CN102020282A - Method for producing trichlorosilane by using silicon tetrachloride - Google Patents
Method for producing trichlorosilane by using silicon tetrachloride Download PDFInfo
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- CN102020282A CN102020282A CN2009101691307A CN200910169130A CN102020282A CN 102020282 A CN102020282 A CN 102020282A CN 2009101691307 A CN2009101691307 A CN 2009101691307A CN 200910169130 A CN200910169130 A CN 200910169130A CN 102020282 A CN102020282 A CN 102020282A
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- silicon tetrachloride
- hydrogenation
- hydrogen
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- tail gas
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Abstract
The invention provides a method for producing trichlorosilane by using silicon tetrachloride, which comprises the following steps of: a) refining the silicon tetrachloride; b) purifying hydrogen; c) mixing the silicon tetrachloride and the hydrogen; d) preheating the mixed gas of the silicon tetrachloride and the hydrogen by using one or two of steam and the tail gas of hydrogenation; e) hydrogenating the preheated mixed gas of the silicon tetrachloride and the hydrogen; and f) recovering the tail gas of the hydrogenation, and fractionating to obtain the trichlorosilane. In the method, before the silicon tetrachloride and the hydrogen are subjected to hydrogenation, the mixed gas of the silicon tetrachloride and the hydrogen is preheated by the steam and the tail gas of the hydrogenation, so that a needed temperature can be reached by consuming a little electricity during the hydrogenation, the energy source is saved, the hydrogenation has high speed and yield, and the reaction time is short. Therefore, the method is suitable for large-scale polycrystalline silicon production.
Description
Technical field
The present invention relates to field of polysilicon production, be specifically related to a kind of method of utilizing hydrogenation of silicon tetrachloride to produce trichlorosilane.
Background technology
Adopt the improvement Siemens Method to produce in the technology of polysilicon and can produce a large amount of silicon tetrachloride as by-product, silicon tetrachloride very easily generates silicon-dioxide and hydrogenchloride with the water reaction, and directly discharging will have a strong impact on ecotope, need deal carefully with silicon tetrachloride.Utilize silicon tetrachloride can prepare white carbon black, organosilicon, but the market capacity of these products is little, can't digests the huger silicon tetrachloride of quantity.Continuous expansion along with domestic polysilicon production capacity, recycle is to solve the better outlet that produces a large amount of silicon tetrachloride problems in the production of polysilicon at present, special process technology is passed through in recycle exactly, silicon tetrachloride is converted into the raw materials for production trichlorosilane of polysilicon, trichlorosilane is used further to produce polysilicon, both avoid environmental pollution, saved resource again.
Produce trichlorosilane and can use the chlorine hydride process, silicon tetrachloride, hydrogen, hydrogenchloride, silica flour are fed trichlorosilane synthetic furnace produce trichlorosilane, but this technical process is long, equipment is complicated, material requires harshness, working pressure is high, condition is difficult to control, be difficult to realize continous-stable operation, poor stability, can not be widely used.
Publication number is that the application for a patent for invention of CN101445245 discloses another kind of method with producing trichlorosilane by using silicon tetrachloride, be that silicon tetrachloride and hydrogen are fed in the high temperature hydrogenation apparatus with certain proportion, take place to generate trichlorosilane behind the hydrogenation, but because the required temperature height of reaction, this method energy consumption is higher.
Summary of the invention
The method of utilizing producing trichlorosilane by using silicon tetrachloride that provides a kind of production energy consumption less is provided the problem that the present invention solves.
In order to solve the problems of the technologies described above, technical scheme of the present invention is:
A kind of method of utilizing producing trichlorosilane by using silicon tetrachloride comprises:
A) silicon tetrachloride is purified;
B) hydrogen is purified;
C) silicon tetrachloride and hydrogen are mixed;
D) mixed gas of silicon tetrachloride and hydrogen is carried out preheating with in the tail gas of steam and hydrogenation one or both;
E) mixed gas with silicon tetrachloride after the preheating and hydrogen carries out hydrogenation.
F) tail gas with hydrogenation reclaims, and fractionates out trichlorosilane.
As preferably, described step a) is purified to purifying to purity more than or equal to 99.99% to silicon tetrachloride.
As preferably, described step b) to hydrogen purify for purify to purity more than or equal to 99.999%.
As preferably, the mol ratio of silicon tetrachloride and hydrogen is 1: 2～1: 4 in the described step c).
