrystalline silicon to descend, and the reactor drum productive rate reduces.
In order to improve the fluidized-bed productive rate and to improve product cut size; The present invention takes to strengthen the mode of virgin gas and auxiliary gas inlet amount; Make air input reach 40～50 times of minimum fluidization velocity, thereby obtain the bigger product granular polycrystalline silicon of particle diameter on the one hand, and bring the fine silica powder that generates into the fluidized-bed top expanded section on the other hand; Reduce because the product contaminating impurity that halogenated silanes absorption causes; And get into the rear end pipeline for fear of fine silica powder, and set up the hydrogen halide feed-pipe in the fluidized-bed top expanded section, feed hydrogen halide; Make fine silica powder in the high density hydrogen halide, regenerated halogenated silanes and discharge reactor drum, can reach the purpose of element recycle with tail gas by reaction.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method and relative unit thereof of producing the high purity granular polysilicon; This method generates halogenated silanes through the fine silica powder reaction that feeds hydrogen halide in the fluidized-bed top expanded section and generate in reactor drum; Increase fluidized-bed raw material air input; Thereby make reactor drum reach bigger productive rate, and eliminate the harm of fine silica powder product and system.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is following:
A kind of method that adopts fluidized-bed process to produce the high purity granular polysilicon; It is characterized in that its raw material inlet mouth bottom fluidized-bed reactor feeds hydrogen and silicon-containing gas feeds hydrogen as fluidizing gas as material mixed gas and by auxiliary gas inlet mouth, material mixed gas and auxiliary gas get in the fluidized-bed through the gas distribution dish; Silicon seed adds fluidized-bed by the silicon seed charging opening that is positioned at fluidized-bed top, and the granular polycrystalline silicon that reaction generates is discharged by the granular silicon discharge port of bottom; Position more than the silicon seed charging opening feeds hydrogen halide through the hydrogen halide inlet pipe, generates the halo silicomethane and discharges from the tail gas outlet with tail gas with being carried secretly to react to the fine silica powder of expanding reach.
Wherein, said silicon-containing gas is preferably the halo silicomethane, particularly preferably is Trichloromonosilane or silicobromoform.
Wherein, the mol ratio of hydrogen and said silicon-containing gas is 1: 0.4～1: 5 in the said material mixed gas, and material mixed gas feeds fluidized-bed reactor after being heated to 250～350 ℃.
Wherein, feed fluidized-bed reactor after said hydrogen as fluidizing gas is heated to 400～1000 ℃.
Wherein, in said silicon-containing gas and the said hydrogen contained impurity molecule ratio less than 0.1ppm.
Wherein, said silicon seed has purity and the resistivity that is not less than target product, and particle diameter is 10～1000 μ m.
Wherein, said fluidized-bed reactor bottom direct tube section temperature is 700～1000 ℃.
Wherein, said fluidized-bed reactor internal pressure is 0.1～10bar, is preferably 0.8～2bar.
Wherein, the said hydrogen halide that is fed by the hydrogen halide inlet pipe is preferably hydrogenchloride or hydrogen bromide, and the position of said hydrogen halide inlet pipe is preferably 300～400 ℃ of scopes in the expanding reach temperature range is 250～550 ℃ scope.
Wherein, the hydrogen halide TR that said hydrogen halide inlet pipe feeds is 50～550 ℃, is preferably 150～350 ℃.
A kind of fluidizer that is used to produce the high purity granular polysilicon; The housing that it is characterized in that it is divided into bottom direct tube section and top expanding reach; The direct tube section bottom is provided with the gas distribution dish, and the gas distribution tray bottom connects virgin gas inlet mouth, auxiliary gas inlet mouth and granular silicon discharge port; Side, housing top is provided with silicon seed charging opening and hydrogen halide inlet pipe, and the top is provided with the tail gas outlet.
Wherein, said enclosure interior is provided with heating installation, preferably adopts electrically heated coil or radiation heating.
Wherein, the direct tube section inwall of said housing is provided with the graphite liner.
Wherein, said graphite inner lining surface preferably is coated with high hardness spray coating, preferably adopts material prepn coatings such as silicon nitride, silit, SP 1 or titanium nitride.
Wherein, said gas distribution panel surface preferably is coated with high hardness spray coating, preferably adopts material prepn coatings such as silicon nitride, silit, SP 1 or titanium nitride.
Wherein, said seed crystal charging opening is located at housing top, preferably is located at housing direct tube section top, preferably is coated with high hardness spray coating in the charging opening, preferably adopts material prepn coatings such as silicon nitride, silit, SP 1 or titanium nitride.
