CN103086380B - Utilize the method and apparatus of reactive distillation process dichloro-dihydro scrap silicon - Google Patents
Utilize the method and apparatus of reactive distillation process dichloro-dihydro scrap silicon Download PDFInfo
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- CN103086380B CN103086380B CN201310022016.8A CN201310022016A CN103086380B CN 103086380 B CN103086380 B CN 103086380B CN 201310022016 A CN201310022016 A CN 201310022016A CN 103086380 B CN103086380 B CN 103086380B
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The present invention relates to a kind of method and apparatus of reactive distillation process dichloro-dihydro scrap silicon, reactive distillation column is divided into three sections, rectifying section, conversion zone and stripping section; Reactive distillation top of tower arranges overhead condenser, and bottom arranges tower bottom reboiler; Arrange water cooler at the bottom of tower, water cooler entrance to be exported with materials at bottom of tower by pipeline and is connected, and cooler outlet is connected with the entrance of subcooler, and the outlet of subcooler is connected to reactive distillation column by pipeline.Raw material silicon tetrachloride and dichlorosilane enter reactive distillation column from the top of conversion zone and bottom respectively, and anti-disproportionation reaction occurs in conversion zone and generates trichlorosilane, under the effect of rectifying separation, trichlorosilane is constantly moved out of conversion zone; Silicon tetrachloride in kettle material, returns rectifying tower by outer loop from conversion zone top and continues reaction, can improve reaction conversion ratio.The transformation efficiency of dichlorosilane can reach 98.50%, and in tower top material, the purity of trichlorosilane can reach 98.48%.
Description
Technical field
The present invention relates to reaction rectification technique field, a kind of method and apparatus utilizing reaction rectification technique to recycle dichloro-dihydro scrap silicon of special proposition.
Background technology
Polysilicon enterprise of current China major part adopts improved Siemens to produce polysilicon, intermediate compound trichlorosilane (SiHCl
3, TCS) and in chemical vapor deposition (CVD) reactor, deposition generates polysilicon, produces a large amount of silicon tetrachloride (SiCl simultaneously
4, STC) and a small amount of dichlorosilane (SiH
2cl
2, DCS), wherein DCS is inflammable and explosive very dangerous, and can enrichment in purification process, does not have good treatment process so far.Use alkali neutralisation to be used as refuse in traditional technology to dispose, not only increase intractability but also increase material consumption.How to process DCS and become improved Siemens urgent problem.
DCS and STC can generate TCS by anti-disproportionation reaction, thus can adopt anti-disproportionation reaction process DCS.Anti-disproportionation reaction equation is SiH
2cl
2+ SiCl
42SiHCl
3, utilize anti-disproportionation reaction, both can dispose waste material DCS, the TCS of high value can be obtained again.Both reduce material consumption, turn improved raw material availability, thus cause the research of Chinese scholars.
Reduction furnace tail gas and STC react and generate TCS by EP0334664A2, and because in reduction furnace tail gas, DCS content is few, processing efficiency is low, but demonstrates the feasibility of anti-disproportionation processes.US2010/0150809A1 designs a kind of DCS/STC reactor, DCS transformation efficiency up to 98%, because STC is excessive, in reaction product, TCS purity is not high, needs through two tower separating-purifyings, by unreacted STC and DCS recycle, and temperature of reaction is on the low side, reaction heat does not make full use of.
Reaction product is removed by reaction rectification technique while reaction, thus can break Equilibrium limit, improves reaction conversion ratio, even reaches 100% transformation efficiency, can utilize reaction heat effect simultaneously, thus saves running cost.Because reactor and rectifying tower are coupled into a reactive distillation column, thus facility investment can be saved.Due to the economic advantages that reaction rectification technique is huge, reactive distillation is introduced the anti-disproportionation processes of DCS, the production cost of this technique can be reduced further.CN101955187A proposes a kind of reactive distillation processes, and theoretical yield can reach 100%, but needs three tower combine operationss, and recycle stream is many, and flow process is complicated.The present invention proposes a kind of novel reactive distillation flow process, can be the TCS of high value by DCS converting waste material, effectively improve raw material availability, significantly reduce production cost, well solve DCS process problem.
Summary of the invention
The object of this invention is to provide a kind of method and apparatus utilizing reactive distillation process dichloro-dihydro scrap silicon, the by product DCS produced is recycled, be converted into the TCS of high value in improved Siemens.