As preferably, described step d) is specially utilizes in the tail gas of steam and hydrogenation one or both to be evaporated to gas phase silicon tetrachloride; Mixed gas after will evaporating again utilizes the tail gas of hydrogenation further to heat.
As preferably, after the described silicon tetrachloride evaporation, the temperature of mixed gas reaches 100 ℃～200 ℃.
As preferably, further after the heating, temperature reaches 200 ℃～400 ℃ to the tail gas that described mixed gas utilizes hydrogenation.
As preferably, the inlet amount of silicon tetrachloride is 2t/h～8t/h in the described step e).
As preferably, the condition of hydrogenation is 1200 ℃～1300 ℃ of temperature in the described step e), pressure 0.3MPa～0.7MPa.
Method provided by the invention is before silicon tetrachloride and hydrogen generation hydrogenation, the tail gas that utilizes steam and hydrogenation carries out preheating to the mixed gas of silicon tetrachloride and hydrogen, expend the temperature that less electric energy just can reach to be needed when carrying out hydrogenation, saved the energy, and hydrogenation speed is very fast, reaction times is shorter, and production capacity is big, is fit to the production of extensive polysilicon.
A kind of preferred embodiment in, warm is divided into two stages, it is more abundant to make that silicon tetrachloride can be evaporated to the preheating of gas phase and mixed gas, enter hydrogenation furnace before temperature can reach more than 300 ℃, can save more electric energy when hydrogenation takes place.
Description of drawings
The schematic flow sheet of the method for utilizing producing trichlorosilane by using silicon tetrachloride that Fig. 1 is provided for a kind of embodiment of the present invention.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, but should be appreciated that these describe just to further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
Please refer to Fig. 1, the schematic flow sheet of the method for utilizing producing trichlorosilane by using silicon tetrachloride that Fig. 1 is provided for a kind of embodiment of the present invention.The method of utilizing hydrogenation of silicon tetrachloride to produce trichlorosilane provided by the invention is:
A) use the method that well known to a person skilled in the art that silicon tetrachloride is carried out rectification and purification, make the purity of silicon tetrachloride more than or equal to 99.99%.
B) use the method that well known to a person skilled in the art that the hydrogen that the electrolysis pure water generates is purified, make the purity of hydrogen more than or equal to 99.999%.
C) silicon tetrachloride and the hydrogen after will purifying mixes, and the mol ratio of the two is 1: 2～1: 4.The mol ratio of silicon tetrachloride and hydrogen is 1: 1 in reaction, increases the amount of hydrogen, helps reaction and carries out to the positive reaction direction, and can improve speed of response.
D) mixed gas with silicon tetrachloride and hydrogen utilizes tail gas to carry out preheating, when reaction begins not carry out hydrogenation most, also do not produce tail gas, at this time utilize steam to carry out preheating, when after hydrogenation carries out, beginning to have tail gas to generate, can utilize tail gas to carry out preheating, regulate according to the needs in the actual production, the amount of steam can reduce does not even use steam.
As preferably, can be preheating to more than 300 ℃ in order to make mixed gas, preheating is divided into two stages carries out.At first mixed gas is fed in the vaporizer, when reaction begins also not produce tail gas, mixed gas is subjected to the preheating of steam in vaporizer, originally gas-liquid phase blended silicon tetrachloride is evaporated to gas phase, there is tail gas to produce after reaction for some time, then in vaporizer, is subjected to the common preheating of steam and tail gas, regulate according to the needs in the actual production, the amount of steam can reduce does not even use steam, and mixed gas is preheated to 100 ℃～200 ℃ in vaporizer.From vaporizer, come out then the back mixed gas enter in the tail gas heat exchanger of hydrogenation furnace, utilize tail gas further to heat, the tail gas here just from hydrogenation furnace outflow temperature higher, mixed gas can be heated to 200 ℃～400 ℃.Be divided into two sections and carry out preheating, can avoid the mixed gas preheating abundant inadequately, temperature does not reach 300 ℃, makes mixed gas also need to consume the temperature that more electric energy just can reach the hydrogenation needs in hydrogenation furnace.And become gas phase by liquid phase through the silicon tetrachloride after the two-stage preheating, and enter the preceding mixed gas of hydrogenation furnace just can reach more than 300 ℃, need not to expend again a large amount of electric energy when making hydrogenation and heat.