Wherein, said hydrogen halide inlet pipe is located at housing top, is positioned at said silicon seed charging opening top, preferably is located at housing expanding reach place.
Wherein, said hydrogen halide inlet pipe is connected on the said enclosure interior endless tube, and said endless tube inboard evenly is provided with nozzle, and said nozzle direction is a level or obliquely.
Wherein, said housing expanding reach inwall material and said endless tube material adopt the high-hardness corrosion-resistant alloy to process.
Beneficial effect: adopt method of the present invention and device to produce granular polycrystalline silicon, compared with prior art, have the following advantages: 1) improved the inlet amount of fluidized-bed reactor, obtained the granular polycrystalline silicon of bigger particle diameter, improved the productive rate of single device; 2) reduce halogen impurities pollution in the product, improve product purity; 3) eliminate fine silica powder and carry the harm that produces to fluidized-bed rear end pipeline secretly.
Description of drawings
Fig. 1 is that fluidized-bed involved in the present invention is produced granular polycrystalline silicon process synoptic diagram.Wherein, 1, housing; 2, virgin gas inlet mouth; 3, auxiliary gas inlet mouth; 4, granular silicon discharge port; 5, gas distribution dish; 6, granular polycrystalline silicon; 7, silicon seed charging opening; 8, hydrogen halide inlet pipe; 9, fine silica powder; 10, tail gas outlet.
Fig. 2 is a hydrogen halide air inlet endless tube structural representation involved in the present invention.Wherein, 801, endless tube; 802, nozzle.
Embodiment
Below through concrete embodiment and combine accompanying drawing that method among the present invention and device are elaborated, but these embodiment only are illustrative purposes, are not intended to scope of the present invention is carried out any qualification.
Embodiment:
Referring to Fig. 1, Fig. 1 is that the fluidized-bed that relates among the present invention is produced granular polycrystalline silicon process synoptic diagram.It comprises housing 1, virgin gas inlet mouth 2, auxiliary gas inlet mouth 3, granular silicon discharge port 4, gas distribution dish 5, granular polycrystalline silicon 6, silicon seed charging opening 7, hydrogen halide inlet pipe 8, fine silica powder 9 and tail gas outlet 10.
Direct tube section bottom, housing 1 bottom is fixed on the gas distribution dish 5; Gas distribution dish 5 bottoms connect virgin gas inlet mouth 2 and auxiliary gas inlet mouth 3; Being heated to about 300 ℃ material mixed gas gets in the fluidized-bed through virgin gas inlet mouth 2; Be heated to about 700～800 ℃ pure hydrogen and get in the fluidized-bed through the duct, inside of auxiliary gas inlet mouth 3 through gas distribution dish 5, the direct tube section upper side connects silicon seed charging opening 7, is heated to about 700～900 ℃ purity and is about 8～9N; Particle diameter is that the silicon seed of 100～500 μ m feeds fluidized-bed by silicon seed charging opening 7; In direct tube section, contact and form the fluidization bed with gas, direct tube section inwall heater coil is heated to about 1000 ℃, and particle diameter reaches the granular polycrystalline silicon 6 of about 3～6mm from granular silicon discharge port 4 discharging current fluidized bed reactors; Expanding reach side, housing 1 top connects hydrogen halide inlet pipe 8; The top connects tail gas outlet 10; Hydrogen halide inlet pipe 8 connects the endless tube 801 that is positioned at expanding reach inside; Be heated to about 300 ℃ hydrogen halide and feed hydrogen halide inlet pipe 8 and get into endless tube 801 as shown in Figure 2 and spray in the expanding reach, generate halogenated silanes with fine silica powder 9 reactions of being carried secretly, and discharge by tail gas outlet 10 with the main body air-flow to expanding reach by nozzle 802.
Tail gas obtains hydrogen, hydrogen halide and multiple halogenated silanes, reusable edible material through separation after discharging.
The practical implementation condition:
1) fluidized-bed direct tube section diameter is 1m, and high 6m, expanding reach diameter are 2.5m, high 8m.
2) the silicon seed charging opening is positioned at the direct tube section top, the hydrogen halide inlet pipe be positioned at expanding reach apart from the top 5m place.
3) the fluidized-bed internal pressure is 2bar.
4) material mixed gas adopts Trichloromonosilane to mix with hydrogen, and the Trichloromonosilane flow is 5m
3/ h, hydrogen flowing quantity are 10m
3/ h, assist gas adopts pure hydrogen, and flow is 20m
3/ h.