The present invention utilizes the equipment of reactive distillation process dichloro-dihydro scrap silicon to comprise reactive distillation column 19, overhead condenser 15, tower bottom reboiler 16, water cooler 17 and subcooler 18.It is characterized in that reactive distillation column 19 is divided into three sections, epimere is rectifying section 12, and stage casing is conversion zone 13, and hypomere is stripping section 14; Reactive distillation column 19 top arranges overhead condenser 15, and bottom arranges tower bottom reboiler 16; Arrange water cooler 17 at the bottom of tower, water cooler 17 entrance to be exported with materials at bottom of tower by pipeline and is connected, and water cooler 17 outlet is connected with the entrance of subcooler 18, and the outlet of subcooler 18 is connected to reactive distillation column 19 by pipeline.Rectifying section 12 and stripping section 14 adopt column plate, random packing or structured packing.Conversion zone 13 adopt be filled with catalyzer tie up bag.
The present invention proposes a kind ofly to utilize the method for reactive distillation process dichloro-dihydro scrap silicon: raw material silicon tetrachloride 1 enters reactive distillation column 19 from conversion zone 13 top, dichloro-dihydro scrap silicon 2 enters reactive distillation column 19 bottom conversion zone 13, anti-disproportionation reaction is there is and generates trichlorosilane in two bursts of chargings in conversion zone 13, gas phase mixture material containing trichlorosilane enters rectifying section 12 from conversion zone 13, and enters stripping section 14 containing the liquid-phase mixing material of silicon tetrachloride.Under the effect of rectifying, containing the trichlorosilane that purity is higher in top gaseous phase material 3, after overhead condenser 15, be divided into liquid-phase reflux material 4 and overhead extraction material 5.At the bottom of tower, liquid phase material 6 contains the higher silicon tetrachloride of purity, is divided into two portions, and a part forms back tower steam 7 and returns reactive distillation column 19 after tower bottom reboiler 16 heats, and another part is used for outer loop.High-temperature material 8 is divided into two strands of materials after supercooler 17, and one material is discharged as the height raffinate 9 that boils, and another strand of material is middle temperature material 10, becomes low-temperature material 11 and return reactive distillation column 19 after subcooler 18.
In the present invention, reactive distillation column tower top pressure is 110kPa ~ 300kPa, and tower top temperature is 40 DEG C ~ 60 DEG C, and reflux ratio is 6 ~ 10.The feed entrance point of low-temperature material 11 is conversion zone top or middle part, and temperature of charge is 0 DEG C ~ 30 DEG C, and the temperature of conversion zone 13 is 60 DEG C ~ 80 DEG C.
The present invention has the following advantages:
(1) DCS is changed into the intermediate compound TCS of this technique, improve yield and the output of polysilicon, the transformation efficiency of dichlorosilane can reach 98.50%, and in tower top material, the purity of trichlorosilane can reach 98.48%;
(2) a large amount of basic cpds has been saved, as NaOH and Ca (OH)
2deng;
(3) in hydrogenation furnace, be converted into TCS compared to STC, transformation efficiency can be improved and save a large amount of electric energy;
(4) protection of the environment, reduces three waste discharge.
(5) adopt reaction rectification technique, both reduced facility investment, and reduced running cost again.
Accompanying drawing explanation
Fig. 1 is the process schematic representation utilizing reactive distillation process dichloro-dihydro scrap silicon;
Wherein: 1. raw material silicon tetrachloride, 2. waste material dichlorosilane, 3. top gaseous phase material, 4. liquid-phase reflux material, 5. overhead extraction material, 6. liquid phase material at the bottom of tower, 7. time tower steam, 8. high-temperature material, 9. height boils raffinate, 10. warm material in, 11. low-temperature materials, 12. rectifying sections, 13. conversion zones, 14. stripping sections, 15. condensers; 16. reboilers, 17. water coolers, 18. subcoolers, 19. reactive distillation columns.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further details:
This implementation method utilizes the equipment of reactive distillation process dichloro-dihydro scrap silicon to comprise reactive distillation column 19, overhead condenser 15, tower bottom reboiler 16, water cooler 17 and subcooler 18.It is characterized in that reactive distillation column 19 is divided into three sections, epimere is rectifying section 12, and stage casing is conversion zone 13, and hypomere is stripping section 14; Reactive distillation column 19 top arranges overhead condenser 15, and bottom arranges tower bottom reboiler 16; Arrange water cooler 17 at the bottom of tower, water cooler 17 entrance to be exported with materials at bottom of tower by pipeline and is connected, and water cooler 17 outlet is connected with the entrance of subcooler 18, and the outlet of subcooler 18 is connected to reactive distillation column 19 by pipeline.Rectifying section 12 and stripping section 14 adopt column plate, random packing or structured packing.Conversion zone 13 adopt be filled with catalyzer tie up bag.