E) mixed gas with silicon tetrachloride after the preheating and hydrogen carries out hydrogenation, the present invention feeds mixed gas in the hydrogenation furnace to react, inlet amount according to silicon tetrachloride is 2t/h～8t/h charging, the temperature of hydrogenation is preferably 1200 ℃～1300 ℃, and pressure is 0.3MPa～0.7MPa.Near the red-hot electrode surface that mixed gas is switched on, the hydrogenation of silicon tetrachloride takes place in stove, generate trichlorosilane, principal reaction is in the production process: SiCl
4+ H
2=SiHCl
3+ HCl.
F) contain hydrogen, the hydrogenchloride of gas phase in the tail gas that hydrogenation produces, dichloro-dihydro silicon, trichlorosilane, silicon tetrachloride with liquid phase, sending into separating device after the tail gas that generates is lowered the temperature through heat exchange separates, gas after the separation can reclaim respectively and carry out recycle, improves raw-material utilization ratio greatly and reduces the waste discharge amount.Wherein hydrogen is used for participating in once more hydrogenation after purifying; Hydrogenchloride can be used for carrying out the synthetic of trichlorosilane, and reaction formula is Si+3HCl=SiHCl
3+ H
2Liquid phase dichloro-dihydro silicon, trichlorosilane, silicon tetrachloride separate through fractionation, and the trichlorosilane of separating enters reduction furnace and produces polysilicon, SiHCl after purifying
3+ H
2=Si+3HCl, silicon tetrachloride carries out hydrogenation with hydrogen after purifying once more.
In the method for production trichlorosilane provided by the invention since hydrogenation after exhaust temperature higher, therefore in step d), utilize the waste heat and the steam of tail gas earlier mixed gas to be carried out preheating, mixed gas temperature when entering hydrogenation furnace and carry out hydrogenation is higher like this, consume less electric energy and just can reach the temperature of hydrogenation, saved the energy; And because the mixed gas that reacts has certain temperature through preheating, therefore when carrying out hydrogenation, speed of response is very fast, reaction times is shorter, thereby has improved inlet amount, avoids mixed gas also fully just not react and is released hydrogenation furnace by follow-up charging.Preferably be divided into the preheating of two stages, make silicon tetrachloride be evaporated to gas phase, and the preheating of mixed gas is more abundant, enter that temperature reaches more than 300 ℃ before the hydrogenation furnace, can save more electric energy when entering hydrogenation furnace and reacting.
Embodiment 1:
Silicon tetrachloride after the purification and hydrogen are that 1: 2 mixing back feeds preheating in the vaporizer, 3 tons/hour of inlet amounies with mol ratio.
Embodiment 2:
Silicon tetrachloride after the purification and hydrogen are that 1: 3 mixing back feeds preheating in the vaporizer, 5 tons/hour of inlet amounies with mol ratio.
Embodiment 3:
Silicon tetrachloride after the purification and hydrogen are that 1: 2 mixing back feeds preheating in the vaporizer, 6 tons/hour of inlet amounies with mol ratio.
Embodiment 4:
Silicon tetrachloride after the purification and hydrogen are that 1: 3 mixing back feeds preheating in the vaporizer, 7 tons/hour of inlet amounies with mol ratio.
Respectively with the mixed gas among each embodiment through after the two-stage preheating, feed again and carry out hydrogenation in the hydrogenation furnace and produce trichlorosilane, experimental result sees Table 1:
The experimental result that table 1 method of the present invention is produced trichlorosilane
Method provided by the invention has certain temperature owing to enter the mixed gas of hydrogenation furnace, so it is shorter to be raised to the needed temperature-time of hydrogenation, speed of response is very fast, reaction times is short, therefore improved inlet amount, also as can be seen, the inlet amount of silicon tetrachloride is more from table 1, and the transformation efficiency that silicon tetrachloride generates trichlorosilane still can reach 20%～24%.And because preheating, reach the electric energy that the temperature of hydrogenation need consume and reduce, can save 1 degree through calculating one kilogram of trichlorosilane of general every production.
More than the method for producing trichlorosilane by using silicon tetrachloride of utilizing provided by the present invention is described in detail.Used specific case herein principle of the present invention and embodiment are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (9)
1. a method of utilizing producing trichlorosilane by using silicon tetrachloride is characterized in that, comprising:
A) silicon tetrachloride is purified;
B) hydrogen is purified;
C) silicon tetrachloride and hydrogen are mixed;
D) mixed gas of silicon tetrachloride and hydrogen is carried out preheating with in the tail gas of steam and hydrogenation one or both;
E) mixed gas with silicon tetrachloride after the preheating and hydrogen carries out hydrogenation;
F) tail gas with hydrogenation reclaims, and fractionates out trichlorosilane.