5) top feeds hydrogen chloride gas, and flow is about 20m
3/ h.
6) silicon seed employing purity is the polysilicon preparation of 9N, and particle diameter is 150～500 μ m.
Feed assist gas when 7) fluidized-bed starts earlier, to purging in the FBR and heating up, the assist gas flow finally is adjusted to 20m
3/ h.Add seed crystal from the silicon seed charging opening; The electric heating assembly that the fluidized-bed direct tube section is opened in stable back heats; When temperature rises to about 1000 ℃; Begin to feed material mixed gas and begin to feed hydrogenchloride, treat that fluidized-bed direct tube section inner top and bottom pressure reduction can begin to take out the product granular silicon from discharge port after stable at the top.Continuous and stable production 100 hours drops into the about 100kg of seed crystal altogether, and by obtaining about 230kg product in the discharge port, per pass conversion is about 21%, and the product median size is 4～5mm, and ultimate production is about 130kg, and unit power consumption is about 29kWh/kg, and purity is 8N.Move and detect rear end pipeline, no silicon powder deposit after 100 hours.
In the foregoing description; Use bigger fluidized-bed air input will react the fine silica powder that forms and bring to the fluidized-bed expanding reach; And feed high density chlorination hydrogen and fine silica powder reaction, and eliminate the harm of fine silica powder to the rear end pipeline, obtain the bigger product granular polycrystalline silicon of particle diameter simultaneously; And be mixed in the product owing to eliminated the fine silica powder that is adsorbed with more chlorosilane, the product purity that is obtained is also higher.
Although the preceding text specific embodiments of the invention has given to describe in detail and explanation; But should indicatedly be; Can carry out various equivalences to above-mentioned embodiment according to conception of the present invention changes and modification; When the function that it produced does not exceed spiritual that specification sheets and accompanying drawing contain yet, all should be within protection scope of the present invention.
Claims (12)
1. method that adopts fluidized-bed process to produce granular polycrystalline silicon; Comprise the silicon-containing gas and the hydrogen that in fluidized-bed reactor, feed as unstripped gas; And said unstripped gas generates the step of granular polycrystalline silicon at the fluidized-bed reactor internal-response that is added with seed crystal; The top expanding reach that it is characterized in that said fluidized-bed reactor partly is provided with the Halogen gas inlet, and said Halogen gas is carried secretly to the fine silica powder reaction generation halo silicomethane of expanding reach and with tail gas with quilt and discharged from the tail gas outlet.
2. the method for production granular polycrystalline silicon according to claim 1; It is characterized in that said unstripped gas is fed by fluidized-bed reactor bottom virgin gas inlet mouth; Hydrogen or rare gas element as auxiliary gas are fed by auxiliary gas inlet mouth, and said unstripped gas and said auxiliary gas get into fluidized-bed reactor through the gas distribution dish.
3. the method for production granular polycrystalline silicon according to claim 1 is characterized in that said silicon-containing gas is any one in chlorosilane, the bromo-silicane, is preferably in Trichloromonosilane, the silicobromoform any one.
4. the method for production granular polycrystalline silicon according to claim 1 is characterized in that said Halogen gas is any one in chlorine, hydrogenchloride, bromine gas, the hydrogen bromide, is preferably hydrogenchloride or hydrogen bromide.
5. the method for production granular polycrystalline silicon according to claim 1 is characterized in that said fluidized-bed reactor internal pressure is 0.1～10bar.
6. the method for production granular polycrystalline silicon according to claim 1 is characterized in that the interior temperature of bottom direct tube section of said fluidized-bed reactor is 700～1000 ℃.
7. the top expanding reach temperature range that the method for production granular polycrystalline silicon according to claim 1, the position that it is characterized in that said Halogen gas inlet pipe are located at fluidized-bed reactor is in 250～550 ℃ the scope, to be preferably 300～400 ℃ of scopes.
8. the method for production granular polycrystalline silicon according to claim 1 is characterized in that the Halogen air temperature ranges that said Halogen gas inlet pipe feeds is 50～550 ℃, is preferably 150～350 ℃.
9. fluidizer that is used to produce granular polycrystalline silicon; It is characterized in that device case (1) comprises bottom direct tube section and top expanding reach; The direct tube section bottom is provided with gas distribution dish (5), and gas distribution dish (5) bottom connects virgin gas inlet mouth (2), auxiliary gas inlet mouth (3) and granular silicon discharge port (4); Housing (1) top expanding reach is provided with silicon seed charging opening (7) and Halogen gas inlet pipe (8), and housing (1) top is provided with tail gas outlet (10).