Raw material silicon tetrachloride 1 enters reactive distillation column 19 from conversion zone 13 top, dichloro-dihydro scrap silicon 2 enters reactive distillation column 19 bottom conversion zone 13, anti-disproportionation reaction is there is and generates trichlorosilane in two bursts of chargings in conversion zone 13, gas phase mixture material containing trichlorosilane enters rectifying section 12 from conversion zone 13, and enters stripping section 14 containing the liquid-phase mixing material of silicon tetrachloride.Under the effect of rectifying, containing the trichlorosilane that purity is higher in top gaseous phase material 3, after overhead condenser 15, be divided into liquid-phase reflux material 4 and overhead extraction material 5.At the bottom of tower, liquid phase material 6 contains the higher silicon tetrachloride of purity, is divided into two portions, and a part forms back tower steam 7 and returns reactive distillation column 19 after tower bottom reboiler 16 heats, and another part is used for outer loop.High-temperature material 8 is divided into two strands of materials after supercooler 17, and one material is discharged as the height raffinate 9 that boils, and another strand of material is middle temperature material 10, becomes low-temperature material 11 and return reactive distillation column 19 after subcooler 18.
Reactive distillation column tower top pressure is 110kPa ~ 300kPa, and tower top temperature is 40 DEG C ~ 60 DEG C, and reflux ratio is 6 ~ 10.The feed entrance point of low-temperature material 11 is conversion zone top or middle part, and temperature of charge is 0 DEG C ~ 30 DEG C, and the temperature of conversion zone 13 is 60 DEG C ~ 80 DEG C.
Embodiment 1:
Reactive distillation process dichloro-dihydro scrap silicon 1700 tons/year, produces trichlorosilane 5000 tons/year.
The feed conditions of dichlorosilane, silicon tetrachloride and recycle stock is in table one.
Table one
Reactive distillation column working pressure is 150kPa, and full tower pressure drop is 20kPa, and overhead extraction amount is 624kg/h, and trim the top of column amount is 4500kg/h, and tower diameter is 0.9m, and the amount of catalyzer is 0.1m
3/ m
3filler, specific liquid rate is 25m
3/ (m
2h), the height of rectifying section, conversion zone and stripping section filler is respectively 4m, 8m and 4m.The feed entrance point of dichlorosilane is bottom conversion zone, and the feed entrance point of silicon tetrachloride and recycle stock is conversion zone top.
Commerical test data presentation: tower top temperature is 46.4 DEG C, column bottom temperature is 69.7 DEG C, trichlorosilane content 91.46% in overhead extraction material, content of silicon tetrachloride 7.17%, and the content of dichlorosilane only has 1.37%, the transformation efficiency of dichlorosilane, up to 96.04%, illustrates that dichlorosilane converting waste material can be effectively the trichlorosilane of high value by this technique.
Embodiment 2:
Reactive distillation process dichloro-dihydro scrap silicon 1700 tons/year, produces trichlorosilane 5000 tons/year.
The raw materials components mole ratio of adjustment dichlorosilane and silicon tetrachloride is 1:1, and the feed conditions of dichlorosilane, silicon tetrachloride and recycle stock is in table two.
Table two
Reactive distillation column working pressure is 150kPa, and full tower pressure drop is 20kPa, and overhead extraction amount is 579kg/h, and trim the top of column amount is 5000kg/h, and tower diameter is 0.9m, and the amount of catalyzer is 0.1m
3/ m
3filler, specific liquid rate is 25m
3/ (m
2h), the height of rectifying section, conversion zone and stripping section filler is respectively 4m, 8m and 4m.The feed entrance point of dichlorosilane is bottom conversion zone, and the feed entrance point of silicon tetrachloride and recycle stock is conversion zone top.
Tower top temperature is 44.0 DEG C, and column bottom temperature is 70.1 DEG C, trichlorosilane content 98.48% in overhead extraction material, content of silicon tetrachloride 0.96%, the content 0.56% of dichlorosilane.The transformation efficiency of dichlorosilane is up to while 98.50%, and the purity of trichlorosilane can reach 98.48%, illustrates that dichlorosilane converting waste material can be effectively the trichlorosilane of high value by this technique.
For other operational conditions, when reactive distillation column tower top pressure scope is 110kPa ~ 300kPa, reflux ratio scope is 6 ~ 10, and when the temperature range of low-temperature material 11 is 0 DEG C ~ 30 DEG C, dichlorosilane converting waste material can be effectively all the trichlorosilane of high value by this technique.