2. method according to claim 1 is characterized in that, described step a) is purified to purifying to purity more than or equal to 99.99% to silicon tetrachloride.
3. method according to claim 1 is characterized in that, described step b) to hydrogen purify for purify to purity more than or equal to 99.999%.
4. method according to claim 1 is characterized in that, the mol ratio of silicon tetrachloride and hydrogen is 1: 2～1: 4 in the described step c).
5. method according to claim 1 is characterized in that, described step d) is specially utilizes in the tail gas of steam and hydrogenation one or both to be evaporated to gas phase silicon tetrachloride; Mixed gas after will evaporating again utilizes the tail gas of hydrogenation further to heat.
6. method according to claim 5 is characterized in that, after the described silicon tetrachloride evaporation, the temperature of mixed gas reaches 100 ℃～200 ℃.
7. method according to claim 5 is characterized in that, after described mixed gas utilized the tail gas of hydrogenation further to heat, temperature reached 200 ℃～400 ℃.
8. method according to claim 1 is characterized in that, the inlet amount of silicon tetrachloride is 2t/h～8t/h in the described step e).
9. according to claim 1 or 8 described methods, it is characterized in that the condition of hydrogenation is 1200 ℃～1300 ℃ of temperature in the described step e), pressure 0.3MPa～0.7MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101691307A CN102020282A (en) | 2009-09-09 | 2009-09-09 | Method for producing trichlorosilane by using silicon tetrachloride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101691307A CN102020282A (en) | 2009-09-09 | 2009-09-09 | Method for producing trichlorosilane by using silicon tetrachloride |
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|---|---|
| CN102020282A true CN102020282A (en) | 2011-04-20 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102530960A (en) * | 2011-12-31 | 2012-07-04 | 中国天辰工程有限公司 | Trichlorosilane production method used during polycrystalline silicon production |
| CN103787338A (en) * | 2012-10-29 | 2014-05-14 | 王红卫 | Trichlorosilane plasma preparation method and preparation apparatus thereof |
| CN104891501A (en) * | 2014-03-07 | 2015-09-09 | 新特能源股份有限公司 | Silicon tetrachloride high-temperature hydrogenation method and device |
| CN106276912A (en) * | 2015-05-27 | 2017-01-04 | 内蒙古盾安光伏科技有限公司 | polysilicon production process |
| CN110422847A (en) * | 2019-08-30 | 2019-11-08 | 中石化南京工程有限公司 | A kind of silicon tetrachloride vaporization and heat recovery system and method |
| CN116639699A (en) * | 2023-07-12 | 2023-08-25 | 江苏中圣高科技产业有限公司 | Production process and system for preparing trichlorosilane |
-
2009
- 2009-09-09 CN CN2009101691307A patent/CN102020282A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102530960A (en) * | 2011-12-31 | 2012-07-04 | 中国天辰工程有限公司 | Trichlorosilane production method used during polycrystalline silicon production |
| CN102530960B (en) * | 2011-12-31 | 2013-08-14 | 中国天辰工程有限公司 | Trichlorosilane production method used during polycrystalline silicon production |
| CN103787338A (en) * | 2012-10-29 | 2014-05-14 | 王红卫 | Trichlorosilane plasma preparation method and preparation apparatus thereof |
| CN104891501A (en) * | 2014-03-07 | 2015-09-09 | 新特能源股份有限公司 | Silicon tetrachloride high-temperature hydrogenation method and device |
| CN106276912A (en) * | 2015-05-27 | 2017-01-04 | 内蒙古盾安光伏科技有限公司 | polysilicon production process |
| CN106276912B (en) * | 2015-05-27 | 2018-11-06 | 内蒙古盾安光伏科技有限公司 | polysilicon production process |
| CN110422847A (en) * | 2019-08-30 | 2019-11-08 | 中石化南京工程有限公司 | A kind of silicon tetrachloride vaporization and heat recovery system and method |
| CN116639699A (en) * | 2023-07-12 | 2023-08-25 | 江苏中圣高科技产业有限公司 | Production process and system for preparing trichlorosilane |
| CN116639699B (en) * | 2023-07-12 | 2024-02-02 | 江苏中圣高科技产业有限公司 | Production process and system for preparing trichlorosilane |
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Application publication date: 20110420 |