10. fluidizer according to claim 9 is characterized in that said silicon seed charging opening (7) preferably is positioned at said housing (1) direct tube section top or expanding reach bottom.
11. fluidizer according to claim 9 is characterized in that said Halogen gas inlet pipe (8) is positioned at the above position of said seed crystal charging opening (7), preferably is located on said housing (1) expanding reach.
12. device according to claim 9 is characterized in that said Halogen gas inlet pipe (8) is connected on the inner endless tube of said housing (1) (801), said endless tube (801) inboard evenly is provided with nozzle (802), and said nozzle (802) direction is a level or obliquely.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201010603238.5A CN102530951B (en) | 2010-12-24 | 2010-12-24 | Produce method and the device of granular polycrystalline silicon |
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|---|---|---|---|
| CN201010603238.5A CN102530951B (en) | 2010-12-24 | 2010-12-24 | Produce method and the device of granular polycrystalline silicon |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102815702A (en) * | 2012-08-09 | 2012-12-12 | 浙江中宁硅业有限公司 | Device and process of producing high-purity granular polycrystalline silicon by silanizing fluidized bed |
| WO2014026588A1 (en) * | 2012-08-13 | 2014-02-20 | 江苏中能硅业科技发展有限公司 | Method for preparing high sphericity seed crystal and fluidized bed particle silicon |
| CN107304050A (en) * | 2016-04-18 | 2017-10-31 | 新特能源股份有限公司 | Polycrystalline silicon reduction exhaust recovery method and recovery system |
| CN117105230A (en) * | 2023-08-25 | 2023-11-24 | 乐山协鑫新能源科技有限公司 | Method and device for producing granular polycrystalline silicon |
| WO2024027341A1 (en) * | 2022-08-03 | 2024-02-08 | 江苏中能硅业科技发展有限公司 | Method for cleaning deposited silicon on inner wall of fluidized bed |
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| US20020102850A1 (en) * | 2001-01-03 | 2002-08-01 | Korea Research Institute Of Chemical Technology | Method and apparatus for preparing polysilicon granules |
| CN101318654A (en) * | 2008-07-04 | 2008-12-10 | 清华大学 | Method for preparing high purity polysilicon particle with fluidized bed and bed fluidizing reactor |
| CN101676203A (en) * | 2008-09-16 | 2010-03-24 | 储晞 | Reactor for producing high purity granular silicon and method thereof |
| CN101696013A (en) * | 2009-10-27 | 2010-04-21 | 江苏中能硅业科技发展有限公司 | Method and device for producing polysilicon by using plasma assisting fluidized bed process |
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2010
- 2010-12-24 CN CN201010603238.5A patent/CN102530951B/en active Active
Patent Citations (4)
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| US20020102850A1 (en) * | 2001-01-03 | 2002-08-01 | Korea Research Institute Of Chemical Technology | Method and apparatus for preparing polysilicon granules |
| CN101318654A (en) * | 2008-07-04 | 2008-12-10 | 清华大学 | Method for preparing high purity polysilicon particle with fluidized bed and bed fluidizing reactor |
| CN101676203A (en) * | 2008-09-16 | 2010-03-24 | 储晞 | Reactor for producing high purity granular silicon and method thereof |
| CN101696013A (en) * | 2009-10-27 | 2010-04-21 | 江苏中能硅业科技发展有限公司 | Method and device for producing polysilicon by using plasma assisting fluidized bed process |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102815702A (en) * | 2012-08-09 | 2012-12-12 | 浙江中宁硅业有限公司 | Device and process of producing high-purity granular polycrystalline silicon by silanizing fluidized bed |
| WO2014026588A1 (en) * | 2012-08-13 | 2014-02-20 | 江苏中能硅业科技发展有限公司 | Method for preparing high sphericity seed crystal and fluidized bed particle silicon |
| CN107304050A (en) * | 2016-04-18 | 2017-10-31 | 新特能源股份有限公司 | Polycrystalline silicon reduction exhaust recovery method and recovery system |
| CN107304050B (en) * | 2016-04-18 | 2019-07-23 | 新特能源股份有限公司 | Polycrystalline silicon reduction exhaust recovery method and recovery system |
| WO2024027341A1 (en) * | 2022-08-03 | 2024-02-08 | 江苏中能硅业科技发展有限公司 | Method for cleaning deposited silicon on inner wall of fluidized bed |
| CN117105230A (en) * | 2023-08-25 | 2023-11-24 | 乐山协鑫新能源科技有限公司 | Method and device for producing granular polycrystalline silicon |
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