The method and apparatus utilizing reactive distillation process dichloro-dihydro scrap silicon that the present invention proposes, be described by embodiment, person skilled obviously can not depart from content of the present invention, spirit and scope system and method as herein described is changed or suitably change with combination, realize technology of the present invention.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the art, they are deemed to be included in spirit of the present invention, scope and content.
Claims (1)
1. one kind utilizes the method for reactive distillation process dichloro-dihydro scrap silicon, it is characterized in that raw material silicon tetrachloride (1) enters reactive distillation column (19) from conversion zone (13) top, dichloro-dihydro scrap silicon (2) enters reactive distillation column (19) from conversion zone (13) bottom, anti-disproportionation reaction is there is and generates trichlorosilane in two bursts of chargings in conversion zone (13), gas phase mixture material containing trichlorosilane enters rectifying section (12) from conversion zone (13), and enters stripping section (14) containing the liquid-phase mixing material of silicon tetrachloride; Under the effect of rectifying, containing the trichlorosilane that purity is higher in top gaseous phase material (3), after overhead condenser (15), be divided into liquid-phase reflux material (4) and overhead extraction material (5); Liquid phase material at the bottom of tower (6) is containing the higher silicon tetrachloride of purity, be divided into two portions, a part forms back tower steam (7) and returns reactive distillation column (19) after tower bottom reboiler (16) heating, and another part is used for outer loop; An above-mentioned other part is used for outer loop, also the high-temperature material (8) coming from liquid phase material at the bottom of tower (6) is divided into two strands of materials after supercooler (17), one material as height boil raffinate (9) discharge, another strand of material is middle temperature material (10), becomes low-temperature material (11) and return reactive distillation column (19) after subcooler (18); Described reactive distillation column tower top pressure is 110kPa ~ 300kPa, and tower top temperature is 40 DEG C ~ 60 DEG C, and reflux ratio is 6 ~ 10; The feed entrance point of described low-temperature material (11) is conversion zone top or middle part, and temperature of charge is 0 DEG C ~ 30 DEG C; The temperature of described conversion zone (13) is 60 DEG C ~ 80 DEG C.
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| CN103253676B (en) * | 2013-05-10 | 2015-04-08 | 河北工业大学 | Preparation method of trichlorosilane |
| CN103553057B (en) * | 2013-11-11 | 2016-01-20 | 新特能源股份有限公司 | A kind of method utilizing reaction rectification technique process chlorosilane waste gas |
| CN103626186B (en) * | 2013-11-19 | 2015-09-02 | 新特能源股份有限公司 | The high efficiente callback equipment and technology of production of polysilicon by product |
| CN104437295B (en) * | 2014-12-24 | 2016-11-02 | 赤峰盛森硅业科技发展有限公司 | Prepare the device and method of tetramethoxy-silicane |
| CN104556054B (en) * | 2015-01-19 | 2017-03-29 | 新疆大全新能源有限公司 | The recoverying and utilizing method and device of light component in trichlorosilane synthesis material |
| CN104909371A (en) * | 2015-07-14 | 2015-09-16 | 黄国强 | Device and method of purifying silane by complexation and rectification |
| CN104925815A (en) * | 2015-07-14 | 2015-09-23 | 黄国强 | Device and method for treating silane exhaust through reactive distillation |
| CN104986770B (en) * | 2015-07-14 | 2017-12-12 | 天津市净纯科技有限公司 | The rectifying of trichlorosilane disproportionated reaction produces the device and method of silane |
| CN106554021B (en) * | 2015-09-30 | 2019-06-25 | 新特能源股份有限公司 | A kind of rectification tail gas recovery system |
| CN105948059B (en) * | 2016-05-03 | 2018-05-08 | 宜昌南玻硅材料有限公司 | Recycle the system and method for chlorosilane tail gas |
| CN110639221A (en) * | 2019-10-15 | 2020-01-03 | 天津大学 | Method and device for purifying dimethyldichlorosilane by reactive distillation and impurity removal |
| CN110559678B (en) * | 2019-10-21 | 2024-02-27 | 无锡赫利邦化工科技有限公司 | Rectifying tower for synthesizing and separating polymethoxy dimethyl ether and application method thereof |
| CN110694293A (en) * | 2019-10-30 | 2020-01-17 | 新疆东方希望新能源有限公司 | Reaction rectifying tower for recovering DCS through side line extraction |
| CN110980742A (en) * | 2019-12-31 | 2020-04-10 | 天津大学 | Reactive distillation purification method and device for removing carbon-containing impurities in chlorosilane |
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